Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
  • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
  • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl 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
  • C08G18/08—Processes
  • C08G18/088—Removal of water or carbon dioxide from the reaction mixture or reaction components
  • C08G18/0885—Removal of water or carbon dioxide from the reaction mixture or reaction components using additives, e.g. absorbing agents
• • 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
  • C08G18/4804—Two or more polyethers of different physical or chemical nature
  • C08G18/4808—Mixtures of two or more polyetherdiols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0066—Flame-proofing or flame-retarding additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2110/00—Foam properties
  • C08G2110/0008—Foam properties flexible
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2290/00—Compositions for creating anti-fogging

Definitions

• This invention relates generally to flexible polyurethanes. More particularly, this invention relates to highly filled, flexible polyurethane foams.
• High-density polyurethane foams and solid polyurethanes are useful materials for a wide variety of applications, particularly sealing gaskets for electronic devices. These foams preferably have densities in the range from about 10 to about 65 pounds per cubic foot (pc ). It is also important that the foams have acceptable compression set, compressive force deflection, tensile strength, elongation, tear strength, low outgassing, and non-corrosiveness.
• U.S. Patent No. 4,022,718 teaches the preparation of high resilience cold-cured polyurethane foams incorporating 2,3-dibromo-l,4-butenediol as a chain extender and flame-retardant component.
• U.S. Patent No. 4,147,847 teaches a method of preparing flexible, flame- retarded, polyurethane foams by employing specific foam stabilizers, which reduce the required amount of normal flame-retardant additives.
• 4,162,353 teaches the preparation of flexible polyurethane foams incorporating therein a halo- substituted alkyl phosphate such as tris(2-chloroethyl)-phosphate and an unsubstituted trialkylphosphate such as triethylphosphate.
• U.S. Patent No. 4,849,459 describes a flame retardant flexible polyurethane foam comprising the reaction product of a polyether polyol and a toluene diisocyanate and incorporating melamine and another flame retardant. All of the foregoing are incorporated herein by reference.
• the above-described flexible polyurethane foams are low density, have lower tensile strength, lower tear strength, lower compressive force deflection, and poor compression set resistance. Because of these deficiencies, these low-density prior art foams are not suitable for use as gaskets. Consequently, there is a need for a high-density polyurethane foam composition, which is highly flame retardant, and yet which still retains the required degree of compression set, compressive force deflection, tensile elongation, tear strength, low outgassing, and non-corrosiveness.
• a composition for the formation of a flame retardant polyurethane foam comprising an organic polyisocyanate component, an active hydrogen-containing component reactive with the polyisocyanate component, wherein the active hydrogen-containing component preferably has an overall viscosity of less than about 500 centipoise, a catalyst component, a surfactant, and a flame retarding composition comprising an antimony-based compound, a halogenated, active hydrogen-containing component reactive with the polyisocyanate component, and a halogenated flame-retarding agent, preferably wherein the composition, without the polyisocyanate component, has a viscosity of less than about 8,000 centipoise prior to foaming.
• Preferred antimony-based compounds include antimony trioxide
• preferred halogenated, active hydrogen-containing components include liquid brominated diols
• preferred halogenated flame-retarding agents are solid
• a composition for the formation of a flame retardant, low outgassing, low fogging polyurethane foam comprises a low NOC organic polyisocyanate component, a low NOC active hydrogen-containing component reactive with the polyisocyanate component, wherein the active hydrogen- containing component preferably has an overall viscosity of less than about 500 centipoises, a catalyst component, a surfactant, and a flame retarding composition comprising a halogenated, active hydrogen-containing component reactive with the polyisocyanate component, preferably wherein the composition, without the polyisocyanate component, has a viscosity of less than about 8,000 centipoises prior to foaming.
• foams have a UL-94 rating of V-l and/or HBF. Even more preferably, foams having a thickness of about 31 to about 250 mils and a density of about 15 to about 30 pcf have a UL 94 V-0 rating, and foams having a thickness of about 28 to about 40 mils and a density of about 15 to about 30 pcf have a UL 94 V-0 rating.
• the foams have excellent physical properties, low outgassing (preferably less than 1% by weight), and non-corrosiveness.
• a composition particularly suitable for the formation of polyurethane foams having incorporated therein a flame retardant composition comprises an organic polyisocyanate component, an active hydrogen-containing component substantially reactive with the low functionality isocyanate to form a polyurethane, wherein the active hydrogen- containing component has a viscosity of less than about 500 centipoise; a surfactant for structurally stabilizing the froth produced according to the procedure below, during the period that the liquid phase of said froth is chemically stable, and until said froth is cured; a catalyst having substantial catalytic activity in the curing of said mixture; and a flame retarding composition comprising a halogenated, active hydrogen- containing component reactive with the polyisocyanate component.
• the viscosity of the total composition without the inclusion of the polyisocyanate component has a viscosity of less than about 8,000 centipoises prior to foaming.
• the process of forming the foam comprises forming the above-described composition; substantially uniformly dispersing inert gas throughout the mixture by mechanical beating of the mixture to form a heat curable froth which is substantially structurally and chemically stable, but workable at ambient conditions; and curing said froth to form a cured foam.
• the organic polyisocyanate components preferably are those having the general formula: Q(NCO),- wherein i is an integer of two or more and Q is an organic radical having the valence of i.
• the average value of i is low, i.e., in the range from 2.0 to about 2.6, and preferably in the range from 2.0 to about 2.2.
• Q can be a substituted or unsubstituted hydrocarbon group (i.e., an alkylene or an arylene group).
• Q can be a group having the formula Q ⁇ -Z-Q 1 wherein Q 1 is an alkylene or arylene group and Z is -O-, -O-Q 1 -, -CO-, -S-, -S-Q ⁇ S-, -SO-, or -SO 2 -.
• Examples of such compounds include hexamethylene diisocyanate, 1,8-diisocyanato- p-methane, xylyl diisocyanate, dusocyanatocyclohexane, phenylene diisocyanates, tolylene diisocyanates, including 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and crude tolylene diisocyanate, bis(4-isocyanatophenyl)methane, chlorophenylene diisocyanates, diphenylmethane-4,4'-diisocyanate (also known as.4,4'-diphenyl methane diisocyanate, or MDI) and adducts thereof, naphthalene-l,5-diisocyanate, triphenylmethane-4,4',4"-triisocyanate, and isopropylbenzene-alpha-4-diisocyanate.
• Q(NCO); is a composition conventionally known as a prepolymer.
• prepolymers are formed by reacting a stoichiometric excess of a polyisocyanate as set forth hereinbefore and hereinafter with an active hydrogen-containing component as set forth hereinafter, especially the polyhydroxyl-containing materials or polyols described below.
• the polyisocyanate is employed in proportions of from about 30 percent to about 200 percent stoichiometric excess, the stoichiometry being based upon equivalents of isocyanate group per equivalent of hydroxyl in the polyol.
• dimers and trimers of isocyanates and diisocyanates and polymeric diisocyanates such as those having the general formula:
• Q 2 (NCO) [Q 2 (NCO) ; h m which i is an integer of one or more, j is an integer of two or more, and Q is a polyfunctional organic radical.
• An example is polymethylene polyphenyl isocyanate.
• Q 2 may also be a compound of the general formula:
• L(NCO) L(NCO) ; - in which i is one or more and L is a monofunctional or polyfunctional atom or radical.
• this type include ethylphosphonic diisocyanate, C 2 H 5 P(O)(NCO) 2 , phenylphosphonic diisocyanate, C 6 H 5 P(O)(NCO) 2 , compounds containing a trivalent siliconcyanate group, isocyanates derived from sulfonamides (QSO 2 NCO), cyanic acid, and thiocyanic acid.. Combinations of all of the foregoing may also be used.. In general, the aromatic polyisocyanates are preferred because of their greater reactivity.
• the amount of polyisocyanate employed will vary slightly depending upon the nature of the polyurethane being prepared.
• the total -NCO equivalent to total active hydrogen equivalent should be such as to provide a ratio of 0.8 to 1.2 equivalents of - NCO per equivalent of active hydrogen, e.g., hydroxyl hydrogen, of the active hydrogen reactant, and preferably a ratio of about 1.0 to 1.05 equivalents of -NCO per active hydrogen.
• the active hydrogen-containing component generally includes a mixture of polyhydroxyl-containing compounds, such as hydroxyl-terminated polyhydrocarbons (U.S. Pat. No.
• polyhydroxyl-containing materials are the polyether polyols obtained by the chemical addition of alkylene oxides, such as ethylene oxide, propylene oxide and mixtures thereof, to water or polyhydric organic compounds, such as ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5 -pentanediol, 1,2-hexylene glycol, 1,10- decanediol, 1,2-cyclohexanediol, 2-butene-l,4-diol, 3-cyclohexene-l,l-dimethanol, 4- methyl-3-cyclohexene-l,l-dimethanol, 3-methylene-l,5-pentanediol, diethylene glycol, (2-hydroxyethoxy)-l-propanol, 4-(2-hydroxyethoxy)-l-butanol, 5-(2- hydroxypropyl
• alkylene oxides employed in producing polyoxyalkylene polyols normally have from 2 to 4 carbon atoms. Propylene oxide and mixtures or propylene oxide with ethylene oxide are preferred.
• the polyols listed above can be used per se as the active hydrogen compound.
• a preferred class of polyether polyols is represented generally by the following formula
• R is hydrogen or a polyvalent hydrocarbon radical
• a is an integer (i.e., 1 or 2 to 6 to 8) equal to the valence of R
• n in each occurrence is an integer from 2 to 4 inclusive (preferably 3)
• z in each occurrence is an integer having a value of from 2 to about 200, preferably from 15 to about 100.
• Additional active hydrogen-containing compounds are the polymers of cyclic esters.
• the preparation of the cyclic ester polymers from at least one cyclic ester monomer is well documented in the patent literature as exemplified by U.S. Pat. Nos. 3,021,309 through 3,021,317; 3,169,945; and 2,962,524.
• Suitable cyclic ester monomers include but are not limited to delta-valerolactone; epsilon-caprolactone; zeta-enantholactone; the monoalkyl-valerolactones, e.g., the monomethyl-, monoethyl-, and monohexyl-valerolactones.
• Cyclic ester/alkylene oxide copolymers can also be prepared by reacting a mixture comprising cyclic ester and alkylene oxide monomers, an interfacial agent such as a solid, relatively high molecular weight poly(vinylstearate) or lauryl methacrylate/vinyl chloride copolymer (reduced viscosity in cyclohexanone at 30°C from about 0.3 to about 1.0), in the presence of an inert normally-liquid saturated aliphatic hydrocarbon vehicle such as heptane and phosphorus pentafluoride as the catalyst therefor, at an elevated temperature, e.g., about 80°C.
• an interfacial agent such as a solid, relatively high molecular weight poly(vinylstearate) or lauryl methacrylate/vinyl chloride copolymer (reduced viscosity in cyclohexanone at 30°C from about 0.3 to about 1.0)
• Another type of active hydrogen-containing material includes the polymer polyol compositions obtained by polymerizing ethylenically unsaturated monomers in a polyol as described in U.S. Pat No. 3,383,351, the disclosure of which is incorporated herein by reference.
• Suitable monomers for producing such compositions include acrylonitrile, vinyl chloride, styrene, butadiene, vinylidene chloride and other ethylenically unsaturated monomers as identified and described in the above-mentioned U.S. patent.
• Suitable polyols include those listed and described hereinabove and in the U.S. patent.
• the polymer polyol compositions can contain from 1 to about 70 weight percent (wt%), preferably about 5 to about 50 wt%, and most preferably about 10 to about 40 wt% monomer polymerized in the polyol.
• Such compositions are conveniently prepared by polymerizing the monomers in the selected polyol at a temperature of 40°C to 150°C in the presence of a free radical polymerization catalyst such as peroxides, persulfates, percarbonate, perborates, and azo compounds.
• Preferred active hydrogen-containing components are polyether polyols, mixtures of polyether polyols and mixtures of polyether and polyester polyols.
• Preferred polyetlier polyols include polyoxyalkylene diols and triols, and polyoxyalkylene diols and triols with polystyrene and/or polyacrylonitrile grafted onto the polymer chain, and mixtures thereof.
• Preferred polyester polyols are based on caprolactone.
• the polyol components are reformulated to yield a wide range of moduli. Chain extenders and crosslinking agents may further be included, to the extent that such chain extenders and cross-linking agents are low VOC.
• Exemplary chain extenders and cross-linking agents are low molecular weight diols, such as alkane diols and dialkylene glycols, and/or polyhydric alcohols, preferably triols and tetrols, having a molecular weight from about 200 to 400.
• the polyol component comprises one or a mixture of a polyether polyol having a molecular weight in the range from about 500 to about 1500, one or a mixture of a polyether oxide diol having a molecular weight in the range from about 1000 to about 3000, and one or a mixture of a polyether diol having polystyrene and polyacrylonitrile grafts and having a molecular weight in the range from about 1500 to about 4000.
• This component may be used to produce a low CFD (compression force deflection) foam.
• the polyol component comprises one or a mixture of a low molecular weight polyether oxide diol having a molecular weight in the range from about 250 to about 750; one or a mixture of a polyether oxide diol having a molecular weight in the range from about 1000 to about 3000; and one or a mixture of a polypropylene oxide diol having polystyrene and polyacrylonitrile grafts having a molecular weight in the range from about 2000 to about 3000.
• This polyol component is useful for the production of a high CFD foam.
• polyol or polyol mixture can have hydroxyl numbers that vary over a wide range. In general, the hydroxyl numbers of the polyols or mixtures thereof, including other cross-linking additives, if employed, can be from about 28 to about 1000, and higher, preferably from about 100 to about 800.
• the hydroxyl number is defined as the number of milligrams of potassium hydroxide required for the complete neutralization of the hydrolysis product of the fully acetylated derivative prepared from 1 gram of polyol or mixtures of polyols with or without other cross-linking additives used in the invention.
• the exact polyol or polyols employed depends upon the end-use of the polyurethane foam. In particular, variation in the polyol component can yield a wide range of moduli and toughness.
• the molecular weight and the hydroxyl number are selected properly to result in flexible foams.
• the polyol or polyols including cross- linking additives, if used, preferably possess a hydroxyl number of from about 45 to about 70 or more when employed in flexible foam formulations. Such limits are not intended to be restrictive, but are merely illustrative of the large number of possible combinations of the polyols that can be employed.
• a wide variety of surfactants can be employed for purposes of stabilizing the froth, organosilicone surfactants being preferred.
• a preferred organosilicone surfactant is a copolymer consisting essentially of SiO (silicate) units and (CH 3 ) SiO 0 . 5 (trimethylsiloxy) units in a molar ratio of silicate to trimethylsiloxy units of about 0.8: 1 to about 2.2: 1, preferably about 1 : 1 to about 2.0: 1.
• Another preferred organosilicone surfactant stabilizer is a partially cross-linked siloxane- polyoxyalkylene block copolymer and mixtures thereof wherein the siloxane blocks and polyoxyalkylene blocks are linked by silicon to carbon, or by silicon to oxygen to carbon, linkages.
• the siloxane blocks are comprised of hydrocarbon-siloxane groups and have an average of at least two valences of silicon, per block combined in said linkages. At least a portion of the polyoxyalkylene blocks are comprised of oxyalkylene groups and are polyvalent, i.e., have at least two valences of carbon and/or carbon-bonded oxygen per block combined in said linkages. Any remaining polyoxyalkylene blocks are comprised of oxyalkylene groups and are monovalent, i.e., have only one valence of carbon or carbon-bonded oxygen per block combined in said linkages. Additionally, conventional organopolysiloxane-polyoxyalkylene block copolymers such as those described in U.S. Pat. Nos.
• 2,834,748, 2,846,458, 2,868,824, 2,917,480, and 3,057,901 can be employed.
• the amount of the organosilicone polymer employed as a foam stabilizer in this invention can vary over wide limits, e.g., from about 0.5 weight parts to 10 weight parts or greater, per hundred weight parts of the active hydrogen component.
• the amount of organosilicone copolymer present in the foam formulations varies from about 1.0 weight parts to about 6.0 parts on the same basis.
• Catalysts include various inorganic metal compounds and metal compounds that include certain organic groups.
• Metal acetyl acetonates are preferred, based on metals such as aluminum, barium, cadmium, calcium, cerium (III), chromium (III), cobalt (II), cobalt (III), copper (II), indium, iron (II), lanthanum, lead (II), manganese (II), manganese (III), neodymium, nickel (II), palladium (II), potassium, samarium, sodium, terbium, titanium, vanadium, yttrium, zinc and zirconium.
• a common catalyst is bis(2,4-pentanedionate) nickel (II) (also known as nickel acetylacetonate or diacetylacetonate nickel) and derivatives thereof such as diacetonitrilediacetylacetonato nickel, diphenylnitrilediacetylacetonato nickel, bis(triphenylphosphine)diacetyl acetylacetonato nickel, and the like.
• Ferric acetylacetonate is particularly preferred, due to its relative stability, good catalytic activity, and lack of toxicity.
• the metal acetylacetonate is most conveniently added by predissolution in a suitable solvent such as dipropylene glycol or other hydroxyl containing compound which will then participate in the reaction and become part of the final product.
• acetyl acetone (2,4-pentanedione), as disclosed in commonly assigned U.S. Pat. No. 5,733,945 to Simpson, which is incorporated herein by reference. It has been discovered that the acetyl acetone can be used to delay or inhibit the normally reactive metal acetyl acetonate at the lower temperatures needed to achieve proper mixing and casting. In other words, the acetyl acetone provides heat latency, which allows time for the required mixing, casting, and other procedures, and avoids deleterious premature curing during low temperature processing.
• the acetyl acetone is driven off. With the acetyl acetone removed together with its associated delaying function, the metal acetyl acetonate is allowed to resume its normally high reactivity and provide a very high level of catalysis at the end of the polyurethane reaction. This high reactivity late in the processing cycle is advantageous and provides improved physical properties such as compression set.
• the ratio of metal acetyl acetonate to acetyl acetone is about 2:1 on a weight basis.
• the amount of catalyst present in the liquid phase is preferably in the range of 0.03 to 3.0 weight parts per hundred weight parts of the active hydrogen compound.
• the polyurethanes are formulated to provide low fogging and outgassing.
• the flame retarding composition comprises an antimony-based compound, a halogenated, active hydrogen-containing component reactive with the polyisocyanate component, and a halogenated flame-retarding agent, wherein the molar ratio of halogen to antimony is about 2.0:1 to about 18.0:1.
• halogenated and phosphorus-based flame retarding agents contribute to fogging and outgassing problems.
• the inventors hereof have unexpectedly discovered that tough, highly flame resistant polyurethane foams with no or minimal fogging or outgassing may be achieved by the use of the above-described flame retarding composition having a specified ratio of antimony and bromine.
• the viscosity of the active hydrogen-containing component is selected so as to allow incorporation of the improved flame retarding composition, while at the same time maintaining advantageous physical properties in the cured urethane. Appropriate selection of viscosity also allows incorporation of other fillers and reactive or non-reactive additives.
• the components of the flame retarding composition are selected to be either solid or reactive, and thus are low NOC.
• flame resistance and low fogging and outgassing is imparted to the cured compositions by use of a combination of low NOC components and a low NOC flame retarding composition comprising at least a low VOC halogenated, active hydrogen-containing component.
• the curable compositions accordingly comprise a low VOC isocyanate, a low VOC active hydrogen-containing component, a low VOC surfactant, a low VOC catalyst, and a low VOC flame retarding composition.
• the low VOC flame retardant composition comprises at least a low VOC, halogenated, active hydrogen-containing containing component, and may optionally further comprise other low VOC components.
• the viscosity of the active hydrogen-containing component is selected so as to allow incorporation of the flame retarding composition.
• low VOC refers to compounds having low (2% or less by weight) volatile organic compound levels.
• Volatile organic compounds as used herein refers to compounds capable of being driven off as a vapor at room temperature or slightly elevated temperatures, e.g., up to about 125 °C.
• Preferred antimony-based compounds for use in the flame retarding compositions include antimony trioxide, which is a solid.
• Preferred reactive, halogenated, active hydrogen-containing components are similar to those described above for the formation of the polyurethane, except that a halogen, preferably bromine, is present.
• Especially preferred reactive components include brominated diols that are liquid at the reactive temperature, for example 25°C, such as tetrabromophthalate diol. Solid, brominated diols that dissolve in the reactive composition are also suitable, for example, dibromoneopentyl alcohol and/or tribromoneopentyl alcohol.
• halogenated flame-retarding agents that are not reactive are generally the solid, bromine-containing organic compounds known for use in polyurethanes.
• Such agents include, but are not limited to, hexabromocyclododecane, brominated indan, ethylenebistetrabromophthalimide, bis(tribromophenoxy) ethane, tris(tribromophenyl) cyanurate, decabromodiphenyl oxide, tetradecabromodiphenoxybenzene, ethane- 1 ,2-bis(pentabromophenyl), and brominated polystyrene.
• flame retarding fillers may be used, for example aluminum trihydrate and melamine cyanurate.
• Particularly advantageous flame retardant fillers are those with high surface area such as carbon blacks and nanoclays.
• Nanoclays have the additional advantage of high aspect ratio but may require special treatment to separate the nanolayers to achieve the desired high surface area (exfoliation).
• An exemplary nanoclay is natural montmorillonite, produced, for example, by Southern Clay using various organic modifiers, under the trade names CLOISITE 10A, 15 A, 20A, 25 A, 30B, and 93 A. i order to get exfoliation of layers, CLOISITE 30B is preferred. Exfoliation of CLOISITE 20A was performed in PHT4-DIOL at elevated temperature (100°C).
• the flame retarding composition is present in an effective amount, which is readily determined by one of ordinary skill in the art based on the degree of flame resistance, processability of the formulation, and desired polyurethane properties. Effective quantities will generally be about 20 to about 60 weight percent of the non- isocyanate containing mixture.
• the relative amount of antimony (when present) and total bromine is adjusted to provide a molar ratio of total bromine to antimony of greater than or equal to about 2.0:1, preferably greater than or equal to about 2.5:1, more preferably greater than or equal to about 3.0:1 and most preferably greater than or equal to about 4.0:1.
• molar ratio of total bromine to antimony less than or equal to about 24.0: 1 , less than or equal to about 18.0:1, less than or equal to about 16.0:1, or less than or equal to about 14.0:1. It has been unexpectedly discovered that molar ratios of about 10.0:1 and higher can be used to proved excellent flame retardance in combination with desirable properties.
• a molar ratio of total bromine to antimony of 2.0:1 is approximately equivalent to a weight ratio of 1.25 : 1
• a molar ratio of 18.0 : 1 is approximately equal to a weight ratio of about 9.3:1.
• the weight percent of bromine (based on the total composition) is selected so as to provide a desired level of flame resistance, preferably at least HBF, more preferably at least V-l as measured in accordance with UL-94.
• bromine comprises at least about 12, preferably at least about 14 weight percent of the total composition.
• a lower concentration of bromine may be used where other flame retardant additives are present, such as melamine cyanurate.
• higher levels of bromine and antimony containing components, other additives, or combinations thereof can also be used to obtain improved flame resistance as long as the total viscosity is within processable limits.
• additives may be added to the polyurethane froth mixture in the manufacturing process.
• conventionally used additives such as other fillers (silica, talc, calcium carbonate, clay, and the like), dyes, pigments (for example titanium dioxide and iron oxide), and the like can be used.
• appropriate selection of anti-oxidant also results in improved high temperature resistance together with low fogging and outgassing.
• BHT for example, is a commonly used antioxidant, which is a solid at room temperature, but which sublimes at slightly elevated temperatures. When replaced with phenolic and amine-based antioxidants, such at those available under the trade names IRGANOX 1135, CAS No. 125643-61-0, and IRGANOX 5057, CAS No.
• Effective quantities are of from about 0.05 to about 0.25 weight percent of IRGANOX 1135 antioxidant and from about 0.005 to about 0.07 weight percent of IRGANOX 5057, preferably from about 0.07 to about 0.10 weight percent of IRGANOX 1135 and preferably from about 0.015 to about 0.03 weight percent of the polyol component.
• Use of hindered amine light stabilizers further imparts UV resistance.
• auxiliary blowing agent Small amounts of an auxiliary blowing agent can be employed.
• high boiling fluorocarbons e.g., boiling above about 40°C can be used.
• Specific fluorocarbons include for example l,l,2-trichloro-l,2,2-trifluoroethane and isomers of tetrachlorodifluoroethane, tefrachloromonofluoroethane, and the like.
• Other auxiliary blowing agents such as small amounts of water, although it is not necessary, can be employed for purposes of providing an added expansion during heat curing in those cases where such added expansion is desired.
• the gas phase of the novel froths in most preferably air because of its cheapness and ready availability.
• other gases can be used which are gaseous at ambient conditions and which are substantially inert or non-reactive with any component of the liquid phase.
• gases include, for example, nitrogen, carbon dioxide, and even fluorocarbons, which are normally gaseous at ambient temperatures.
• the inert gas is incorporated into the liquid phase by mechanical beating of the liquid phase in high shear equipment such as in a Hobart mixer or an Oakes mixer.
• the gas can be introduced under pressure as in the usual operation of an Oakes mixer or it can be drawn in from the overlying atmosphere by the beating or whipping action as in a Hobart mixer.
• the mechanical beating operation preferably is conducted at pressures not greater than 100 to 200 p.s.i.g. It is significant, however, to note that conventional, readily available, mixing equipment is used and no special equipment is necessary.
• the mechanical beating is conducted over a period of a few seconds to a minute in an Oakes mixer, or 3 to 30 minutes in a Hobart mixer, or however long it takes to obtain the desired froth density in the mixing equipment employed.
• the froth as it emerges from the mechanical beating operation is substantially chemically stable and is structurally stable but easily workable at ambient temperatures, e.g., about 10°C to about 40°C.
• the froth viscosity depends on the initial viscosity of the unfrothed composition.
• the density of the cured foams is generally about 10 to about 65 pcf, preferable about 15 to about 40 pcf, most preferably about 15 to about 30 pcf.
• the foams formed from the above-described compositions are flame resistant, having a UL-94 rating of V-2 and/or HBF, and/or passing MVSS No. 302.
• foams having a thickness of about 10 to about 500 mils, more preferably about 31 mils to about 250 mils and a density of about 15 to about 30 pcf have a UL 94 rating of V-l and/or HF-2, most preferably V- 0 and/or HF- 1.
• the foams are low fogging as measured in accordance with S AE
• the foams are low modulus, i.e., the CFD is about 3 to about 30 at foam densities of about 10 to about 50, more preferably about 15 to about 30 pcf, and tough, as reflected by high tear strengths, high tensile strengths, and high elongations relative to the modulus.
• the foams have a preferred compression set of less than about 20%, and a more preferred compression set of less than about 10% (after 50% compression for 22 hours at 70°C).
• the foams have a preferred compressive force deflection of less than about 85 psi, a more preferred compressive force deflection of less than about 30 psi, a preferred elongation greater than about 100, a preferred tensile strength of greater than about 50 psi, a more preferred tensile strength of greater than about 80 psi, a preferred tear strength greater than about 5, and a more preferred tear strength greater than about 8 pli.
• the foams are high modulus, i.e., the CFD is above about 30, preferably above about 50, more preferably above about 100, up to about 200 CFD, at a density of about 30 to about 65 pcf.
• the foams have a tensile strength of about 200 to about 500, an elongation greater than about 80, a tear strength greater than about 30, and a compression set of less than about 10% (after 25% compression for 22 hours at 70°C).
• the cured product may be overprinted with a UN-curable acrylic composition.
• a UN-curable acrylic composition may typically be used to prevent the material from sticking to itself during manufacture.
• Suitable acrylic compositions include for example RCE01496R which is commercially available from Sun Chemical.
• the foams produced from these compositions are useful for example in the vehicle industry, for example in the automotive, aircraft, and shipbuilding industries, and in the refrigeration and construction industries for foam filling and foam backing of cavities, for example boards and control panels, as interim layers for sandwich elements or for foam filling refrigerator and freezer casings.
• the polyurethane foams are also suitable as seals and gaskets, for vibration damping, and as insulation materials, for example as a gasket and seal for LED displays in electronic devices, and as wall linings, housing parts, cushion materials, armrests, headrests, device safety covers, and central consoles.
• the polyurethane foams are further described by the following non-limiting examples:
• Polyurethane foams having the compositions set forth in Table 2 and Table 3 below were formulated as follows.
• the non-isocyanate components i.e., the polyol mix, which contains the active hydrogen component, catalyst, flame retarding composition, and any fillers or additives
• the isocyanate was separately pumped into the mixing head. Dry air was introduced into the mixing head using a Matheson gas flow rate controller to adjust the flow so that the cured material had the desired density.
• the composition was cast onto coated release paper that had been dried by passing it through a high air flow oven at 275- 300°F just prior to the point where the foam was introduced.
• the cast foam was then passed under a knife over plate (KOP) coater to spread the foam to the desired thickness.
• KOP knife over plate
• the cast foam was then passed through heated platens (400°F upper, 250- 375°F lower) to cure, and subsequently cooled.
• the foams were then overcoated with a UV-curable acrylic composition.
• the foams thus synthesized were tested as follows. Results are shown in Table 2 and Table 3.
• Modulus as reflected by compression force deflection was determined on an histron using 2-inch by 2-inch die-cut samples stacked to a minimum of 0.250 inches, usually about 0.375 inches, using two stacks per lot or run, and a 20,000 pound cell mounted in the bottom of the Instron. CFD was measured by calculating the force in pounds per square inch (psi) required to compress the sample to 25% of the original thickness.
• Tensile strength and elongation were measured using an Instron fitted with a 50- pound load cell and using 10-20 pound range depending on thickness and density. Tensile strength is calculated as the amount of force (psi) at the break divided by the sample thickness and multiplied by two. Elongation is reported as percent extension. Tear strength was measured using an Instron fitted with a 50-pound load cell and using a 2, 5, or 10-pound load range depending on sample thickness and density. Tear strength is calculated by dividing the force applied at tear by the thickness of the sample.
• Outgassing was measured by ASTM E595 or by determining the percent weight loss of a sample held at 125°C for 24 hours. Outgassing for these and similar formulations is generally less than 1 weight percent.
• Compression set was determined by measuring the amount in percent by which a standard test piece of the foam fails to return to its original thickness after being subjected to a 50% or 25% compression for 22 hours at 70°C.
• the above-described flame retardant composition is of further utility in the manufacture of solid polyurethanes, e.g., polyurethane elastomers.
• Suitable compositions and methods for preparing elastomeric polyurethane polymers are described, for example, in U.S. Pat. Nos. 4,297,444; 4,218,543; 4,444,910; 4,530,941 and 4,269,945.
• Such elastomers are typically prepared by intimately mixing the reaction components at room temperature or a slightly elevated temperature for a short period and then casting the mixture or pouring the resulting mixture into an open mold, or injecting the resulting mixture into a closed mold, which in either case is heated.
• the mixture Upon completion of the reaction, the mixture takes the shape of the mold to produce a polyurethane elastomer of a predefined structure, which can then be sufficiently cured and removed from the mold with a minimum risk of incurring deformation greater than that permitted for its intended end application.
• Suitable conditions for promoting the curing of the elastomer include a mold temperature of typically from about 20 to about 150°C, preferably from about 35 to about 75°C, and more preferably from about 45 to about 55°C. Such temperatures generally permit the sufficiently cured elastomer to be removed from the mold typically in about 1 to 10 minutes and more typically in about 1 to 5 minutes after intimately mixing the reactants.

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• 2002
  • 2002-04-25 WO PCT/US2002/013136 patent/WO2003091308A1/en active Application Filing
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