PatentDe  


Dokumentenidentifikation EP1501891 20.12.2007
EP-Veröffentlichungsnummer 0001501891
Titel MISCHUNGEN VON TETRAHALOGENPHTHALATEN UND PHOSPHORVERBINDUNGEN ALS FLAMMSCHUTZMITTEL FÜR POLYURETHANE
Anmelder Pabu Services, Inc., Wilmington, Del., US
Erfinder BUSZARD, David, Woodford, Cheshire SK7 1QQ, GB;
PHILLIPS, Matthew D., Camden, IN 46917, US;
ROSE, Richard S., West Lafayette, IN 47906, US;
FALLOON, Stephen B., Lafayette, IN 47909, US
Vertreter derzeit kein Vertreter bestellt
DE-Aktenzeichen 60317320
Vertragsstaaten AT, BE, BG, CH, CY, CZ, DE, DK, EE, ES, FI, FR, GB, GR, HU, IE, IT, LI, LU, MC, NL, PT, RO, SE, SI, SK, TR
Sprache des Dokument EN
EP-Anmeldetag 05.05.2003
EP-Aktenzeichen 037244076
WO-Anmeldetag 05.05.2003
PCT-Aktenzeichen PCT/US03/13804
WO-Veröffentlichungsnummer 2003095544
WO-Veröffentlichungsdatum 20.11.2003
EP-Offenlegungsdatum 02.02.2005
EP date of grant 07.11.2007
Veröffentlichungstag im Patentblatt 20.12.2007
IPC-Hauptklasse C08K 5/12(2006.01)A, F, I, 20051017, B, H, EP

Beschreibung[en]
Technical Field

The present invention relates to flame retardant polyurethane compositions, and more particularly to flame retardant flexible polyurethane foam compositions, methods of flame retarding flexible polyurethane foam compositions, articles made therefrom and flame retardants that comprise blends of tetrahalophthalate esters and phosphorus-containing flame retardant additives.

Background Art

The production of materials based on polyurethane and other polymer systems derived from organic polyisocyanates is well established. Depending upon the formulations used in their manufacture, the products can vary in texture from the rubbery, elastomeric thermoplastic polyurethanes to the soft flexible foams used as cushioning materials to the rigid foams used as insulating or structural materials.

Flexible polyurethane foams are produced by reacting a polyol with a polyisocyanate in the presence of a foam-forming agent. Flexible polyurethane foams are used to make resilient structural materials such as cushioning or padding materials in the furniture and automotive industries. It is known to incorporate fire-retardant additives into such foam materials. However, care has to be taken so that adequate fire retardancy can be achieved without adversely affecting the desired physical properties of such foam materials.

Rigid polyurethane foams are produced by reacting a polyol with a polyisocyanate in the presence of blowing agents, surfactants and catalysts. Rigid polyurethane foams are typically used to in insulation applications, including insulation panels and light-weight laminated structural applications.

Blends of alkylated triphenyl phosphate with pentabromodiphenyl oxide have been used as flame retardants for flexible polyurethane foams and as flame retardant plasticizers in polyvinyl chloride (PVC) products. Due to environmental concerns, the use of pentabromodiphenyl oxide is being phased out of use, and alternative substitutes are being sought.

Dialkyltetrahalophthalate esters have been extensively researched. Di(2-ethylhexyl)tetrabromophthalate (DEHTBT) is a well known, commercially available flame retardant that is recommended for use in PVC, thermoplastic elastomers, and adhesives/coatings and is disclosed in International Publication No. WO 89/03854 to Pennwalt Corp.

The broad class of organophosphorus compounds, optionally halogenated, have long been used to reduce the flammability of substrates containing these materials. In particular, trialkyl phosphates, mixed alkylaryl phosphates, alkylated triaryl phosphates, and halohydrocarbyl phosphates are recognized flame retardant additives for a number of applications, including PVC and flexible polyurethane foams. Mixtures of different types of flame retardants are also known. Blends of alkyldiphenyl phosphate with DEHTBT are disclosed, and blends of alkylated triaryl phosphates with DEHTBT for use in PVC are suggested in United States Patent Nos. 4,892,683 to Naseem and 5,036,121 to Coaker et al . Alkylated triaryl phosphate blends with DEHTBT as flame retardant hydraulic fluids are disclosed in United States Patent No. 5,328,627 to Bohen et al .

The use of organophosphorus flame retardants, combined with halogenated flame retardants, in polyether flexible urethane foams are disclosed in United States Patent No. 4,880,844 to Fesman . Similarly, United States Patent No. 4,407,981 to Aaronson discusses the use of separate sources of organophosphorus and organohalogen flame retardants in polyurethanes and discloses the classes of "esters and imides of tetrabromophthalic anhydride" in a broad list of suitable organohalogen substances.

European Patent Application Publication No. 0 005 903 to Imperial Chemical Industries Ltd. discloses the use of dialkyl tetrabromophthalates with triaryl phosphates in rigid polyurea foams, with no suggestion of the applicability to flexible polyurethane foams.

United States Patent No. 5,728,760 to Rose et al . describes a family of brominated benzoate esters that are especially suited to use in flexible polyurethane foams. A means of producing the esters is via decarboxylation of half esters made from tetrabromophthalate anhydride.

Disclosure of the Invention

Subject-matter of the present invention are reaction mixtures for producing a flame retardant flexible polyurethane form according to claims 1 and 20 ; a flexible foamed article according to claim 10 ; and a method for providing a flame retardant flexible polyurethane composition according to claim 11.

According to various features, characteristics and embodiments of the present invention which will become apparent as the description thereof proceeds, the present invention provides a flame retardant composition which includes a non-reactive dialkyl tetrahalophthalate ester, a phosphorus-containing flame retardant having at least about 5 wt.% phosphorus and a flexible polyurethane foam reaction mixture.

The present invention further provides a method of providing flame retarded flexible polyurethane compositions which involves including, preferably (calculated on weight of polyol) about 2 to about 20 % by weight of, a blend of a dialkyl tetrahalophthalate ester and a phosphorus-containing flame retardant having at least about 5 wt.% phosphorus as a component of a flexible polyurethane foam reaction mixture.

The present invention also provides a flexible polyurethane foam reaction mixture which includes a dialkyl tetrahalophthalate ester, a phosphorus-containing flame retardant having at least about 5 wt.% phosphorus, and a flexible polyurethane foam reaction mixture.

According to the present invention, the combined weight of the dialkyl tetrahalophthalate ester and the phosphorus-containing flame retardant preferably comprises about 5 to about 20 % by weight of the polyol portion of the compositions to which they are added and the ratio of the dialkyl tetrahalophthalate ester to the phosphorus-containing flame retardant is from about 80:20 to about 20:80 percent by weight and preferably from about 60:40 to about 40:60 percent by weight.

The flame retardants provided according to the present invention for use in flexible polyurethane foam compositions comprise two components: (A) a dialkyl tetrahalophthalate ester; and (B) a phosphorous-containing flame retardant additive having at least about 5 wt.% phosphorus and optionally also having organically bound halogen.

The dialkyl tetrahalophthalate ester component generally useful for purposes of the present invention has the general structure: wherein R1 and R2 can be the same or different and represent a C1 to C20 linear, branched or cyclic alkyl group, and X is Cl or Br. In a preferred embodiment R1 and R2 are linear or branched C1 to C12 alkyl groups and X is Br. Di(2-ethylhexyl)tetrabromophthalate has been found to be particularly useful for purposes of the present invention.

The phosphorous-containing flame retardant additive used as component (B) can be any phosphorus-containing flame retardant additive that has at least about 5 wt.% phosphorus. It may optionally also have organically bound halogen, preferably chlorine or bromine. Compounds having less than about 5 wt.% phosphorus may also be used, but it has been determined that excessively high amounts of such compounds would be required to provide the desired levels of flame retardancy.

Suitable phosphorus sources include phosphates, phosphonates, phosphinates, phosphites and phosphine oxides. These may contain various alkyl, aryl, or alkaryl groups (optionally halogenated) provided that the size of the group does not cause the phosphorus content to be lower than about 5 wt.%. The phosphorous-containing flame retardant additive may be monomeric, dimeric or oligomeric.

Particularly suitable phosphorous-containing flame retardant additives include phosphates and phosphonates having one or two phosphorus atoms per molecule. Examples include: triethyl phosphate, tri-n-butyl phosphate, tri-isobutyl phosphate, tris(2-ethylhexyl) phosphate, dimethylmethyl phosphonate, resorcinol bis(diphenyl phosphate), dimethylpropyl phosphonate, triphenyl phosphate, and isodecyl diphenyl phosphate. Examples of halogenated phosphorus additives include tris(1,3-dichloro-2-propyl) phosphate also known as TDCP or Antiblaze® 195 (from Rhodia), and a chloroethyl diphosphate ester commercially available as Antiblaze 100 (from Rhodia).

More preferred phosphorous-containing flame retardant additives include (alkyl substituted) aryl phosphates having one or two (or mixtures of one or two) phosphorus atoms per molecule. Such phosphates are represented by the general formula: wherein each R3 is independently either H or a linear or branched C1 to C6 alkyl group, X is a residue of an aromatic or aliphatic diol, and n is 0 or 1. Specific, nonlimiting examples of the X precursor diol include resorcinol, catechol, neopentyl glycol, bisphenol-A and bisphenol-S.

Examples of specific (alkyl substituted) aryl phosphates include: neopentyl bis(diphenyl phosphate), tricresyl phosphate, bisphenol-A bis(diphenyl phosphate), butylated triphenyl phosphate, and isopropylated triphenyl phosphate.

(Alkyl substituted) aryl phosphates that are particularly suitable for purposes of the present invention include isopropylated triphenyl phosphates. It is to be understood that these include pure compounds such as 4-isopropylphenyl (diphenyl phosphate), as well as mixed triaryl phosphates in which the individual rings might contain 0, 1 or 2 isopropyl groups. In general, these alkylated triaryl phosphates will contain anywhere from about 9 wt.% phosphorus down to about 7 wt.% phosphorus depending on the degree of alkylation.

In the blends, components (A) and (B) are used in ratios that are readily determined to provide the best balance of properties. Such ratios are typically from about 80:20 to about 20:80 wt.%, and preferably about 60:40 to about 40:60 wt%. The most preferred ratio is about 40 wt.% of the brominated dialkyl phthalate and about 60 wt.% of the phosphorus source.

In order to incorporate the blends of tetrahalophthalate esters and phosphorus-containing flame retardant additives into polyurethane foam compositions, the components (A) and (B) may be combined together such that (A) and (B) are provided as a single flame retardant package. Otherwise the components (A) and (B) may be added separately and individually to the other urethane foam reactants.

When used as a precombined package the overall blend of components (A) and (B) is typically used in an amount of from about 2 to about 20 wt.% when calculated on the weight of the polyol used in the formulations.

The flexible polyurethane foam compositions in which the blends of tetrahalophthalate esters and phosphorus-containing flame retardant additives are used according to the present invention include all well known, industrial compositions. Basically, flexible polyurethane foam compositions can be made according to the present invention by reacting toluene isocyanate with a polyol in the presence of a foam-forming agent and a blend of tetrahalophthalate esters and phosphorus-containing flame retardant additives.

The flame retardant flexible polyurethane foams of the present invention are useful as cushioning materials in home furnishing and automotive applications and other applications that typically involve the use of flexible foam materials.

Generally polyurethane examples were prepared according to the following procedure.

The specified fire retardant component is first combined with the polyol component. When the polyol component and fire retardant appear to be mixed, the remaining components of the formulations, except for the isocyanate, are added and mixed. When the composition appears to be mixed, isocyanate is added as the last component and mixed until the mixture appears homogeneous. Unless otherwise indicated measurement units are by weight.

The reaction mixture is poured into a box and allowed to expand fully. The box containing expanded foam is placed in a ventilated 110°C oven for 30 minutes to accelerate curing. Foam samples are removed from their boxes and stored under ambient conditions for at least twenty four hours prior to testing.

Examples 1 - 8

The formulations of the foam yield a polyurethane composition having a density of 22.7 kg/m3 (1.5 1b/ft3) according to Table 1. The measurement 'Index' is a measure of the quantity of reactant required to react stoichiometrically with the sum of all hydroxyl moities present in the reaction mixture from the polyol and water. A 100 index represents 1:1 stoichiometry. A 110 index represents a ten percent excess of reactant for the sum of hydroxyls present. Table 1 Polyurethane Component Parts per Hundred Parts Polyol (php) conventional polyether polyol prepared from polyethylene oxide having a hydroxyl number of 56 and a molecular weight of 3000 100 water 4.4 Dabco 8264 amine catalyst from Air Products & Chemicals Inc. 7201 Hamilton Boulevard, Allentown, PA 18195 United States. 0.48 Osi L-620 silicone surfactant a polyalkalene oxide - methyl siloxane co-polymer Crompton Corporation, One American Lane, Greenwich, CT, 06831, United States 1.0 stannous octoate catalyst 0.29 toluene diisocyanate 110 index

Various fire retardant components are added to the foam composition of Table 1. The fire retardants are evaluated to determine a loading level required to meet or exceed the standard of Federal Motor Vehicle Safety Standard No. 302, Published in the United States Code of Federal Regulations, 49 CFR section 571.302 (FMVSS-302) - Flammability of interior materials; and the test standard published by the State of California, Department of Consumer Affairs, Bureau of Home Furnishings and Thermal Insulation Technical Information Bulletin 117.

For the fire retardants tested according to the test methods Table 2 sets forth the level of fire retardant required to achieve the fire retardant standards of the tests for the polyurethane foam of Table 1. Table 2 Example Fire Retardant California 117 Test (php) MVSS-302 Loading (php) 1* a blend of 3 part of pentabromodiphenyloxide and 1 part triisopropylated arylphosphate 15 14 2* a blend of 1 part benzoate of tetrabromo phthalic anhydride and 1 part triisopropylated arylphosphate 15 14 3* tris dichloropropyl phosphate 14 13 4 a blend 4 parts 2-ethylhexylphthalate of tetrabromophthalic anhydride and 6 parts triisopropylated arylphosphate 15 14 5 a blend of 4 parts 2-ethylhexylphthalate of tetrabromophthalic anhydride and 6 parts resorcinol diphosphate 17 16 6 a blend of 4 parts 2-ethylhexylphthalate of tetrabromophthalic anhydride and 6 parts tris chloroethyl phosphate 15 14 7 a blend of 4 parts 2-ethylhexylphthalate of tetrabromophthalic anhydride and 6 parts tris dichloropropyl phosphate 14 13 8 a blend of 4 parts 2-ethylhexylphthalate of tetrabromophthalic anhydride and 6 parts phosphoric acid, 2,2-bis(chloromethyl)-1,3-propanediyltetrakis(2-chloroethyl)ester. 14 14 * comparative example

Examples 9 - 16

The formulations of the foam yield a polyurethane composition having a density of 27.3 kg/m3 (1.8 lb/ft3) according to Table 3. Table 3 Polyurethane component parts per hundred parts polyol (php) conventional polyether polyol prepared from polyethylene oxide having a hydroxyl number of 56 and a molecular weight of 3000 100 water 3.4 Dabco 8264 amine catalyst 0.48 Osi L-620 silicone surfactant 1.0 stannous octoate catalyst 0.28 toluene diisocyanate 110 index

For the fire retardants tested according to the test method, Table 4 sets forth the level of fire retardant required to achieve the fire retardant standards of the FMVSS-302 test for the polyurethane foam of Table 3. Table 4 Example Fire Retardant MVSS-302 Load Level (php) 9* a blend of 3 part of pentabromodiphenyloxide and 1 part triisopropylated arylphosphate 4 10* a blend of 1 part benzoate of tetrabromo phthalic anhydride and 1 part triisopropylated arylphosphate 4 11* tris dichloropropyl phosphate 4 12 a blend 4 parts 2-ethylhexylphthalate of tetrabromophthalic anhydride and 6 parts triisopropylated arylphosphate 4 13 a blend of 4 parts 2-ethylhexylphthalate of tetrabromophthalic anhydride and 6 parts resorcinol diphosphate 5 14 a blend of 4 parts 2-ethylhexylphthalate of tetrabromophthalic anhydride and 6 parts tris chloroethyl phosphate 4 15 a blend of 4 parts 2-ethylhexylphthalate of tetrabromophthalic anhydride and 6 parts tris dichloropropyl phosphate 4 16 a blend of 4 parts 2-ethylhexylphthalate of tetrabromophthalic anhydride and 6 parts phosphoric acid, 2,2-bis(chloromethyl)-1,3-propanediyltetrakis(2-chloroethyl)ester. 4 * comparative example

Although the present invention has been described with reference to particular means, materials and embodiments, from the foregoing description, one skilled in the art can easily ascertain the essential characteristics of the present invention and various changes and modifications can be made to adapt the various uses and characteristics.

The foregoing examples demonstrate that commercial fire retardant standards can be achieved in flexible polyurethane foams without the need the use of pentabromodiphenyloxide. Rather, at comparable loading levels, blended fire retardants including tetrahalophthalate esters and phosphorus-containing flame retardant additives provide comparable, if not improved fire retardant properties.


Anspruch[de]
Reaktionsmischung, die, wenn sie zur Reaktion gebracht wird, einen flammhemmenden, flexiblen Polyurethanschaum erzeugt, wobei die Mischung Folgendes enthält: ein Polyol; einen Dialkyltetrahalophthalatester; einen phosphorhaltigen Flammhemmer mit mindestens etwa 5 Gewichtsprozent Phosphor, wobei das Verhältnis des Dialkyltetrahalophthalatesters zum phosphorhaltigen Flammhemmer von 60:40 bis 40:60 Gewichtsprozent reicht; und ein Schaumbildnermittel; und Toluendiisocyanat. Mischung gemäß Anspruch 1, wobei das kombinierte Gewicht des Dialkyltetrahalophthalatesters und des phosphorhaltigen Flammhemmers von 5 bis 20 Gewichtsprozent des Polyolanteils der Zusammensetzung ausmacht. Mischung gemäß einem der vorangehenden Ansprüche, wobei der Dialkyltetrahalophthalatester folgende allgemeine Formel hat: wobei R1 und R2 gleich oder unterschiedlich sein können und lineare oder verzweigte C1 bis C12 Alkylgruppen sind und wobei X Br ist. Mischung gemäß Anspruch 3, wobei der Dialkyltetrahalophthalatester Di(2-ethylhexyl)tetrabromophthalat umfasst. Mischung gemäß einem der vorangehenden Ansprüche, wobei der phosphorhaltige Flammhemmer mindestens eines aus einem Phosphat, einem Phosphonat, einem Phosphinat, einem Phosphit und einem Phosphinoxid umfasst. Mischung gemäß Anspruch 5, wobei der phosphorhaltige Flammhemmer mindestens eines aus Triethylphosphat, Tri-n-butylphosphat, Triisobutylphosphat, Tris(2-ethylhexyl)phosphat, Dimethylmethylphosphonat, Resorcinol-bis(diphenylphosphat), Dimethylpropylphosphonat, Triphenylphosphat und Isodecyldiphenylphosphat umfasst. Mischung gemäß Anspruch 5, wobei der phosphorhaltige Flammhemmer folgende allgemeine Formel hat: wobei jedes R3 unabhängig entweder H oder eine lineare oder verzweigte C1 bis C6 Alkylgruppe, X ein Rest eines aromatischen oder aliphatischen Diols und n 0 oder 1 ist. Mischung gemäß Anspruch 7, wobei der phosphorhaltige Flammhemmer mindestens eines aus einem Neopentyl-bis(diphenylphosphat), einem Tricresylphosphat, einem Bisphenol-A-bis(diphenylphosphat), einem butylierten Triphenylphosphat und einem isopropylierten Triphenylphosphat umfasst. Mischung gemäß Anspruch 8, wobei der phosphorhaltige Flammhemmer ein isopropyliertes Triphenylphosphat umfasst. Flexibler geschäumter Artikel, der durch die Reaktion und Schäumung einer Mischung gemäß einem der vorangehenden Ansprüche hergestellt wird. Verfahren zur Bereitstellung einer flammhemmenden, flexiblen Polyurethanzusammensetzung, wobei das Verfahren eine Reaktion eines Polyols mit Toluendiisocyanat und einem Schaumbildnermittel zur Herstellung eines flexiblen Polyurethanschaums umfasst und wobei die Reaktionsmischung einen Dialkyltetrahalophthalatester und einen phosphorhaltigen Flammhemmer mit mindestens etwa 5 Gewichtsprozent Phosphor umfasst, wobei das Verhältnis des Dialkyltetrahalophthalatesters zum phosphorhaltigen Flammhemmer von 60:40 bis zu 40:60 Gewichtsprozent reicht. Verfahren gemäß Anspruch 11, wobei der Dialkyltetrahalophthalatester und der phosphorhaltige Flammhemmer vorgemischt werden, bevor sie der flexiblen Polyurethanschaum-Reaktionsmischung zugegeben werden. Verfahren gemäß Anspruch 11, wobei der Dialkyltetrahalophthalatester folgende allgemeine Formel hat: wobei R1 und R2 gleich oder unterschiedlich sein können und lineare oder verzweigte C1 bis C12 Alkylgruppen sind und X Br ist. Verfahren gemäß Anspruch 13, wobei der Dialkyltetrahalophthalatester Di(2-ethylhexyl)tetrabromophthalat umfasst. Verfahren gemäß Anspruch 11, wobei der phosphorhaltige Flammhemmer mindestens eines aus einem Phosphat, einem Phosphonat, einem Phosphinat, einem Phosphit und einem Phosphinoxid umfasst. Verfahren gemäß Anspruch 15, wobei der phosphorhaltige Flammhemmer mindestens eines aus Triethylphosphat, Tri-n-butylphosphat, Triisobutylphosphat, Tris(2-ethylhexyl)phosphat, Dimethylmethylphosphonat, Resorcinol-bis(diphenylphosphat), Dimethylpropylphosphonat, Triphenylphosphat und Isodecyldiphenylphosphat umfasst. Verfahren gemäß Anspruch 15, wobei der phosphorhaltige Flammhemmer folgende allgemeine Formel hat: wobei jedes R3 unabhängig entweder H oder eine lineare oder verzweigte C1 bis C6 Alkylgruppe ist, X ein Rest eines aromatischen oder aliphatischen Diols und n 0 oder 1 ist. Verfahren gemäß Anspruch 17, wobei der phosphorhaltige Flammhemmer mindestens eines aus einem Neopentyl-bis(diphenylphosphat), einem Tricresylphosphat, einem Bisphenol-A-bis(diphenylphosphat), einem butylierten Triphenylphosphat und einem isopropylierten Triphenylphosphat umfasst. Verfahren gemäß Anspruch 18, wobei der phosphorhaltige Flammhemmer ein isopropyliertes Triphenylphosphat umfasst. Reaktionsmischung, die, wenn sie zur Reaktion gebracht wird, einen flammhemmenden flexiblen Polyurethanschaum produziert, wobei die Mischung Folgendes umfasst: ein Polyol; Toluendiisocyanat; und ein Schaumbildnermittel; und Flammhemmer, wobei die Flammhemmer aus zwei Komponenten bestehen, einer ersten Komponente, die Dialkyltetrahalophthalatester ist, und einer zweiten Komponente, die ein phosphorhaltiger Flammhemmer mit mindestens etwa 5 Gewichtsprozent Phosphor ist.
Anspruch[en]
A reaction mixture which, when reacted, produces a flame retardant flexible polyurethane foam, the mixture comprising: a polyol; a dialkyl tetrahalophthalate ester; a phosphorus-containing flame retardant having at least about 5 wt % phosphorus, wherein the ratio of the dialkyl tetrahalophthalate ester to the phosphorus-containing flame retardant is from 60:40 to 40:60 percent by weight; and a foam-forming agent; and toluene diisocyanate. A mixture according to claim 1, wherein the combined weight of the dialkyl tetrahalophthalate ester and the phosphorus-containing flame retardant comprises from 5 to 20 % by weight of the polyol portion of the composition. A mixture according to any one of the preceding claims, wherein the dialkyl tetrahalophthalate ester has the general formula: wherein R1 and R2 can be the same or different and are linear or branched C1 to C12 alkyl groups and X is Br. A mixture according to claim 3, wherein the dialkyl tetrahalophthalate ester comprises di(2-ethylhexyl)tetrabromophthalate. A mixture according to any one of the preceding claims, wherein the phosphorus-containing flame retardant comprises at least one of a phosphate, a phosphonate, a phosphinate, a phosphite and a phosphine oxide. A mixture according to claim 5, wherein the phosphorus-containing flame retardant comprises at least one of triethyl phosphate, tri-n-butyl phosphate, tri-isobutyl phosphate, tris(2-ethylhexyl) phosphate, dimethylmethyl phosphonate, resorcinol bis (diphenyl phosphate), dimethylpropyl phosphonate, triphenyl phosphate, and isodecyl diphenyl phosphate. A mixture according to claim 5, wherein the phosphorus-containing flame retardant has the general formula: wherein each R3 is independently either H or a linear or branched C1 to C6 alkyl group, X is a residue of an aromatic or aliphatic diol, and n is 0 or 1. A mixture according to claim 7, wherein the phosphorus-containing flame retardant comprises at least one a neopentyl bis(diphenyl phosphate), a tricresyl phosphate, a bisphenol-A bis(diphenyl phosphate), a butylated triphenyl phosphate, and an isopropylated triphenyl phosphate. A mixture according to claim 8, wherein the phosphorus-containing flame retardant comprises an isopropylated triphenyl phosphate. A flexible foamed article made by reacting and foaming a mixture as claimed in any one of the preceding claims. A method of providing a flame retarded flexible polyurethane composition which method comprises reacting a polyol with toluene diisocyanate and a foam-forming agent to produce a flexible polyurethane foam, wherein the reaction mixture comprises a dialkyl tetrahalophthalate ester and a phosphorus-containing flame retardant having at least about 5 wt.% phosphorus wherein the ratio of the dialkyl tetrahalophthalate ester to the phosphorus-containing flame retardant is from 60:40 to 40:60 percent by weight. A method according to claim 11, wherein the dialkyl tetrahalophthalate ester and phosphorus-containing flame retardant are preblended together before being added to the flexible polyurethane foam reaction mixture. A method according to claim 11, wherein the dialkyl tetrahalophthalate ester has the general formula: wherein R1 and R2 can be the same or different and are linear or branched C1 to C12 alkyl groups, and X is Br. The method according to claim 13, wherein the dialkyl tetrahalophthalate ester comprises di(2-ethylhexyl)tetrabromophthalate. The method according to claim 11, wherein the phosphorus-containing flame retardant comprises at least one of a phosphate, a phosphonate, a phosphinate, a phosphite and a phosphine oxide. The method according to claim 15, wherein the phosphorus-containing flame retardant comprises at least one of triethyl phosphate, tri-n-butyl phosphate, tri-isobutyl phosphate, tris(2-ethylhexyl) phosphate, dimethylmethyl phosphonate, resorcinol bis (diphenyl phosphate), dimethylpropyl phosphonate, triphenyl phosphate, and isodecyl diphenyl phosphate. The method according to claim 15, wherein the phosphorus-containing flame retardant has the general formula: wherein each R3 is independently either H or a linear or branched C1 to C6 alkyl group, X is a residue of an aromatic or aliphatic diol, and n is 0 or 1. The method according to claim 17, wherein the phosphorus-containing flame retardant comprises at least one a neopentyl bis(diphenyl phosphate), a tricresyl phosphate, a bisphenol-A bis(diphenyl phosphate), a butylated triphenyl phosphate, and an isopropylated triphenyl phosphate. The method according to claim 18, wherein the phosphorus-containing flame retardant comprises an isopropylated triphenyl phosphate. A reaction mixture which, when reacted, produces a flame retardant flexible polyurethane foam, the mixture comprising: a polyol; toluene diisocyanate, and a foam-forming agent; and flame retardants, wherein the flame retardants consist of two components, a first component, which is dialkyl tetrahalophthalate ester, and a second component, which is a phosphorus-containing flame retardant having at least about 5 wt % phosphorus.
Anspruch[fr]
Mélange réactionnel qui, lorsqu'il est mis à réagir, produit une mousse de polyuréthane souple ignifuge, le mélange comprenant : un polyol ; un ester de dialkyltétrahalophtalate ; un agent ignifugeant contenant du phosphore dont la teneur en phosphore est d'au moins environ 5 % en poids, le rapport de l'ester de dialkyltétrahalophtalate sur l'agent ignifugeant contenant du phosphore allant de 60 : 40 à 40 : 60 pour cent en poids ; un agent moussant ; et du diisocyanate de toluène. Mélange selon la revendication 1, dans lequel le poids combiné de l'ester de dialkyltétrahalophtalate et de l'agent ignifugeant contenant du phosphore constitue d'environ 5 à environ 20 % en poids de la proportion de polyol de la composition. Mélange selon l'une quelconque des revendications précédentes, dans lequel l'ester de dialkyltétrahalophtalate répond à la formule générale : dans laquelle R1 et R2 peuvent être identiques ou différents et sont des groupes alkyle en C1 à C12 linéaires ou ramifiés et X représente Br. Mélange selon la revendication 3, dans lequel l'ester de dialkyltétrahalophtalate comprend le di(2-éthylhexyl)tétrabromophtalate. Mélange selon l'une quelconque des revendications précédentes, dans lequel l'agent ignifugeant contenant du phosphore comprend au moins un phosphate et/ou phosphonate et/ou phosphinate et/ou phosphite et/ou oxyde de phosphine. Mélange selon la revendication 5, dans lequel l'agent ignifugeant contenant du phosphore comprend au moins du phosphate de triéthyle et/ou phosphate de tri-n-butyle et/ou phosphate de tri-isobutyle et/ou phosphate de tris(2-éthylhexyle) et/ou phosphonate de diméthylméthyle et/ou résorcinol bis(diphényle phosphate) et/ou phosphonate de diméthylpropyle et/ou phosphate de triphényle et/ou phosphate d'isodécyle diphényle. Mélange selon la revendication 5, dans lequel l'agent ignifugeant contenant du phosphore répond à la formule générale : dans laquelle chaque R3 est indépendamment soit H soit un groupe alkyle en C1 à C6 linéaire ou ramifié, X représente un résidu de diol aromatique ou aliphatique, et n vaut 0 ou 1. Mélange selon la revendication 7, dans lequel l'agent ignifugeant contenant du phosphore comprend au moins du néopentyl bis(diphényl phosphate) et/ou phosphate de tricrésyle et/ou bisphénol-A bis(diphényl phosphate) et/ou phosphate de triphényle butylé et/ou phosphate de triphényle isopropylé. Mélange selon la revendication 8, dans lequel l'agent ignifugeant contenant du phosphore comprend un phosphate de triphényle isopropylé. Article en mousse souple réalisé par réaction et moussage d'un mélange tel que revendiqué dans l'une quelconque des revendications précédentes. Procédé de préparation d'une composition de polyuréthane souple ignifuge, comprenant la réaction d'un polyol avec du diisocyanate de toluène et un agent moussant afin de produire une mousse de polyuréthane souple, le mélange réactionnel comprenant un ester de dialkyltétrahalophtalate et un agent ignifugeant contenant du phosphore dont la teneur en phosphore est d'au moins environ 5 % en poids, le rapport de l'ester de dialkyltétrahalophtalate sur l'agent ignifugeant contenant du phosphore allant de 60 : 40 à 40 : 60 pour cent en poids. Procédé selon la revendication 11, dans lequel l'ester de dialkyltétrahalophtalate et l'agent ignifugeant contenant du phosphore sont préalablement mélangés l'un à l'autre avant d'être ajoutés au mélange réactionnel de mousse de polyuréthane souple. Procédé selon la revendication 11, dans lequel l'ester de dialkyltétrahalophtalate répond à la formule générale : dans laquelle R1 et R2 peuvent être identiques ou différents et sont des groupes alkyle en C1 à C12 linéaires ou ramifiés et X représente Br. Procédé selon la revendication 13, dans lequel l'ester de dialkyltétrahalophtalate comprend le di(2-éthylhexyl)tétrabromophtalate. Procédé selon la revendication 11, dans lequel l'agent ignifugeant contenant du phosphore comprend au moins un phosphate et/ou phosphonate et/ou phosphinate et/ou phosphite et/ou oxyde de phosphine. Procédé selon la revendication 15, dans lequel l'agent ignifugeant contenant du phosphore comprend au moins du phosphate de triéthyle et/ou phosphate de tri-n-butyle et/ou phosphate de tri-isobutyle et/ou phosphate de tris(2-éthylhexyle) et/ou phosphonate de diméthylméthyle et/ou résorcinol bis(diphényle phosphate) et/ou phosphonate de diméthylpropyle et/ou phosphate de triphényle et/ou phosphate d'isodécyle et de diphényle. Procédé selon la revendication 15, dans lequel l'agent ignifugeant contenant du phosphore répond à la formule générale : dans laquelle chaque R3 est indépendamment soit H soit un groupe alkyle en C1 à C6 linéaire ou ramifié, X représente un résidu de diol aromatique ou aliphatique, et n vaut 0 ou 1. Procédé selon la revendication 17, dans lequel l'agent ignifugeant contenant du phosphore comprend au moins du néopentyl bis(diphényl phosphate) et/ou phosphate de tricrésyle et/ou bisphénol-A bis(diphényl phosphate) et/ou phosphate de triphényle butylé et/ou phosphate de triphényle isopropylé. Procédé selon la revendication 18, dans lequel l'agent ignifugeant contenant du phosphore comprend un phosphate de triphényle isopropylé. Mélange réactionnel qui, lorsqu'il est mis à réagir, produit une mousse de polyuréthane souple ignifuge, le mélange comprenant : un polyol ; du diisocyanate de toluène ; un agent moussant ; et des agents ignifugeants, les agents ignifugeants consistant en deux composants, un premier composant constitué par l'ester de dialkyltétrahalophtalate, et un second composant constitué par un agent ignifugeant contenant du phosphore dont la teneur en phosphore est d'au moins environ 5 % en poids.






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