TW201202504A - Liquid flame retardant formulation useful for flame lamination applications - Google Patents

Abstract

This invention relates to a liquid flame retardant formulation for use in flexible foam applications. More particularly this invention relates to a liquid flame retardant formulation useful for flexible foams in flame lamination applications.

Description

201202504 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a liquid flame retardant formulation for flexible foam applications. More specifically, the present invention relates to a liquid flame retardant formulation for use in flexible foams in flame bonding applications. [Prior Art] Polyacetal foam is used in many applications, such as furniture, (chairs, sofas, mattresses, pillows), motor vehicles (seats, headrests and armrests, roof linings, dashboards), carpet mats, Filter media and insulators, etc. Like all carbon-based products, polyurethane foams have the potential to burn, but polyurethane foams are particularly prone to combustion because of their large specific surface area and the presence of open pores to allow easy access to the oxygen required for combustion. Many of the research aims to impart flame retardant properties to these foams. However, in contrast to the prior art, technology bursts always pursue suitable flame retardant compositions that are superior or have better performance. Examples of flexible foam applications include automotive interiors, seating and furniture applications. In one application, the flexible foam is attached or adhered to the textile by flame bonding. Flame bonding is a term used in the method of joining textiles to foams, which uses a flame to initially melt one side of the foam sheet and then immediately press the textile web against the side. The requirements of this application are that the resulting textiles have good flame retardant properties, good adhesion between textiles and foams' and some customers require good scorch and low atomization/volatile organic carbon (VOC). emission. 201202504 SUMMARY OF THE INVENTION The present invention is directed to a liquid flame retardant composition for a flexible polyurethane foam for use in flame bonding applications, comprising: (a) a liquid flame retardant; (b) an aromatic polyester polyol; a low molecular weight diol; (d) a cyclic phosphonate flame retardant; and (e) an optionally alkylated diphenylamine or hindered phenol antioxidant. Fig. 1 shows the scorch test data in Table 2 of Comparative Example 1 and Comparative Examples 2 to 5 and 1 2 of the present invention. Embodiments The present invention relates to a liquid flame retardant composition comprising: a liquid flame retardant, an aromatic polyester polyol, a low molecular weight glycol, a cyclophosphonate flame retardant, and optionally a hindered phenol antioxidant . The liquid flame retardant may be any suitable liquid flame retardant used industrially. Preferably, the liquid flame retardant is a phosphorus-based flame retardant or a phosphorus halide-based flame retardant. For example, a phosphorus-based flame retardant which can be used is a chloroalkyl phosphate or a phosphonate flame retardant. Examples of such liquid flame retardants include, but are not limited to, bis(2-chloroethyl)2-chloroethylphosphonate tris(monochloropropyl) phosphate, tris(1,3-dichloroisopropyl) Phosphate, 2,2-bis(chloromethyl)trimethylene, bis(bis(2-chloroethyl)phosphate) 'bisphenol A bis(diphenyl phosphate), isopropylated phenol phosphate Esters (IP PP) 'dimethylmethylphosphonate, diethylethylphosphonate, or mixtures thereof. -4- 201202504 The amount of liquid flame retardant that can be used can range from about 1% to about 90% by weight, more specifically from about 7.5 to about 80% by weight of the total weight of the composition. Most particularly it is about 15 weight. /. Up to about 70 weight. /. . The aromatic polyester polyol is formed by a reaction between (a) an aromatic acid-based material (e.g., an phthalic acid-based material), (b) a hydroxylated material, and optionally (c) a hydrophobic material. The term "aromatic polyester polyol," as used herein, means a polyol having an ester bond and an aromatic component. The aromatic polyester polyol has an advantage in that the average functionality is from about 1.5 to 8.0, preferably From about 1.6 to 6 · 0, more preferably from about 1.8 to 4.0. Their average number of hydroxyl groups 値 is usually in the range of from about 5 Torr to about 400' or from about 10,000 to about 325, or The range of from about 150 to about 250. The "number of warp groups" refers to the concentration of hydroxyl groups capable of reacting with isocyanate groups per unit weight of polyol. The number of hydroxyl groups is reported as mg KOH / g, and according to standard ASTM D Measured at 1638. The viscosity of the aromatic polyester polyol is from about 300 to about 25,0 centipoise at a temperature of about 25 ° C. The aromatic component of the aromatic polyester polyol composition may be For example, phthalic acid-based components such as phthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride, phthalic anhydride, dimethyl terephthalate, polyparaphenylene Ethylene glycol dicarboxylate, trimellitic anhydride, and their bottom residues, derivatives, and combinations. The phthalic acid-based material used in the space refers to a phthalic acid or a phthalic acid derivative. The preferred phthalic acid-based material for preparing the aromatic polyester polyol is phthalic anhydride or p-benzoic acid. The anhydride may have an aromatic component of, for example, from about 20% by weight to about 70% by weight of the aromatic polyester polyol component, alternatively from about 30% by weight to about 60% by weight of the aromatic polyester polyol. The hydroxylated component of the aromatic polyester polyol component of the present invention may be, for example, at least one aliphatic diol, at least one derivative thereof, or a combination thereof. The hydroxylated component may be a general formula. (1) An aliphatic diol: HO-R^OH, wherein R1 is selected from the group consisting of divalent groups (a) each having an alkylene group of 2 to 18 carbon atoms, and (b) a group of 2): -(R20)n-R2-, wherein R2 is an alkylene group having 2 to 3 carbon atoms, and η is an integer from 1 to 3, and (Ο a mixture thereof) Examples of suitable aliphatic diols of 1) include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, trimethylene a poly(oxyalkylene) which contains 2 to 4 alkylene groups derived from the condensation of ethylene oxide, butylene glycol, 1,2-cyclohexanediol, by condensation of ethylene oxide, propylene oxide or a mixture thereof. Bases) Polyols, etc. In the preparation of mixed poly(ethylene oxide-propylene oxide) polyols, those skilled in the art realize that ethylene oxide and propylene oxide can be added in a mixed or sequential manner. The starting reactant containing a hydroxyl group may be a mixture of these glycols if necessary. The aliphatic diol of the formula (I) of the present invention is most preferably diethylene glycol. Further, an amine fat may be used. Group hydroxylated materials (i.e., hydroxylamines), such as monoethanolamine, diethanolamine, and triethanolamine. -6- 201202504 Alternatively, for example, a mixture of glycols can be incorporated into a low molecular weight polyol (ie, a compound containing less than 7 carbon atoms per molecule but containing at least 3 hydroxyl groups per molecule), typically in an amount of The total hydroxylated material is greater than 0% up to 100%. The polyol includes, for example, glycerin, trimethylolpropane, 1,1,1-trimethylolethane, 2,2-dimethyl-1,3-propanediol, pentaerythritol, a mixture thereof and the like. The hydroxylated component of the aromatic polyester polyol component can comprise, for example, from about 30% to about 80% by weight based on the total weight of the aromatic polyester polyol component. Alternatively, the hydroxylated component of the aromatic polyester polyol may be from about 30% to about 65% by weight based on the total weight of the aromatic polyester polyol. Alternatively, the hydroxylated material in the polyester polyol is from about 4 Å to 60% by weight based on the total weight of the aromatic polyester polyol. Optionally, the aromatic polyester polyol may contain a hydrophobic component. Examples of such hydrophobic components include, but are not limited to, carboxylic acids (especially fatty acids), lower alkyl esters of carboxylic acids (especially fatty acid methyl esters), fatty acid alkanolamines, and natural derived from renewable energy sources. Oil (such as 'triglycerides (especially fats and oils)). The natural oil may not be modified (e.g., does not contain a hydroxyl functional group), nor is it functionalized (natural oil polyol) or both. Suitable natural oils provided by the present invention include, for example, triglyceride oil, coconut oil, cochin oil, corn oil, cottonseed oil, linseed oil, olive oil, palm oil, palm kernel oil, peanut oil, soybean oil, sunflower oil , Lol oil, animal fat oil, lesquerella oil, tung oil, oil, Yuhao oil 'sesame oil, safflower oil' rapeseed oil, fish oil, derivatives of the above substances and combinations thereof. Suitable derivatives of the natural oil include, but are not limited to, 'residual acids (eg, 'fat 201202504 acid, lower alcohol ester (eg, fatty acid methyl ester)) and fatty acid alkanolamines. Examples of fatty acids include, but are not limited to: Acid, caprylic acid, citric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, and mixtures thereof. Other suitable acids are 2-ethylhexanoic acid. Examples of fatty acid methyl esters include, but are not limited to, methyl hexanoate, methyl octanoate, methyl decanoate, methyl laurate, methyl myristate, methyl palmitate, methyl oleate, stearic acid Esters, methyl linoleate, methyl linolenate, and mixtures thereof. Examples of fatty alkanolamines include, but are not limited to, halal oil fatty acid diethanolamine, lauric acid diethanolamine and oleic acid monoethanol Guanidines. These suitable natural oils can be functionalized by epoxidation and/or hydroxylation. In some embodiments of the aromatic polyester polyol blend, the hydrophobic material comprises the total weight of the aromatic polyester polyol. About 1% to about 40% Optionally, from about 5% to about 20%. Suitably, the hydrophobic material is a natural oil component. The aromatic acid based polyester polyol reaction product is hydroxylated from an aromatic acid based material (eg, phthalic acid) The reaction of the material and optionally the hydrophobic material is formed. The reaction usually occurs at a temperature of from about 180 ° C to about 22 ° (:, although other temperatures can satisfactorily occur the desired reaction. Commercially available aromatics can be used Examples of family polyester polyols are those sold under the trade names Terate® (available from Invista), Terol® (available from 〇xid) and Stepanpol® (available from Stepan Chemical). 201202504 Based on the total composition The amount of aromatic polyester polyol that can be used can range from about 10% by weight to about 80% by weight, or from about 20% by weight to about 70% by weight, or from about 25% by weight to about 5% by weight. 0% by weight. The low molecular weight diols that can be used typically have a molecular weight of less than about 200, or less than about 175 or less than about 150. Examples of low molecular weight diols that may be used include, but are not limited to, ethylene glycol. Propylene glycol, butylene glycol, pentanediol, a diol, octanediol, diethylene glycol, dipropylene glycol 'dihexylene glycol, trimethylene glycol, butylene glycol, 1,2-cyclohexanediol, or a mixture thereof. Based on the total weight of the composition The amount of low molecular weight diol that can be used can range from about 0.5% to about 10% by weight, or from about 1% to about 7% by weight, from about 1% to about 5% by weight. Agents are known in the industry. In one embodiment of the cyclic phosphonate flame retardant, two P-alkylphosphonic acid diesters are present. One diester contains one (5-ethyl-2-methyl-) 2-epoxy-1,3,2-dioxaphosphorane-5-yl)methyl ester group, and another diester containing two (5-ethyl-2-methyl-2-ring Oxy-1,3,2-dioxaphosphol-5-yl)methyl ester group. In the P-alkylphosphonic acid moiety of the P-alkylphosphonic acid diester, the alkyl group has from 1 to about 6 carbon atoms. Examples of suitable alkyl groups include methyl, ethyl, n-propyl 'isopropyl, n-butyl, sec-butyl, pentyl, hexyl and the like. Preferred alkyl groups of the P-alkylphosphonic acid moiety include a methyl group and an ethyl group (i.e., the P-alkylphosphonic acid moiety is P-methylphosphonic acid or P-ethylphosphonic acid), and a methyl group is more preferred. For a diester containing a (5-ethyl-2-methyl-2-epoxy-1,3,2-dioxaphosphin-5-yl)methyl ester group, the alkyl ester The group has from 1 to about 6 carbon atoms. Suitable alkyl packages -9 - 201202504 include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, pentyl, hexyl and the like. Preferred alkyl groups for alkyl esters include methyl and ethyl, more preferably methyl. A particularly preferred P-alkylphosphonic acid diacetate in the practice of this invention is a methylphosphonic acid (5-ethyl-2-methyl-2-epoxy-1,3,2-dioxaphosphane). 5-yl)methyl ester (CAS No. 41203-8b 0) and p-methylphosphonic acid bis[(5-ethyl-2-methyl-2-epoxy-1,3,2-dioxa) Phosphacyclo-5-yl)methyl]ester (CAS No. 42595-45-9). P-alkylphosphonic acid diester having one (5-ethyl-2-methyl-2-epoxy-1,3,2-dioxaphosphin-5-yl)methyl ester group and a b-alkylphosphonic acid diester having two (5-ethyl-2-methyl-2-epoxy-1,3,2-dioxaphosphorane-5-yl)methyl ester groups The ratio may range from about 2 5:1 to about 1:5, or from about 1 〇: 1 to about 1:1' or from about 5:1 to about 2:1. In the practice of the invention 'P- having a (5-ethyl-2-methyl-2-epoxy-1,3,2-dioxaphosphol-5-yl)methyl ester group Alkylphosphonic acid diester and p having two (5-ethyl-2-methyl-2-epoxy-1,3,2-dioxaphosphol-5-yl)methyl ester groups A particularly preferred ratio of -alkylphosphonic acid diester is from about 3.35 to 3.5 5 : 1 - a commercial example of a cyclic phosphonate flame retardant is Am guar dTM CU, which is P-methylphosphonic acid ( 5-ethyl-2-methyl-2-epoxy-1,3,2-dioxaphosphol-5-yl)methylmethyl ester (~3_5 parts) and P-methylphosphonic acid A mixture of bis[(5-ethyl-2-methyl-2-epoxy-1,3,2-dioxaphosphin-5-yl)methyl]ester (~1 part). The alternative design of the Am guard Cu component is phosphonic acid 'methyl-(5-ethyl-2-methyl-1,3,2-dioxaphosphol-5-yl)methyl Methyl ester 'P-oxide (Cas#41203-81-0) and phosphonic acid, methyl-bis[(5- -10- 201202504 ethyl-2-methyl-1,3,2-dioxaphosphorus Heterocyclohexane-5-yl)methyl ester, 1», 1»,-dioxide (Cas #42595-45-9). The amount of cyclophosphonate flame retardant that can be used can range from about 0.1% to about 1% by weight, or from about 0.25% to about 7.5% by weight, or about 0.5% by weight, based on the total weight of the composition. About 5% by weight. Optionally, the composition may further comprise an antioxidant such as an alkylated diphenylamine or a hindered phenol antioxidant. The alkylated diphenylamine has the general formula: Ra-NH-Rb, wherein 1 and Rb each independently represent a substituted or unsubstituted phenyl group. The substituent on the benzene ring may include, but is not limited to, an alkyl group having 1 to 20 carbon atoms, an alkylaryl group, a hydroxyl group, a carboxyl group, and a nitro group. In one embodiment of the invention, one or two phenyl groups are substituted by an alkyl group. In another embodiment of the invention, both phenyl groups are replaced by a hospital base. Examples of the alkylated diphenylamine which can be used in the present invention include 3-hydroxydiphenylamine, N-phenyl-1,2-phenylenediamine, N-phenyl-1,4-phenylenediamine, and butyl. Diphenylamine, dibutyldiphenylamine, octyldiphenylamine, dioctyldiphenylamine, di-t-octyldiphenylamine decyldiphenylamine, dimethyldiphenylamine, heptyldiphenylamine, diheptyldiyl Aniline, methylstyryldiphenylamine, mixed butyl/octylalkylated diphenylamine, mixed butyl/styryl alkylated diphenylamine, mixed ethyl/mercaptoalkylated diphenylamine A combination of mixed octyl/styryl alkylated diphenylamines, mixed ethyl/methylstyryl alkylated diphenylamines, and those of varying purity commonly used in the petroleum industry. The 201202504 hindered phenol compound preferably includes at least one group represented by the following formula:

Wherein R3 is fluorene, methyl or tert-butyl, and R4 is a substituted or unsubstituted or unsubstituted thioether' and 〜 represents phenylhydrazine and other groups attached. Examples of the sterically hindered oxime are: 2,6-tert-butyl cresol, 2-tert-butylxylene, bis-tert-butyl Iethylbenzene, 2,6-di-tert-butyl. 4·n-butylphenylhydrazine, 2, di-tert-butyl-4,isobutylbenzene, 2,6-dicyclopentyl]-formamidine, W methylcyclohexylbu^^(4), 2,6· . 4 Α dicyclohexyl phenol, 2,6-di-tert-butyl 4-octadecyl-4-methyl phenol, 2,4,6--take u+ 4 cresol, 2,6-di-tert-butyl- 4_methoxymethoxy cresol, 2,6-dimercapto_4卞β μ butyl lysine, 2,5-di-t-pentyl p-benzoquinone, 2,6-phenol, 2 , 5-di-tert-butyl to this one

2, _ thiobis (6-tert-butyl-4-cresol), diphenyl-4-octyl-nonylphenol, 2,2 W-ship), 4,4,-thio-bis (6 -tert-butyl-3 -methyl 2,2,-thiobis (4-octyl)

Cresol) '2,2'-methylenebis(6-tert-phenol), 4,4,-thiobis(6-tert-butyl 2Danji J w its double (6-tert-butyl-4_ Ethylbenzene, 2,2'-butyl-4-methylphenol), 2,2,-methylene hydrazine 1 / from a cyclohexyl phenol], 2,2'-methylene bisylene Bis-[4-methyl-6-(α-carbamazine. 9 2,-methylenebis(6-fluorenyl-4-ylphenol), (4-methyl-6-cyclohexylphenol), 2 '2 ^ ^ •Κ7Τ*ylbenzoquinone), 2,2'_ethylene bis (4,6_a 2,2,-methylene double (4,6-di-unclear game% 7) Bis(6-tert-butyl-4-isobutylphenol), -tert-butylphenol), 2,2,-ethylidene 1 ^ 甘β)-4-mercaptobenzoquinone], 2,2 '-Methylene-2,2,-methylenebis[6-(α-methylindolyl) 隹隹 隹隹 "a / 一^1甘#^4-壬-Phenol-phenol], 4,4' _Methylene double (2,6-bis[6-(α,α-monomethyl)]-4--1 2- 201202504 di-tert-butylphenol), 4,4'-methylene double ( 6-tert-butyl-2-cresol bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-methyl-2-hydroxybenzyl) 4-methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxyphenyl)butane, 1 1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)dialkyldecylbutane, ethylene glycol bis[3,3-bis(3'-tert-butyl- 4'. Butyrate], bis(3-tert-butyl-4-hydroxy-5-methylphenyl)diene, bis[2-(3'-tert-butyl-2'-hydroxy-5'-- Benzyl)-6-tert-butylphenyl]terephthalate, 1,3,5-tris(3,5-di-tert-butyl-4-yl)-2,4,6-trimethyl Benzobenzene, bis(3,5-di-tert-butyl-4-hydroxybenzyl, 3,5-di-tert-butyl-4-hydroxybenzylthioacetic acid isooctyl ester, bis-yl-3-hydroxy- 2,6-Dimethylbenzyl)dithioterephthalate, (3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-three _3_hydroxy-2,6-dimethylbenzyl)isocyanurate, di-octyl-癸g-tert-butyl-4-hydroxybenzylphosphonate, and monoethyl 3, 5-di a calcium salt of tert-butylbenzylphosphonic acid, β-(3,5-di-tert-butyl-4-hydroxyphenyl and β-(5-tert-butyl-4-) having a monohydroxy group or a polyhydroxy group Hydroxyphenyl)propionic acid, for example with methanol, octyl decyl alcohol, 1,6-hexanediol, diol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol Ethyl)isocyano Urate, hydrazine, Ν'-bis(hydroxyethyl) acetonide amines of the acid, such as hydrazine, Ν'-bis(3,5-di-tert-butyl 4-hydroxyindole) cyclohexanediamine ,Ν,Ν'-bis(3,5-di-tert-butyl-4-hydroxyphenyl-propylenediamine/ and N,N'-bis(3,5-di-tert-butyl-4-hydroxybenzene) Base-amines/or mixtures thereof. , 1,1-Butyl-5-yl-2-methyl-3-n-l-hydroxybenzenecyclopentyldiyl-4-methylhydroxybenzyl)sulfide (4-tert-butyl l,3,5-tri ( Heart-tert-butyl S 3,5-diyl-4-hydroxy)propionic acid as 3-methyl neopentyl: tetraol, decylamine and phenyl-propionyl) cyanohydrazide)-13 - 201202504 based The amount of the alkylated diphenylamine or hindered phenol antioxidant that can be used is from 〇% by weight to about 10% by weight 'or from about 0.01% by weight to about 5% by weight, or about 0.1% by weight based on the total weight of the composition. % to about 3% by weight. Another embodiment of the invention is a process for the preparation of a polyurethane foam composition. The method comprises: combining a liquid flame retardant composition of the present invention and a polymerization formulation comprising an isocyanate and a polyol, and at least one surfactant, at least one blowing agent, at least one catalyst, and Optional other additives, such as antistatic agents, antibacterial agents, and dyes; and reacting the mixture to form a flexible polyurethane foam. In order to impart flame retardancy to the polyurethane foam, the liquid flame retardant composition is usually included as a component in the formation of the polyurethane foam. The polyurethane foam is generally formed under ordinary polyurethane foam forming conditions and by a conventional polyurethane foam forming method/process. For more information on the formation of polyurethane foams, see, for example, U.S. Patent Nos. 3,9 5 4,684; 4,209,609; 5,356,943; 5,563,180 and 6,121,338. Additional information on polyurethane foams can be found at Herrington and Hock, Flexible Polyurethane Foams, The Dow Chemical Company, 1 9 9 1,9.2 5 - 9 · 2 7 or R 〇eg 1 er, M · “Slabstock Foams”; in Polyu, rethane Handbook; Oertel, G.,

Ed·; Hanser Munich, 1 9 8 5,1 7 6- 1 7 7 or Woods, G. Flexible

Found in Polyurethane Foams, Chemistry and Technology; Applied Science Publishers, London, 1982, 257-260 |J. The flexible polyurethane foam is usually formed by mixing at least two liquids, isocyanuric acid, and a polyhydric alcohol. The polyol is a polyether or a polyacetate -14-201202504 alcohol, a natural oil based polyol, or a copolymer polyol. The reaction readily occurs at room temperature in the presence of a blowing agent such as water, a volatile hydrocarbon, a halocarbon, or a halogenated hydrocarbon, or a mixture of two or more substances. Catalysts for influencing the reaction include amine catalysts, tin-based catalysts, rhodium-based catalysts or other organometallic catalysts. Surfactants such as substituted anthrone compounds are often used to facilitate nucleation or to maintain core uniformity in the polymerization system. Preferred catalysts include dipropylene glycol containing triethylenediamine (3 3%) and stannous octoate. In the practice of the present invention, in addition to those used in liquid flame retardant compositions, the one or more polyols used in forming the polyurethane foam can be any polyol useful in the preparation of flexible polyurethane foams. When forming a flexible polyurethane foam, the polyol is typically a polyol or polyol mixture having a hydroxyl group content of up to about 150 mg KOH/g, preferably from 0 to about 100 mg KOH/g of a polyol or The polyol mixture, and more preferably from about 10 to about 10 mg KOH/g of a polyol or polyol mixture. Suitable polyols for flexible polyurethane foams include polyether polyols. Preferred polyols for forming flexible polyurethane foams in the practice of the present invention include Voranol® 3010 polyols, polyether polyols having a molecular weight of about 3,000 and a hydroxyl number of about 56 mg KOH/g; Dow Chemical Company , Midland, MI), Pluracol® 1718-polydecyl alcohol (polyether polyol with a molecular weight of approximately 3000 and a hydroxyl number of approximately 58 mg KOH/g, BASF's 'Florham Park, NJ) and Pluracol® 1388-polysterol (molecular weight approx. 3100 polyether triol, BASF, Florham Park, NJ). 201202504 In the practice of the invention, when forming a flexible polyurethane foam, the isocyanate is any isocyanate used in the conventional production of flexible polyurethane foams. Usually, the isocyanate contains at least one isocyanate group, more preferably two isocyanate groups, and it is also possible to have more than two isocyanate groups in the molecule. Preference is given to using diisocyanates. The isocyanate is an aliphatic or aromatic isocyanate. Isocyanates which may be used in the practice of the invention to form flexible polyurethane foams include, but are not limited to, 1,4-cyclobutyl diisocyanate, 1,5-cyclopentyl diisocyanate, 2-methyl-1,5-cyclopentane Diisocyanate, 1,6-cyclohexyl diisocyanate (HMDI), 1,7-cycloheptyl diisocyanate, 1,1 fluorene-cyclodecyl diisocyanate, cyclohexyl diisocyanate, isophorone diisocyanate (IPDI , 2,2,4-trimethylcyclohexyl diisocyanate, 2,4,4-trimethylcyclohexyl diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), phenylene diisocyanate , toluene diisocyanate (TDI), xylene diisocyanate, other alkylated phenyl diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane diisocyanate (MDI, sometimes referred to as methylene diisocyanate), and A mixture of any two or more of the above compounds. Preferred isocyanates for flexible polyurethane foams include toluene diisocyanate and diphenylmethane diisocyanate. Flexible polyurethane foams can be prepared by a single step, quasi- or semi-prepolymer process. Further, the flexible polyurethane foam can be used to form various products such as a template foam, a block foam, and a hydrophilic foam which may be used as a cushioning substance for a furniture and a motor vehicle seat cushion, a seat cushion, a carpet mat surface, and a diaper. And as a packaging bubble. -16- 201202504 A flame retardant amount of a liquid flame retardant composition is used in forming the polyurethane foam of the present invention. The flame retardant dose is the amount of liquid flame retardant composition used to achieve the desired level of flame retardancy. At least for flexible polyurethane foams, typical flame retardant doses are from about 1 php to about 45 php 'preferably from about 3 php to about 35 php, more preferably from about 3 php to about 25 php' where the "php" indicates flame retardant The amount of flame retardant used per 1 part of the polyol of the polyurethane formulation. Suitable foaming agents in the practice of this invention include water, volatile hydrocarbons, halocarbons or halogenated hydrocarbons, or mixtures of two or more, when forming flexible polyurethane foams. Preferred blowing agents for flexible polyurethane foams include water and a combination of dichloromethane, Freon 1 or acetone. The weight ratio of water to the other ingredients in the component is from about 1:2 to about 2:1; water and dichloromethane are preferred combinations. Catalyst systems for forming flexible polyurethane foams include amine catalysts such as dimethylethylamine, triethylenediamine, and bis(dimethylaminoethyl)ether. A preferred catalyst system is a combination or blend of an amine catalyst such as methyl ethylamine, triethylenediamine, and bis(dimethylaminoethyl)ether. The catalyst is usually used in an amount of from about 0.001 to about 2 parts by weight per 100 parts by weight of the polyol or polyol mixture. When forming a flexible polyurethane foam, one or more optional additives may be included, including optional surfactants, antioxidants, diluents, chain extenders or crosslinking agents, synergists (preferably melamine) ), stabilizers, colorants, tanning agents, antistatic agents, and cell openers. -17- 201202504 Cell Expander, a specific type of surface polyalkylene oxide. In the practice of the present invention, the cell pore expander comprises polyethylene glycol monoallyl ether methyl ether, polyethylene glycol monoallyl acetate, polyethylene glycol glyceryl ether, polyethylene-poly Propylene glycol olefin-polypropylene glycol monoallyl monomethyl diether c ethylene glycol allyl acetate. Preferred cell expansion fee 8239, (Evonik Industries AG, Esse:

Tegostab® B 8 2 29 (Evonik Industries, Es Surfactants can also be used in the form of polyurethane foams if required. They serve as a surfactant for the compatibility of the fractions and control the structure of the pores. Suitable as emulsifiers, such as castor oil a sodium salt or a lipid salt, for example, an ammonium salt of diethyl oleate and a diglycolate, for example, dodecylbenzenedisulfonic acid and ricin ammonium; a foam stabilizer, for example, a oxime olefin machine The oxane, ethoxyalkyl phenol, ethoxy group is based on 100 parts by weight of the polyol blend, usually in an amount of from 0.01 to 5 parts by weight. The following examples are intended to describe the invention. The disclosure and the details of the appended claims are limited. The active agent is typically a suitable polyalkylene oxide, polyethylene glycol allyl glycol monomethyl ether, monoallyl ether, polyethyl hydrazine And polyethylene-polypropylene fl! including Tegostab® B n, Germany) and sen, Germany) ° Examples of surfactants that are flexible or semi-flexible in improving the formulation. Fatty acid: Ammonium fatty acid ammonium salt of fatty acid Sulfur oil Copolymers and alkali metal or other I have fatty alcohols and castor oil. For surface-active substances, it should be understood that this is required by the following Examples -18-201202504 Example Example 1 and Comparative Example 2-5 Bubble Formulations' Example 1 and Comparative Example 2-5 in a foam formulation In the above, the following ingredients were additionally added to the formulation to prepare a lumpy polyurethane foam: 100 parts of polyether polyol (1^:(^1乂0?-3001 from 1<:(^6&?〇1丫) 〇1), 3.5 parts water, 1 part fluorenone stabilizer (Tegostab® B8239 from TH. Goldschmidt AG)' 0.16 parts of triethylenediamine catalyst (Dabco® 33LV from Air Products, GMBH), 0.28 parts of tin octoate (Dabxco) ® T-9 from Air Products) ' 4 parts of dichloromethane as blowing agent (from Reagent & HV Chemical), 105 parts of toluene diisocyanate (TDI-80 from BASF) and effective amount (from 3.5 to 10 parts) The liquid flame retardant composition of Example 1 and Comparative Examples 2-5 below (all concentrations are php-parts of ingredients/1 part by weight of polyether polyol). The polyol, surfactant, flame retardant The formulation, water, and triethylenediamine catalyst are in a half-gallon container as follows The weights were weighed as indicated in Table 1. The mixture was premixed at 2000 rpm for 60 seconds in a cyclotron until the mixture was homogeneous and there was no visible phase separation. Once the mixing was completed, the rpm dropped to 50,000 and the timer started. Timing and mixing for 4 sec, during which TDI (isocyanate) was added. At 50 sec, stannous octoate was added and the duration of the mixture was recorded (reaction time). The mixture was poured into 1 4 x 1 4 x 1 4 inch. The carton is recorded and the time of the start is recorded. The time starts from the mixing to the observation point. For this system, the typical reactivity is that the whitening time is 35 seconds, the gel time is 1 minute and 5 seconds, and the tack free time is 1 minute and 35 seconds. And the free rise time is 2 minutes and 5 seconds. 201202504 The bulk foam material uses the Federal Motor Vehicle Safety Standard (FM VS S) Flame Retardant Test 3 02. The test has 4 possible levels, which are self-extinguishing (" SE")> No Burning Rate ("NBR") >Qualified> Failed. The bond strength of the resulting laminate was tested according to the following procedure. First, a foam was prepared from the desired formulation. After treatment (in the room) temperature The foam was cut into 40x40x3 0mm samples. Each sample required 5 samples. The density of the fabric was about 126±22g/m2. The fabric sheets were cut into 60x 60mm slices. Flame adjustment of the burner. It is 5 5 mm high and propane is used as a combustible gas. The sample was placed over the burner and the bottom edge of the sample (40*40 mm side) was held approximately 40 mm above the burner. The sample was exposed to a flame for 3 seconds and the surface of the foam partially melted. The fabric was immediately pressed against the foam with a steel plate and held for 3 seconds. After the flame was bonded, the samples were aged at room temperature for 24 hours and tested for bonding strength by a universal test machine. The test procedure for testing the bond strength is to first calibrate the universal test machine with a 1 KN load. Pneumatic handles are used to test and adjust the load. The foam is attached to the lower portion of the handle and the cotton fabric is attached to the upper portion of the handle. A load of 1 N was preloaded at a pulling speed of 5 mm/min, after which the load was automatically tested and the test was continued at a speed of 5 Omm/mi η until the foam was completely peeled off from the fabric. The bonding strength was calculated by bonding strength = maximum load (Ν) / foam width (40 mm). The foam sample step without FR is slightly different because the foam still burns after exposure to an open flame. In these samples, the foam was exposed to the flame for only 2 seconds and the fabric was immediately pressed against the foam. The f Μ V S S flame retardant and bond strength test results of the examples are shown in Table 1 below. -20- 201202504 Table 1 FMVSS Flame Retardant and Bond Strength Test Results Ingredient Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Aromatic Polyester Polyol 1 3.5 3.5 — — 3.5 Liquid FR 2 6 — 6 6 — Cyclophosphonate 3 0.1 — 0.1 — 0.1 Low molecular weight diol (DEG) 0.3 — 0.3 — 0.3 Diphenylamine antioxidant 4 0.1 — 0.1 — 0.1 FMVSS 302 NBR Unqualified NBR Qualified failure strength kN/M 0.58 0.057 0.433 0.295 0.117 htepanpol® PS 1 7 5 2 Aromatic Polyester Polyol (Stepan Chemical) 2Antiblaze® 195 Tris(1,3-Dichloroisopropyl) Phosphate (Albemarle)

3Amgard CU 4Irganox® 5 1 5 7 from C i b a® (B A S F subsidiary). Example 6 and Comparative Example 7 - 1 0 Foam Formulation and Charring Resistance The foam formulations of Example 1 and Comparative Examples 2 through 5 were repeated in the foam formulations of Example 6 and Comparative Examples 7 to 10, The difference was that the foam formulation contained 6-5 parts water, 110 parts TDI, and a variable number (from 1 to 22.5 parts) of the liquid flame retardant compositions of Example 1 and Comparative Examples 2 to 5. The 14X14X 14 inch foam prepared according to the above procedure was aged in an oven at 25 ° C for 24 hours. After aging, the foam was cut into a rectangular foam of 70 mm x 70 mm x 50 mm along the center of the larger foam for the scorch test. The yellow index (YI) was tested according to ASTM D 1 925. The results are shown in Table 2 below. -21 - 201202504 Table 2 - Scorch Test - Different Formulations 1 Dop Foam Passing Through the Center of Yellow Index Foam Passing through the Center of Yellow Index Components 1 2 3 4 5 6 7 8 9 Example 1 -1.73 · -1.49 -1.27 -1.13 -1.09 -1.03 -1.15 -1.62 -1.74 Comparative Example 2 -1.39 •0.87 -0.41 -0.15 -0.04 -0.05 -0.13 -0.36 -0.76 Comparative Example 3 -1.70 -1.57 -.084 0.30 1.22 1.19 0.15 -0.89^ -1.52 Comparative Example 4 -1.72 -1.63 -1.36 -0.90 -0.73 -0.71 -0.98 -1.37 -1.84 Comparative Example 5 -1.58 -1.22 -0.72 -0.17 1.12 1.25 0.51 -0.64 -1.36 Comparative Example 12 (see below) - 1.36 -0.81 -0.49 -0.12 -0.21 -0.32 -0.54 -0.87 -1.09 Example 1 1 and Comparative Example 1 2 Foam Formulation In the foaming formulation Example 1 1 and Comparative Example 1 2, the following ingredients were used for preparation. Liquid flame retardant composition. Table 3 Example 1 1 and Comparative Example 1 2 Liquid f 豊 Flame retardant Composition Examples Aromatic Polyester Polyol 1 Liquid FR2 Cyclophosphonate 3 DEG Diphenylamine Antioxidant 4 Example 11 35 wt% 6〇 Weight% 1% by weight 3% by weight 1% by weight Comparative Example 12 35% by weight 62% by weight - 5% by weight 1% by weight

Stepanpol® PS1752 Aromatic Polyester Polyol (Stepan

Chemical Company) 2Antiblaze® 195 Tris(1,3-Dichloroisopropyl) Phosphate (Albemarl)

3Amgard CU 4Irganox® 5157 from Ciba® (a subsidiary of BASF). The liquid flame retardant composition of Example 11 and Comparative Example 1 was mixed with other polyurethane foam components in the same manner as in the above Example 1 to prepare a polyurethane foam according to the following Table 4. •22- 201202504

Table 4 Example 1 1 and Comparative Example 1 2 Foam Formulation and Result Formulation Part/100 Part of Polyacid 1 Polyol (GP-3001) Example 11 10-15 -- Comparative Example 12 — 10 -- 15 GP -3001 100 100 100 100 Water 4 4 9 9 Niax A1 — 0.08 -- 0.08 T9 0.2 0.2 0.2 0.2 L5770 1.1 1.1 1.5 1.5 TDI index 105 105 110 110 Foam density Kg/m3 27.25 26.73 18.04 17.34 Bonding strength N/mm 0.716 0.378 0.418 0.397 FMVSS 302 SE SE SE NBR results show that 'Example 1 of the present invention shows better bond strength and/or flame retardant performance than Comparative Example 1-2. The present specification and claims are directed to anywhere. Components of chemical names and chemical formulas, whether referred to as singular or plural, are identified by their prior contact with other substances referred to by chemical names or chemical types (eg, other ingredients, solvents, or the like). What chemical changes, transformations, and/or reactions are not important (if any), such changes, transformations, and/or reactions that occur in the resulting mixture or solution are within the conditions disclosed herein. Natural results obtained by mixing specific components. Thus, these components are identified as being required to perform the desired operation once or in order to form the components associated with the desired formulation. And, in accordance with the disclosure of the present invention, despite the claims The substances, components and/or ingredients involved are generally present ("C 〇mprises", "is", etc.), and the substances, components and/or ingredients involved are first and for one or Many other substances, components and/or ingredients are already present before contact, mixing or mixing. The fact is that a substance, group -23-201202504 and/or ingredients may be lost by chemical reactions or conversions during contact, mixing or mixing. Having its own characteristics, but if implemented in accordance with the teachings of the present invention, and in accordance with the general technical knowledge of those skilled in the art, such variations do not relate to the substance of the present invention. The present invention is described and claimed herein. The limitations are within the scope of the specific embodiments and embodiments disclosed herein, as these examples and example embodiments are applicable to the explanation of the present invention. The invention is not limited by the scope of the invention. It is also intended to fall within the scope of the appended claims. [Simplified illustration] None. [Main component symbol description] No 0 -24-

Claims (1)

201202504 VII. Patent application scope: 1. A liquid flame retardant composition comprising: (a) a liquid flame retardant; (b) an aromatic polyester polyol; (c) a low molecular weight glycol; (d) a ring a phosphonate flame retardant; and (e) an optional alkylated diphenylamine or hindered phenol antioxidant. 2. The composition of claim 1, wherein the liquid flame retardant is a phosphorus flame retardant or a halogenated phosphorus flame retardant. 3. The composition of claim 1, wherein the liquid flame retardant is bis(2-chloroethyl)2-chloroethylphosphonate, tris(monochloropropyl)phosphate, hydrazine ( 1,3-Dichloroisopropyl)phosphate, 2,2-bis(chloromethyl')trimethylene, bis(bis(2-chloroethyl)phosphate), bisphenol A bis-(diphenyl Phosphate), isopropylated phenol phosphate (IP P), dimethylmethylphosphonate, diethylethylphosphonate, or mixtures thereof. 4. The composition of claim 1, wherein the aromatic polyester polyol contains an aromatic component based on a phthalic acid or a phthalic acid derivative. 5. The composition of claim 1, wherein the aromatic polyester polyol contains a hydroxylated component, wherein the hydroxylated component is an aliphatic diol of the formula ΗΟ-Ι^-ΟΗ, Wherein R1 is a divalent group selected from the group consisting of: -25- 201202504 (a) an alkylene group having 2 to 18 carbon atoms and (b) a group of the formula (2): _(R2〇 n-R2-, wherein R2 is an alkylene group of a carbon atom, and η is an integer from 1 to 3, and (c) a mixture thereof. 6. The composition of claim 5, wherein the hydroxyethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, trimethylene glycol, 1,2-cyclohexanediol, through the epoxy The condensation of the mixture of alkane and propylene oxide contains 2 to 4 alkylene sulfinyl) polyols. 7. The composition of claim 1, wherein the low-alcohol is ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, diethylene glycol, dipropylene glycol, dihexanediol , trimethylene glycol, 1,2-cyclohexanediol, or a mixture thereof. 8. The composition of claim 1, wherein the two acid diesters are hydrazine-methylphosphonic acid diesters. 9. The composition of claim 1, wherein the cyclic phosphine is Ρ-alkylphosphonic acid (5-ethyl-2-methyl-2-epoxy-1,3,2-heterocycle) Hexane_5_yl)methyl ester (Cas#4l2〇3-81-0), and Ρ-bis[(5-ethyl-2-methyl-2-epoxy-1,3,2-dioxo) Heterophosphoryl-3-yl)methyl]ester (Cas# 42595-45-9). The composition of claim 9, wherein the cycling agent comprises about 60% by weight of P-alkylphosphonic acid (5-ethyl-) as a total weight of the monomer and the dimer. 2-methyl-2-epoxy-1,3 contains 2 to 3 components which are I-based diols, alkanes or their β-poly(oxyl diols, octyl diols, hydrazine-alkylphosphonic acids) Ester flame retardant dioxaphosphoryl-alkylphosphonic acid cyclohexane-5-phosphonate hinders t% to about 90,2-dioxa-26- 201202504 phospholan-5-yl) methyl ester (monomer), and from about 5% to about 5% by weight of the ?-alkylphosphonic acid bis[(5-ethyl-2-methyl-2-epoxy-1,3,2-heterophosphorus) Alkyl-5-methyl]ester (dimer). The composition of claim 1, wherein the antioxidant is present. 1 2 · If the scope of the patent application is No. 1-11 The composition of any of the items wherein the amount of the liquid flame retardant may be from about 1% by weight to about 90% by weight; the amount of the group of polyester polyols may be from about 1% by weight to about 80% by weight The amount of the low molecular weight diol may range from about 0.5% by weight to about 10% by weight of the cyclophosphonate block. The amount of the agent may range from about 0.1% by weight to about 10% by weight, and the amount of the optional hindered phenolic antioxidant may range from 0% by weight to 3% by weight. A liquid flame retardant composition is required to be contacted with: (i) an isocyanate or a polyisocyanate; (ii) a polyol; (iii) a blowing agent; and (iv) a catalyst; and reacting the mixture to form Polyurethane Foam I4. A polyurethane foam composition comprising: (i) a liquid flame retardant composition as claimed in claim 1; (Π) isocyanate or polyisocyanate; (iii) polyol; 40 weight dioxin The phenol described in the aroma of about -27-201202504 (iv) a blowing agent; and (v) a catalyst. 1 5 - a product comprising a polyurethane foam as in claim 14 and a textile. 16. The article of claim 15 wherein the foam is attached to the textile by flame bonding.