Reactive flame retardant for flexible polyurethane foam

Abstract

The present invention provides reactive polyfunctional dialkylphosphinate compounds that function as highly efficient reactive flame retardants in flexible polyurethane foams. The present invention further provides flame-retardant polyurethane compositions containing the polyfunctional dialkylphosphinate compounds, as well as uses containing the same.

Description

[Technical Field]

[0001] This application claims the interests of U.S. Provisional Patent Application No. 63 / 037,180, filed on 10 July 2020, the entire contents of which are incorporated herein by reference.

[0002] This disclosure provides for the use of reactive dialkylphosphorus-containing compounds, i.e., hydroxyl-functionalized esters of dialkylphosphinic acids that, when reacted with polyols and isocyanates, act as highly efficient reactive flame retardants in flexible polyurethane foams. The present invention further provides flame-retardant flexible polyurethane foam having the hydroxyl-functionalized dialkylphosphinate reacted and incorporated into the polymer matrix of the flexible polyurethane foam. The terms “fire retardants” and “flame retardants” are used interchangeably herein. [Background technology]

[0003] Brominated or phosphorus-based flame retardants are known to be highly effective and are often the only option for reducing the fire risk of synthetic materials such as flexible polyurethane foam. However, public and government scrutiny of chemicals, particularly flame retardants, has increased over the years. The goal is to develop new products that are more sustainable, reactive, and free of polymers and / or halogens. If the flame retardant reacts with the polymer matrix and does not leach, scrutiny will decrease significantly.

[0004] Therefore, there is a need for reactive phosphorus-containing flame retardants for flexible polyurethanes that have characteristics such as high phosphorus content, a transparent, bright color, and good compatibility with polyether polyols and polyester polyols used in the polyurethane industry.

[0005] Monofunctional dialkyl phosphinates have been used in foams, but their use results in foam products with inferior physical properties, such as compressive strain characteristics. Furthermore, monofunctional dialkyl phosphinates often need to be blended with other phosphate esters for effective use in polyurethane foams. In addition, some conventionally prepared monofunctional dialkyl phosphinates require inefficient, complex, and multi-step processes. [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] The present invention provides a reactive dialkylphosphorus-containing polyhydroxyl-functional aromatic compound that has highly satisfactory flame retardant properties and good compatibility with the polyol component of a flexible polyurethane foam forming system. When used in polyurethane foam, the polyfunctional dialkylphosphinate compounds described herein have physical properties similar to those of polyurethane foam without flame retardants. Furthermore, the polyfunctional dialkylphosphinate compounds described herein can be prepared in an efficient one-step reaction. Finally, the polyfunctional dialkylphosphinate compounds described herein impart excellent flame retardancy similar to that of conventionally used monofunctional dialkylphosphinate compounds and can be produced in a reaction mixture simultaneously with the monofunctional dialkylphosphinate, eliminating the need to further blend such monofunctional components for the purpose of reducing viscosity. [Means for solving the problem]

[0007] In this specification, the term "polyfunctional" as used in the expression "polyfunctional dialkylphosphinate compound" should be understood to mean that each molecule contains two or more hydroxyl groups.

[0008] As used herein, the term "flexible polyurethane foam-forming system" is understood to include the polyols, isocyanates, and polyfunctional dialkylphosphinate compounds described herein.

[0009] The terms "polyfunctional dialkylphosphinate compound" and "polyfunctional aromatic dialkylphosphinate compound" are interchangeable herein.

[0010] Monohydroxyl-functionalized dialkylphosphinate compounds are fully reactive via their hydroxyl functional groups. Surprisingly, the polyfunctionalized dialkylphosphinate compounds described herein have been found to react, for example, with isocyanate components in flexible polyurethane foam-forming systems, without damaging the elastic properties of the flexible polyurethane foam, and to be incorporated into the polymer structure of the flexible polyurethane foam. This means that the flame retardants of the present invention are integrated into the flexible foam substrate, and as a result, they are not released into the environment, are less likely to penetrate the cell membranes of biological tissues, and therefore do not pose a health risk. The present invention further provides the above-mentioned flexible polyurethane foam-forming systems, including but not limited to the polyfunctionalized dialkylphosphinate compounds described herein.

[0011] As used herein, the term “foam” refers to flexible polyurethane foam. Any flexible polyurethane foam described herein or claimed, comprising a reacted polyfunctional dialkylphosphinate compound, is understood to contain the polyfunctional dialkylphosphinate compound as a reactive material, i.e., the polyfunctional dialkylphosphinate compound is reacted in the structure of the flexible polyurethane material, in which case the polyfunctional dialkylphosphinate compound may not be present, may not be present in the same structural formula as described herein, but may be present in the flexible polyurethane material as a reaction product of a diol and / or polyol, an isocyanate, and a polyfunctional dialkylphosphinate compound of the structural formula described herein.

[0012] As used herein, the term “polyol” is understood to mean a diol and / or polyol.

[0013] The present invention provides a polyfunctional dialkylphosphinate compound of general formula (I). [ka] In the formula, each R 1 and R 2 These are independently selected from alkyl groups containing 1 to 4 carbon atoms, preferably methyl or ethyl, most preferably both being ethyl. R is a divalent linear or branched alkyl group containing up to approximately 4 carbon atoms, a divalent aralkyl group containing 7 to 13 carbon atoms, or a bond, preferably a divalent linear or branched alkyl group containing 1 to approximately 3 carbon atoms, more preferably a divalent methylene group or a divalent isopropyl group. X and Y are each independently a divalent aryl group containing 6 to 12 carbon atoms, preferably 6 to 8 carbon atoms, more preferably a divalent phenyl group. The subscripts a and b are 0 or 1, respectively. The subscript c is an integer from 1 to 5, and The subscript 'd' is an integer between 1 and 26, preferably between 1 and 10, most preferably between 1 and 3. however, a+b=1 When a=1, b is 0, and X is an aryl group as defined, except that one of the hydrogen atoms bonded to the aryl group is not part of the group enclosed in the subscript c, where the subscript c is an integer from 1 to 5, and the subscript d is 1, and When b=1, a is 0, c is 1, and d is an integer from 1 to 26, preferably from 1 to 10, most preferably from 1 to 3.

[0014] This specification also provides a process for the preparation of the polyfunctional dialkyl phosphinate compounds described herein, which includes the step of reacting a dialkyl phosphinic acid with an aromatic epoxide.

[0015] Furthermore, a flame-retardant polyurethane foam is provided herein, which comprises a reaction product of a polyol, an isocyanate, and a flame-retardant effective amount of a polyfunctional dialkyl phosphinate compound of general formula (I).

[0016] All of the above and other features and advantages of the present invention will be better understood from the following illustrative and non-limiting detailed description of its preferred embodiments.

Mode for Carrying Out the Invention

[0017] In one embodiment, the polyfunctional dialkyl phosphinate compound of formula (I) can be of the more specific formula (II) and / or (III), where formula (II) is

Chemical formula

Chemical formula

[0018] Specific examples of the above formulas (II) and (III) may include the following formulas (A) and (B). [ka]

[0019] Novel compounds of formulas (I), (II), and (III), or (A) and (B), can be prepared by the reaction of a monohydroxyl-functional dialkylphosphinic acid of formula (IV) with an aromatic epoxide compound, where formula (IV) is [ka] And in the formula, R 1 and R 2 It is as defined.

[0020] The dialkylphosphinic acid (IV) used as a starting material in the process of the present invention is largely well known in the art. Compounds of formula (IV) can be obtained, for example, by the reaction of sodium hypophosphite with ethylene, followed by acidification, or alternatively by the reaction of hypophosphorous acid with ethylene, or less preferably by the hydrolysis of the corresponding dialkylphosphinic acid halide.

[0021] The aromatic epoxide compound is preferably an epoxy-terminated aromatic compound. The aromatic portion of the aromatic epoxide compound is as defined above for X and Y, and preferably the aromatic portion may include the XRY portion of the general formula (I) described above. More preferably, the aromatic portion may be a derivative of a bisphenol compound, such as a derivative of bisphenol A, bisphenol AP, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, 2,2'-biphenol, 4,4'-biphenol, etc. The expression "derivative of a bisphenol compound" will be understood by those skilled in the art as the aromatic portion remaining after removing two hydrogen atoms from the hydroxyl group of a bisphenol compound, such that the oxygen atom of the bisphenol compound is bonded to the other portion of the aromatic epoxide compound (e.g., the epoxy group and / or the ring-opening epoxide portion in the internal portion of the aromatic epoxide compound). Preferably, the derivative of the bisphenol compound is a derivative of bisphenol-A or a derivative of bisphenol-F.

[0022] Specific aromatic epoxides that may be used in the process for preparing compounds of formula (I), more specifically formulas (II) and (III), or formula (A) or formula (B) of the present invention include, for example, [ka] The group is selected from, but is not limited to, combinations thereof. In the formula, R is a divalent linear or branched alkyl group containing up to about 4 carbon atoms, a divalent aralkyl group containing 7 to 13 carbon atoms, or a bond, preferably a divalent linear or branched alkyl group containing 1 to about 3 carbon atoms, more preferably a divalent methylene group or a divalent isopropyl group. X and Y are each independently divalent aryl groups containing 6 to 12 carbon atoms. The subscript c is an integer between 1 and 5, and the subscript e is an integer between 0 and 25, preferably between 1 and 10, more preferably between 1 and 3.

[0023] In a preferred embodiment of the present invention, the reaction between monohydroxyl-functional dialkylphosphinic acid (IV) and an aromatic epoxy compound is carried out in a medium of excess monohydroxyl-functional dialkylphosphinic acid (IV), where the remaining monohydroxyl-functional dialkylphosphinic acid (IV) is consumed by reaction with an epoxy compound such as propylene oxide (other epoxy compounds such as ethylene oxide and epichlorohydrin are also possible).

[0024] The use of propylene oxide in this process should be in excess of the remaining monohydroxyl-functionalized dialkylphosphinic acid (IV), preferably in a molar excess of about 1 to about 200%.

[0025] Based on the process for producing these substances and the fact that the reaction must be completed by the final addition of propylene oxide (PO), it is possible to synthesize the polyfunctional dialkylphosphinate compounds of the present invention, which contain a calculated amount of monofunctional dialkylphosphinate, by using an excess of diethylphosphinic acid relative to the polyfunctional epoxy resin used.

[0026] The reaction of residual monohydroxyl-functional dialkylphosphinate(IV) with an excess epoxy compound (such as propylene oxide) produces a monofunctional dialkylphosphinate as described in U.S. Patent No. 10,208,187, the entirety of which is incorporated herein by reference. The amount of monofunctional dialkylphosphinate that can be produced can be determined by setting the molar ratio of excess monohydroxyl-functional dialkylphosphinate(IV) to aromatic epoxy compound(s) to produce a desired weight percent of monofunctional dialkylphosphinate in situ by reacting with other epoxy compounds such as propylene oxide.

[0027] The amount of monofunctional dialkylphosphinate that can be produced in situ as described above and / or added to the reaction product mixture of the present invention is about 5% to about 45% by weight, preferably about 10% to about 40% by weight, and most preferably about 15% to about 35% by weight, based on the total weight of the monofunctional dialkylphosphinate and polyfunctional dialkylphosphinate compounds of the present invention.

[0028] The viscosity of the reaction mixture (blend) of the polyfunctional dialkylphosphinate compound and the monofunctional dialkylphosphinate of the present invention is preferably about 500 cps to about 3,000 cps, more preferably about 1,000 cps to about 2,500 cps.

[0029] The amount of monohydroxyl-functionalized dialkylphosphinic acid (IV) used in the reaction with aromatic epoxy compounds is either molar equivalent, or, if a larger amount of monofunctional content is desired, a molar excess of monohydroxyl-functionalized dialkylphosphinic acid, e.g., 5-100% molar excess.

[0030] The temperature range for the reaction of monohydroxyl-functionalized dialkylphosphinic acid (IV) with aromatic epoxy compounds is about 50°C to about 120°C, preferably about 70°C to about 90°C. This temperature range can be used for subsequent reactions of epoxy compounds such as propylene oxide.

[0031] The polyfunctional dialkylphosphinate compounds of the present invention have a phosphorus content of about 8 to 15% by weight and a hydroxyl value of about 150 to 300 mg KOH / g, depending on the dialkylphosphinic acid and aromatic epoxy compound used in the reaction.

[0032] To prepare a target polyfunctional dialkylphosphinate compound having the highest possible phosphorus content, it is preferable to react the monohydroxydialkylphosphinic acid (IV) having the highest phosphorus content with the aromatic epoxy compound described herein.

[0033] The reaction is carried out at a temperature between 40 and 120°C, preferably between 70 and 90°C. Below 40°C, the reaction becomes unacceptably slow. On the other hand, temperatures above 120°C are undesirable because they may produce undesirable decomposition products.

[0034] The polyfunctional dialkylphosphinate compounds of the present invention have a high phosphorus content, good hydrolytic properties and thermal stability, and exhibit good compatibility with diol and / or polyol components in flexible polyurethane foam forming systems, making them useful as highly efficient reactive flame retardants in flexible polyurethane foams.

[0035] The compounds of the present invention are useful as reactive flame retardants. These flame retardants can be used as is or as mixtures with halogenated or non-halogenated products. For flexible polyurethane foams, it is preferable to use the halogen-free hydroxyl-functionalized dialkyl phosphinate of the present invention either as a pure product or in combination with other non-halogenated products.

[0036] The present invention further provides a flame-retardant flexible polyurethane comprising reactive residues of the polyfunctional dialkylphosphinate after reacting in a flexible polyurethane foam-forming system to form a flexible polyurethane foam. The polyfunctional dialkylphosphinate compounds described herein may be used alone or in combination with each other, and / or in combination with other flame retardants, including halogen-containing and phosphorus-containing flame retardants, in a flexible polyurethane foam-forming system.

[0037] In one non-limiting embodiment, the polyfunctional dialkylphosphinate may be combined with a monohydroxyl dialkylphosphinate (e.g., an isomer mixture described herein), where the alkyl portion may be derived from a 1-4 carbon atom alkyl group to form a composition, and may be used to produce the polyurethane foam described herein. The amount of the polyfunctional dialkylphosphinate may be 1-40% by weight, preferably 1-30% by weight, based on the total weight of the polyfunctional dialkylphosphinate and the polyfunctional dialkylphosphinate used.

[0038] The compounds of the present invention are highly efficient reactive flame retardants when incorporated into flexible polyurethane foams. It should be noted that the compounds of the present invention are useful over a wide range of isocyanate indices (abbreviated herein as MDI or TDI). This index refers to the ratio of the isocyanate actually used in the formulation to the theoretical stoichiometric amount of isocyanate required, and is expressed as a percentage.

[0039] The flexible polyurethane foam of the present invention contains a typical flame-retardant effective amount of the composition of the present invention. Typically, the composition of the present invention is applied in such an amount that the total phosphorus concentration in the polymer (i.e., flexible polyurethane foam) is 0.01 to 10% by weight based on the total weight of the polymer. Preferably, the total phosphorus concentration in the polymer is 0.1 to 5% by weight, more preferably 0.1 to 3% by weight, based on the total weight of the flexible polyurethane polymer. Most preferably, the amount of the polyfunctional dialkylphosphinate compound of the present invention used is at least sufficient to satisfy the current requirements of the flammability test standard MVSS 302.

[0040] By appropriately selecting the components and conditions, flexible polyurethane foams can be manufactured whose properties can vary in terms of the degree of flexibility. Therefore, flexible foams are generally manufactured from polymer diols or triols having a hydroxyl value of 20 to 80, using water as the primary blowing agent.

[0041] The flexible polyurethane foam of the present invention may include appropriate selections of auxiliary agents, such as catalysts, surfactants, and foam stabilizers.

[0042] The flexible polyurethane foams used herein are prepared using diols and / or polyols having a molecular weight of 3000 to about 6000 as described herein (e.g., polyethertriols prepared by adding propylene oxide to glycerol). The flexible polyurethane foams used herein are characterized by having a core impact elasticity of up to 30% and a glass transition temperature of -80 to -60°C. Herein, the flexible polyurethane foam preferably has a hard segment content of up to 40% by mass. Conventional flexible polyurethane foams have a bulk foam density of 2.5 pounds per cubic foot or less and a foam hardness or IFD (measured according to ASTM 3574-Test B1) of 10 to 90 pounds per 50 square inches.

[0043] The present invention provides a method for producing flexible polyurethane foam, which may include combining a diol and / or polyol component and / or isocyanate component or catalyst with one or more flame-retardant materials of formulas (I) to (III) or (A) or (B) described herein, which may be weighed and pumped into a common mixing vessel, and the resulting mixture may then be easily transferred to a polymerization portion for use in molds, slab stock operations, etc.

[0044] The reactive flame retardant of the present invention may be mixed with a diol and / or polyol reactant before being combined with an isocyanate reactant. Mixing the reactive flame retardant material with an isocyanate before mixing with a diol and / or polyol reactant is also within the scope of the present invention. However, if the isocyanate and the aforementioned flame retardant are mixed and left at room temperature for a certain period of time, a reaction may occur. As used in the claims and specification herein, “reaction product” may, in one embodiment, include reacting the contents of a flexible polyurethane foam-forming system by any one of the methods described herein, and may further include reacting the reactive flame retardant via prepolymer technology, for example, by reacting an excess isocyanate with a polyol to form an isocyanate-terminated prepolymer, and then further reacting the prepolymer with the reactive flame retardant herein.

[0045] The flame retardant materials of formulas (I) to (III) or (A) or (B) described herein may be described as isocyanate-reactive (NCO-reactive) materials, that is, they are reactive with isocyanates via hydroxyl groups.

[0046] The diols and / or polyols used in the manufacture of flexible polyurethane foams described herein may include any organic polyols, including diols and polyols, and polyether polyols, polyester polyols, and polyesteramide polyols having hydrogen atoms that are reactive with isocyanates may be used. Generally, these materials have a molecular weight of about 62 to about 5,000, have 2 to about 10 or more hydroxyl groups per molecule, and a hydroxyl group content of about 0.5 to about 25% by weight. They generally have a hydroxyl value of about 50 to 500, or even 700.

[0047] In polyester-polyol type reactants, the acid value should be less than 10, and is usually as close to 0 as possible. These materials are conveniently referred to as “polyol” reactants. Useful active hydrogen-containing diols and / or polyols include a large family of adducts that result when ethylene oxide, propylene oxide, 1,2-butylene oxide and 2,3-butylene oxide, or other alkylene oxides are added to active hydrogen compounds such as diols, glycols, and polyols (presented by ethylene glycol, propylene glycol, glycerin, methyl glucoside, sucrose, sorbitol, hexanetriol, trimethylolpropane, pentaerythritol, and various alkylamines and alkylenediamines, as well as polyalkylene polyamines, etc.). Various amounts of these alkylene oxides may be added to the base diol, polyol, or amine molecule depending on the intended use of the polyurethane.

[0048] For example, diols and / or polyols for use in the preparation of flexible foams can be well represented by glycerin to which sufficient propylene oxide has been added to give a final hydroxyl content of about 1.7%. Such a material has a molecular weight of about 3000 and a glycerin-to-propylene oxide molar ratio of 50 parts propylene oxide to about 1 part glycerin.

[0049] This technique of controlling flexibility by selecting diol and / or polyol molecules and the amount of alkylene oxide subsequently added is well known to those skilled in the art.

[0050] In addition to glycols and the like that can function as a base polyol molecule for the addition of alkylene oxide and thus produce a “polyol” molecule for reaction with isocyanate, starting molecules containing primary and / or secondary amine groups having hydrogen reactive with alkylene oxide can be used. Here again, the amount of alkylene oxide added depends on the intended use of the final polyurethane product. In the flexible polyurethane product of the present invention, alkylene oxide is used to produce polyols having a lower hydroxyl content (e.g., about 0.1 to about 5% or 10%).

[0051] Typical amines that can function as active hydrogen-containing molecules for reaction with epoxides are those having 1 to about 6 or more amino nitrogen atoms, examples of which include ethylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetrapropylenepentamine, and other linear saturated aliphatic alkyleneamines, the important requirement being that they have at least 2, more preferably 3 to 8 or 10, active hydrogen moieties to which alkylene oxides can be added.

[0052] It is also well known that hydroxyl-containing molecules prepared by esterification reactions from polyfunctional acids or anhydrides and polyfunctional alcohols are used as active hydrogen compounds when preparing polyurethane systems. These compounds are often called polyester polyols. Typical acids used in the production of these polyester polyols are maleic acid, phthalic acid, succinic acid, fumaric acid, tetrahydrophthalic acid, chlorenediic acid, and tetrachlorophthalic acid. Typical diols and / or polyols include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, and dipropylene glycol, polyethylene glycol, and polypropylene glycol, as well as glycerin, trimethylolpropane, hexanetriol, pentaerythritol, and sorbitol. If available, the above acids may be used in the form of anhydrides if desired.

[0053] In preparing polyester-polyols, various polyhydric acids, anhydrides, or mixtures thereof are reacted with a diol, glycol, or polyol, or mixtures thereof, using a stoichiometric excess of hydroxyl groups, so that the final polyol product is predominantly composed of hydroxyl-terminal groups. The degree of hydroxyl functionality and the hydroxyl percentage can be readily varied by techniques known to those skilled in the art to provide the desired polyol.

[0054] In techniques and technologies for producing flexible polyurethanes, the use of so-called prepolymer technology is also known. This is a technique in which some of the reactions involved in the production of flexible polyurethanes are carried out to produce a prepolymer with increased molecular weight, and depending on the stoichiometry used to prepare this prepolymer, either hydroxyl or isocyanate end groups are obtained. Then, using this prepolymer, the final flexible polyurethane product is prepared by reacting it with either an isocyanate or a polyol, depending on whether the end groups of the prepolymer are hydroxyl or isocyanate, as described above.

[0055] More broadly, any of the prior art polyesters having free reactive hydrogen and especially hydroxyl groups, isocyanate-modified polyester prepolymers, polyesteramides, isocyanate-modified polyesteramides, alkylene glycols, isocyanate-modified alkylene glycols, polyoxyalkylene glycols, isocyanate-modified polyoxyalkylene glycols, etc., can be used to produce the polyurethanes described herein.

[0056] Examples of isocyanates that can be used include those having two or more isocyanate groups that have been used to produce flexible polyurethane foams. Examples of such isocyanate compounds include aromatic isocyanates, aliphatic isocyanates and alicyclic isocyanates, mixtures of two or more such isocyanates, and modified isocyanates obtained by modifying such isocyanates. Specific examples of such isocyanates include toluene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate (crude MDI), xylylene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate, as well as modified products of the above isocyanates such as carbodiimide modified products, biuret modified products, dimers, and trimers. Prepolymers having terminal isocyanate groups obtained from such isocyanates and active hydrogen-containing compounds can also be used.

[0057] In one embodiment, the isocyanate index range of the flexible polyurethane foam may be about 130 to about 80, more preferably about 120 to about 90, and most preferably about 115 to about 95.

[0058] As the foaming agent in the flexible polyurethane foam-forming composition of the present invention, conventionally used known foaming agents can be appropriately selected depending on the properties required for foam formation.

[0059] In this invention, a crosslinking agent may also be used as needed.

[0060] The crosslinking agent is preferably a compound having at least two functional groups with active hydrogen, such as hydroxyl groups, primary amino groups, and secondary amino groups. However, when using a polyol compound as a crosslinking agent, the following should be considered. That is, a polyol compound having a hydroxyl value of at least 50 mgKOH / g and having more than four functional groups is considered a crosslinking agent, and polyols that do not satisfy this condition are considered to be any one of the above polyol mixtures (polyol (1), (2), or other polyols). In addition, two or more crosslinking agents may be used in combination. Specifically, these include polyhydric alcohols such as dextrose, sorbitol, and sucrose; polyols obtained by adding alkylene oxides to polyhydric alcohols; amine compounds such as monoethanolamine, diethanolamine, ethylenediamine, 3,5-diethyl-2,4 (or 2,6)-diaminotoluene (DETDA), 2-chloro-p-phenylenediamine (CPA), 3,5-bis(methylthio)-2,4 (or 2,6)-diaminotoluene, 1-trifluoromethyl-4-chloro-3,5-diaminobenzene, 2,4-toluenediamine, 2,6-toluenediamine, bis(3,5-dimethyl-4-aminophenyl)methane, 4,4'-diaminodiphenylmethane, m-xylenediamine, 1,4-diaminohexane, 1,3-bis(aminomethyl)cyclohexane, or isophoronediamine, and compounds obtained by adding alkylene oxides to the above compounds.

[0061] When the above-mentioned crosslinking agent is used, even when a large amount of foaming agent is used to produce a low-density flexible foam, for example, good foaming stability is achieved, and such flexible foams can be manufactured. In particular, when high molecular weight diols and / or polyols are used, low-density flexible foams that were previously thought to be difficult to foam can be manufactured. Furthermore, when a crosslinking agent is used, durability is improved compared to when no crosslinking agent is used. As in the present invention, when high molecular weight diols and / or polyols are used, in particular when relatively high molecular weight compounds such as those with a molecular weight of 4000 or more are used, foaming stability can be easily improved.

[0062] Water is a typical example of such a blowing agent; other examples include methylene chloride, acetone, and carbon dioxide. Depending on the desired density and other properties of the foamed polyurethane, these and other blowing agents may be used alone or in combination of two or more as known in the art.

[0063] The amount of foaming agent used is not particularly limited, but is typically 0.1 to 20 parts by weight per 100 parts by weight of the diol and / or polyol component of the foam-forming composition. Preferably, the amount of foaming agent would be such that it provides a foam density of 0.8 to 2.5 pounds / cubic foot, preferably 0.9 to 2.0 pounds / cubic foot.

[0064] The polyurethane foam-forming compositions described herein may preferably include any catalyst or combination of catalysts previously known or used for the production of polyurethane foam. Examples of useful catalysts include sodium hydroxide, sodium acetate, tertiary amines, or materials that produce tertiary amines (such as trimethylamine, triethylenediamine, N-methylmorpholine, N,N-dimethylcyclohexylamine, and N,N-dimethylaminoethanol). Metal compounds such as hydrocarbon tin alkyl carboxylates, dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, and octoate stannous, as well as other compounds intended to promote the trimerization of isocyanates such as 2,4,6-tris(N,N-dimethylaminomethyl)phenol and 1,3,5-tris(N,N-dimethyl-3-aminopropyl)-S-hexahydrotriazine, potassium octate, potassium acetate, and catalysts such as DABCO TMR® and POLYCAT 43® are also applicable.

[0065] If desired, many other types of catalysts can be used in place of those listed above. The amount of catalyst used can advantageously be 0.05 to 5 weight percent or more based on the total weight of the diol and / or polyol in the foam-forming mixture.

[0066] The isocyanate (NCO) index applied when producing the flexible foam according to the present invention is 95 to 125, preferably 100 to 120. It is generally understood that the NCO index of polyurethane foams is about 80 to 130.

[0067] The density of the flexible polyurethane foam here is 14 to 80 kg / m 3 , preferably 16 to 55 kg / m 3 , and most preferably 20 to 40 kg / m 3 and can be.

[0068] Surfactants, including organic surfactants and silicone-based surfactants, can be added to function as cell stabilizers. Some representative materials, marketed under the names SF-1109, L-520, L-521, and DC-193, are generally polysiloxane polyoxyalkylene block copolymers. Organic surfactants containing polyoxyethylene-polyoxybutylene block copolymers are also included. It is particularly desirable to use small amounts of surfactant to stabilize the foaming reaction mixture until it hardens. Other surfactants that may be useful herein are polyethylene glycol ethers of long-chain alcohols, tertiary amines or alkanolamine salts of long-chain allyl sulfate esters, alkyl sulfonic acid esters, alkylaryl sulfonic acids, and combinations thereof. Such surfactants are used in amounts sufficient to stabilize the foaming reaction against collapse and the formation of large, heterogeneous bubbles. Typically, for this purpose, a total amount of surfactant of about 0.2 to about 3% by weight based on the whole formulation is sufficient. However, in some embodiments, it may be desirable to include a larger amount of several surfactants, for example, DABCO DC-5598 available from Air Products and Chemicals, Inc. From this viewpoint, surfactants may be included in the formulation of the present invention in any amount of 0 to 6% by weight relative to the diol and / or polyol components.

[0069] Finally, other additives such as fillers and pigments may be included in the polyurethane foam-forming formulations described herein. Such additives may include, in non-limiting embodiments, barium sulfate, calcium carbonate, graphite, carbon black, titanium dioxide, iron oxide, microspheres, alumina trihydrate, wollastonite, prepared glass fibers (droplet or continuous), polyester fibers, other polymer fibers, and combinations thereof. Those skilled in the art will know, without further instruction, typical and appropriate means and methods for adapting inventive formulations to produce flexible polyurethane foams that fall within the scope of the claims accompanying this document and benefit from the desired properties and / or processing modifications.

[0070] The flexible polyurethane foam described herein may be used to construct and form a variety of articles such as furniture, bedding, and automobile seat cushions, more specifically for furniture applications, automobile applications, boat applications, bus seat applications, train seat applications, RV seat applications, office furniture seat applications, aviation applications, tractor applications, bicycle applications, engine mount applications, compressor applications, bedding applications, insulation applications, sporting goods applications, shoe applications, carpet cushion applications, packaging applications, textile applications, cushioning cushion applications, HVAC applications, tent applications, life raft applications, luggage applications, and handbag applications.

[0071] Flexible slab stock polyurethane foam can be used in furniture, such as upholstered furniture like cushions, backrests and arms; the automotive industry, such as seats and back cushions and headlinings and headrests for cars and trucks; public transport, such as buses and airplanes, seats; and seats for tractors, bicycles and motorcycles, including but not limited to vehicle seat bottoms and back bolsters and armrests; as well as support rings for run-flat tires and other automotive interior components; bedding such as mattresses; sound insulation materials; automotive interior components such as armrests; steering wheels and shift lever knobs; shoe soles; and sporting goods. [Examples]

[0072] Seven reaction products were prepared using epoxides and diethylphosphinic acid (DEPA), and evaluated as flame retardant additives for flexible polyurethane foam. Examples of the structures of the prepared molecules are shown below.

[0073] Bisphenol A diglycidyl ether phosphinate reaction products (from DER331, 332, and 383): [ka]

[0074] The n values ​​for epoxy resins DER331, DER332, and DER383 can be calculated based on a given epoxy equivalent weight (EEW), which is the weight associated with each epoxy group in the molecule. Each molecule of DER331, DER332, and DER383 has two epoxy groups. The EEW of DER331 is in the range of 182 to 192 grams. Since the EEW of pure diglycidyl ether of bisphenol A is 170.2 grams, if we take the average value of DER 331 as 187, the n value of DER 331 is approximately 1.10. The EEW of DER 332 is 171 to 175 grams, so the calculated n value is approximately 1.02, and the EEW of DER 383 is 176 to 183 grams, so the calculated n value is approximately 1.05.

[0075] Phosphinic acid ester reaction products of epoxy novolac resins (from DEN431): [ka]

[0076] Regardless of the oligomer length, since almost all phenyl groups have one epoxy group, the same calculation method used above to determine n for DER331, DER332, and DER383 cannot be applied to DEN oligomers. The EEW of pure novolac resin, where all phenyl groups have epoxy groups, is 150.17 grams, while the EEW of DEN431 is 172-179 grams. Therefore, not all phenyl groups have epoxy groups. It is not possible to calculate the n value for these products, and the manufacturer's n value (DEN 431) is approximately 1.8.

[0077] Comparative compound 1: Neopentyl glycol diglycidyl ether phosphinate ester reaction product (from Araldite DY-N): [ka]

[0078] The n-value for the above product can be calculated in the same way as described above for the DER product. DY-N has 125-145 grams of EEW, while pure diglycidyl ether has 108.14 grams of EEW. Therefore, the n-value for DY-N is approximately 1.25.

[0079] Comparative compound 2: 1,4-butanediol diglycidyl ether phosphinate reaction product (from Araldite DY-D): [ka]

[0080] The EEW of DY-D is 117-125 grams, while the EEW of pure diglycidyl ether is 101.12 grams. Therefore, the n value for DY-D is approximately 1.20.

[0081] Comparative compound 3: Trimethylolpropane triglycidyl ether phosphinate ester reaction product (from Araldite DY-T): [ka]

[0082] The EEW of DY-T is 111-143g, while the EEW of pure triglycidyl ether is 100.79g, and the n-value of DY-T is approximately 1.26.

[0083] This molecule was prepared using the following general synthetic scheme: [ka]

[0084] Synthesis example Synthesis Example 1 [ka]

[0085] procedure: DER 383 (139.4 g) was placed in a 0.5 liter four-necked round-bottom flask equipped with a water condenser, J-Kem temperature probe, addition funnel, and magnetic stirrer. This batch was heated to 60°C and stirred at this temperature. Next, diethylphosphonic acid (100 g; 0.819 mol) was added to this batch via the addition funnel. A slight exothermic reaction was observed up to 66°C. The batch was stirred at 80°C and held at this temperature for 3.0 hours, then held at 90°C for 4.0 hours. This batch was cooled to room temperature overnight without stirring.

[0086] This batch was heated to 40°C, and a water condenser was attached to the flask. Propylene oxide (32.0 g, 0.55 mol) was added in portions. After the addition of PO, the batch was stirred at 80°C for 8.0 hours. A sample was taken from the batch for acid value analysis, and an acid value of 0.53 mg KOH / g was obtained. This batch was vacuum stripped at 80°C for 2 hours under complete vacuum to obtain a clear glass compound.

[0087] The analysis results were as follows: Acid value=0.05mg KOH / g Water = 990 ppm OH value = 202 mg KOH / g.

[0088] Synthesis Example 2 [ka]

[0089] procedure: DER 332 (139.4 g) was placed in a 0.5 liter four-necked round-bottom flask equipped with a water condenser, J-Kem temperature probe, addition funnel, and magnetic stirrer. This batch was heated to 60°C and stirred at this temperature. Next, diethylphosphinic acid (100 g; 0.819 mol) was added to this batch via the addition funnel. A slight exothermic reaction was observed up to 63°C. The batch was stirred at 80°C and held at this temperature for 3.0 hours, then held at 90°C for 7.0 hours. The batch was allowed to cool to room temperature overnight without stirring.

[0090] This batch was heated to 40°C, and a water condenser was attached to the flask. Propylene oxide (32.0 g, 0.55 mol) was added in portions. After the addition of PO, the batch was stirred at 80°C for 8.0 hours. A sample was taken for acid value analysis, and an acid value of 0.44 mg KOH / g was obtained. This batch was vacuum stripped at 90°C for 2 hours under complete vacuum to obtain a clear glass compound.

[0091] The analysis results were as follows: Acid value=0.03mg KOH / g Water=930ppm OH value = 197 mg KOH / g.

[0092] Synthesis Example 3 [ka]

[0093] procedure: DER 383 (139.4 g) was placed in a 0.5 liter four-necked round-bottom flask equipped with a water condenser, J-Kem temperature probe, addition funnel, and magnetic stirrer. This batch was heated to 60°C and stirred at this temperature. Next, diethylphosphonic acid (100 g; 0.819 mol) was added to this batch via the addition funnel. A slight exothermic reaction was observed up to 61°C. The batch was stirred at 80°C and held at this temperature for 3.0 hours, then held at 90°C for 9.0 hours. The batch was cooled to room temperature overnight without stirring.

[0094] This batch was heated to 40°C, and a water condenser was attached to the flask. Propylene oxide (16.0 g, 0.275 mol) was added in portions. After the addition of PO, the batch was stirred at 80°C for 3 hours and then at 90°C for 4 hours. A sample was taken for acid value analysis, and an acid value of 0.48 mg KOH / g was obtained. This batch was vacuum stripped at 90°C for 2 hours under complete vacuum to obtain a clear glass compound.

[0095] The analysis results were as follows: Acid value = 0.02 mg KOH / g Water=450ppm OH value = 192 mg KOH / g.

[0096] Synthesis Example 4 [ka]

[0097] procedure: DEN 431 (139.4 g) was placed in a 0.5 liter four-necked round-bottom flask equipped with a water condenser, J-Kem temperature probe, addition funnel, and magnetic stirrer. This batch was heated to 60°C and stirred at this temperature. Next, diethylphosphinic acid (100 g; 0.819 mol) was added to this batch via the addition funnel. A slight exothermic reaction was observed up to 62°C. The batch was stirred at 80°C and held at this temperature for 3.0 hours, then held at 90°C for 9.0 hours. The batch was cooled to room temperature overnight.

[0098] This batch was heated to 40°C, and a water condenser was attached to the flask. Propylene oxide (16.0 g, 0.275 mol) was added in portions. After the addition of PO, the batch was stirred at 80°C for 3 hours and then at 90°C for 4.0 hours. A sample was taken for acid value analysis, and an acid value of 0.34 mg KOH / g was obtained. This batch was vacuum stripped at 90°C for 2 hours under complete vacuum to obtain a clear glass compound.

[0099] The analysis results were as follows: Acid value=0.03mg KOH / g Water=2300ppm OH value = 205 mg KOH / g.

[0100] Table 1 below summarizes the analysis results for four synthesis examples of the present invention and three comparative structures: [Table 1]

[0101] Next, the above products were evaluated as flame retardant additives for polyester polyol polyurethane flexible foam. Due to the higher viscosity of the aromatic epoxy products (prepared from aromatic epoxy resins - synthesis examples 1-4), these materials were evaluated below in blends with monofunctional low-viscosity phosphinate ester (MFPE) products, which are mixtures of the isomers shown below. [ka] The formulations are based on the same chemistry as those in Table 3. The aliphatic epoxy products (comparative compounds 1-3) are easy to use in polyurethane formulations due to their low viscosity and do not benefit from dilution with the MFPE isomer mixture described above; therefore, they were evaluated only as neat products. The results of the first evaluation are shown in Table 2 below.

[0102] [Table 2]

[0103] Density is measured by ASTM D3574 (2003) Test A, Density Test.

[0104] Airflow is measured by ASTM D3574(2003) Test G, an airflow test.

[0105] Compression strain is measured by the standard ASTM method D 3574-03 Test D, which is used to measure the foam's ability to recover after compression. In the evaluation described, the applicant adopted the 90% compression specified in section 41.3 of the standard. This test method consists of deforming a foam specimen to a specific strain, exposing it to specific conditions of time and temperature, and measuring the change in the specimen's thickness after a specific recovery period.

[0106] DG173RLF is a polyester polyol available from COIMs,p,a - Chimica OrganicaIndustriale Milanese as DIEXTER G 173 RLF.

[0107] Niax C131 NPF is a bis(2-dimethylaminoethyl) ether; 3-dimethylamino-N,N-dimethylpropionamide (CAS 3033-62-3 17268-47-2) available from Momentive Performance Materials GmbH.

[0108] Niax DMP is an N,N'-dimethylpiperazine (CAS 106-58-1) available from Momentive Performance Materials GmbH.

[0109] Niax Silicone L537LF is a polyalkylene oxide methylsiloxane copolymer available from Momentive Performance Materials.

[0110] TDI 65 is an aromatic isocyanate available from Covestro, LLC as MONDUR TD-65 (CAS 584-84-9 (65%), 91-08-7 (35%)).

[0111] TDI 80 is an aromatic isocyanate available from Everchem Specialty Chemicals as TDI 80 Type 1 ISOCYANATE (CAS 584-84-9 (80%); 91-08-7 (20%)).

[0112] The neat products (i.e., the products of Synthesis Examples 1-4) were glassy substances at room temperature, while the comparative products (comparative compounds 1-3) were medium-viscosity liquids (similar to Fyrol FR-2, i.e., tris(1,3-dichloro-2-propyl) phosphate (TDCP)). In this first evaluation, the products of Synthesis Examples 1-4 had to be heated to 90°C before injection. The seven phosphinate test compounds were slowly added to the polyol along with other polyurethane compounding components. In the case of the products of Synthesis Examples 1-4, they thickened upon contact with the low-temperature polyol, making it difficult to incorporate the material into the compounding mixture. The addition of comparative compounds 1-3 to the polyol and other compounding chemicals proceeded smoothly without problems. While some of the foams using the products of Synthesis Examples 1-4 yielded good results, the difficulty in handling the materials at room temperature led to the conclusion that the use of these high-viscosity products poses challenges in a commercial environment.

[0113] As described above, it was difficult to prepare foams using the neat products of Synthesis Examples 1-4. However, the materials that yielded acceptable foams when mixed into formulations exhibited favorable flammability and physical properties. The products of Synthesis Examples 2 and 3, when 6 pph was added to the formulation, yielded SE ratings in MVSS302 and compressive strain numbers equivalent to non-flammable foams. These results were unexpected, given that it has been previously known that any phosphinic acid ester product based on the chemistry of diethylphosphinic acid adversely affects the compressive strain properties of the resulting flexible foams. The combination of good flame retardancy and favorable physical properties of the foams produced using the products of Synthesis Examples 2 and 3 demonstrates the commercial merits of these products.

[0114] Evaluation of foams using aliphatic products (comparative compounds 1-3) did not yield favorable results compared to the aromatic epoxy products of synthesis examples 1-4. While foams could be prepared using comparative compounds 1-3, they negatively affected the foam's compressive strain properties, similar to the monofunctional diethylphosphinate ester products. A height loss of 70-80% at 90% compressive strain is considered unacceptable for commercially available foams. All three products of comparative compounds 1-3 catalyzed the foaming reaction, resulting in very rapid reactions and significantly shortening the rise time. Comparative compounds 2 and 3 were much faster than comparative compound 1.

[0115] Another problem associated with the comparative compound 1 product was the unpleasant odor imparted to the foam product. Since the end uses of flexible foam are mostly in confined spaces where it comes into contact with customers (e.g., automobiles, furniture), such an odor from this product is unlikely to be acceptable. Finally, the three products of the comparative compound, being trifunctional (three OH groups), exhibited instability during the foaming process and therefore could not be used to create flexible foam.

[0116] This product destabilized the foam, causing the foam mixture to boil instead of expand in the usual manner. The combination of the product's high OH functionality and the inherent catalytic activity of these phosphinates during the foaming process may have contributed to the product's failure. In summary, none of the aliphatic epoxy-based comparative compounds 1-3 yielded an acceptable soft foam product.

[0117] [Table 3]

[0118] To obtain a version of the product more suitable for handling and injection at room temperature, a second application test was completed using the products from Synthesis Examples 1-4. The method used involved blending each product from Synthesis Examples 1-4 with the low-viscosity phosphinate ester product MFPE in a sufficient ratio to achieve a reasonable viscosity. However, since MFPE products are known to impair the properties of foam products, blending was avoided to the extent necessary. The following datasets in Table 3 were generated using 30% and 40% MFPE additions.

[0119] General observations regarding the 30 / 70 blend indicated that the viscosity was acceptable and the blend could be injected and used without problems at room temperature. Adding 5 pph to all blends at this ratio resulted in a strong SE rating in the MVSSS 302 test and had little effect on the foam's compressive strain properties. Furthermore, Synthesis Examples 2 and 3 showed the best performance at this ratio in terms of final foam quality and were therefore selected for additional testing with alternative blend ratios including MFPE. To further reduce viscosity, MFPE was blended into Synthesis Examples 2 and 3 at a 40 / 60 ratio (see Blend Examples 5-8). At this new ratio, both products obtained a strong SE rating at 5 pph in the MVSS 302 test, and a borderline SE rating at just 3 pph. Therefore, it was concluded that for these blends, adding 4 pph to each blend is ideal for obtaining a reliable SE rating in the MVSS 302. However, evidence was shown that blending in more MFPE negatively affected the compressive strain values ​​of the foam produced with this blend. Percentage loss in recovery showed some increase from the 30 / 70 blend. While we do not wish to be bound by theory, the 40% MFPE blend may be the practical limit to how much of this low-viscosity diluent can be added to the products of Synthesis Example 2 and Synthesis Example 3 in order to achieve acceptable handling properties without sacrificing the physical properties of the foam product.

[0120] In summary, Synthesis Example Products 2 and 3 are the most desirable candidates for future development, providing reactive phosphinate ester blends of usable viscosity with excellent FR properties, good physical foaming properties, and zero VOC emissions from the foam due to the reactivity of the polyfunctional aromatic phosphinate and MFPE products, when blended with up to 40% (preferably 30%) of MFPE. The aromatic epoxy products showed superior performance characteristics compared to the aliphatic epoxy products in both foaming properties and the performance of the final prepared foam. The negative viscosity-related properties of Synthesis Example Products 1-4 can be overcome by blending with additional MFPE (which is already present in the product at 5-6% by weight and results from the final finishing step using propylene oxide). Based on the processes used to produce these materials and the fact that the reaction needs to be completed by the final addition of propylene oxide (PO), it is possible to synthesize Synthesis Example Products 1-4 containing a calculated amount of MFPE by using an excess of diethylphosphinic acid compared to the diepoxy resin used. The resulting blend provides a relatively low-viscosity, highly efficient flame retardant that is phenol-free, has zero emissions, and is a fully reactive flame retardant that minimizes compressive strain loss in the final form product.

[0121] While the present invention has been described with reference to specific embodiments, it will be understood by those skilled in the art that various modifications can be made without departing from the scope of the invention, and that equivalents can be used in place of certain elements. In addition, many modifications can be made without departing from its essential scope to adapt specific situations or materials to the teachings of the invention. Thus, the present invention is not limited to the specific embodiments disclosed as the best mode intended for carrying out the invention, but is intended to include all embodiments within the scope of the appended claims.

Claims

1. A polyfunctional dialkylphosphinate compound of general formula (II) or general formula (III), 【Chemistry 1】 【Chemistry 2】 In the formula, each R １ and R ２ These are independently selected from alkyl groups containing 1 to 4 carbon atoms. R is a divalent linear or branched alkyl group containing up to four carbon atoms, a divalent aralkyl group containing seven to thirteen carbon atoms, or a bond. X and Y are each independently divalent aryl groups containing 6 to 12 carbon atoms. however, In general formula (II), the subscript c is an integer from 1 to 5, the subscript d is 1, and In general formula (III), the subscript c is 1, and the subscript d is an integer from 1 to 26. Polyfunctional dialkylphosphinate compounds.

2. R １ and R ２ The polyfunctional dialkylphosphinate compound according to claim 1, wherein each of the groups is an ethyl group.

3. The polyfunctional dialkylphosphinate compound according to claim 1, wherein X and Y are each divalent phenyl groups, and R is a divalent methyl group or a divalent isopropyl group.

4. General formula (II): 【Transformation 3】 (In the formula, R is a divalent linear or branched alkyl group or bond containing up to four carbon atoms.) A polyfunctional dialkylphosphinate compound according to claim 1, having the following characteristics.

5. General formula (III): 【Chemistry 4】 (In the formula, R is a divalent linear or branched alkyl group or bond containing up to four carbon atoms.) A polyfunctional dialkylphosphinate compound according to claim 1, having the following characteristics.

6. A process for producing a polyfunctional dialkylphosphinate compound, comprising the step of reacting a dialkylphosphinic acid with an aromatic epoxide, The aforementioned aromatic epoxide 【Transformation 5】 And, selected from the group consisting of these combinations, In the formula, R is a divalent linear or branched alkyl group or bond containing up to four carbon atoms. X and Y are each independently divalent aryl groups containing 6 to 12 carbon atoms. The subscript c is an integer between 1 and 5, and the subscript e is an integer between 0 and 25. A process for producing polyfunctional dialkylphosphinate compounds.

7. The process according to claim 6, wherein the dialkylphosphinic acid is present in a molar excess relative to the aromatic epoxide, resulting in an excess of dialkylphosphinic acid, which then reacts in situ with the epoxy compound to produce a blend of a polyfunctional dialkylphosphinate compound and a monofunctional dialkylphosphinate.

8. A flame-retardant polyurethane foam comprising a reaction product of a polyol, an isocyanate, and a flame-retardant effective amount of a polyfunctional dialkylphosphinate compound of general formula (II) or general formula (III), 【Transformation 6】 【Transformation 7】 In the formula, each R １ and R ２ These are independently selected from alkyl groups containing 1 to 4 carbon atoms. R is a divalent linear or branched alkyl group containing up to four carbon atoms, a divalent aralkyl group containing seven to thirteen carbon atoms, or a bond. X and Y are each independently divalent aryl groups containing 6 to 12 carbon atoms. however, In general formula (II), the subscript c is an integer from 1 to 5, the subscript d is 1, and In general formula (III), the subscript c is 1, and the subscript d is an integer from 1 to 26. Flame-retardant polyurethane foam.

9. R １ and R ２ The flame-retardant polyurethane foam according to claim 8, wherein each of the groups is an ethyl group, X and Y are each a divalent phenyl group, and R is a divalent methyl group or a divalent isopropyl group.

10. The aforementioned polyfunctional dialkylphosphinate compound has a general formula (II): 【Transformation 8】 (In the formula, R is a divalent linear or branched alkyl group or bond containing up to four carbon atoms.) A flame-retardant polyurethane foam according to claim 8, having the following characteristics.

11. The aforementioned polyfunctional dialkylphosphinate compound has a general formula (III): 【Chemistry 9】 (In the formula, R is a divalent linear or branched alkyl group or bond containing up to four carbon atoms.) A flame-retardant polyurethane foam according to claim 8, having the following characteristics.

12. An article comprising the polyurethane foam described in claim 8.

13. An article comprising the polyurethane foam described in claim 10.

14. An article comprising the polyurethane foam described in claim 11.

15. Use of the article according to claim 12, wherein the use is selected from the group consisting of furniture use, automobile use, boat use, bus seat use, train seat use, RV seat use, office furniture seat use, aviation use, tractor use, bicycle use, engine mount use, compressor use, bedding use, insulation use, sports equipment use, shoe use, carpet cushion use, packaging use, textile use, cushioning cushion use, HVAC use, tent use, life raft use, luggage use, and handbag use.

16. The use according to claim 15, wherein the furniture use is upholstered furniture.

17. The use according to claim 15, wherein the automotive use is selected from the group consisting of automotive seat cushions, headlinings and headrests, back cushions for automobiles and trucks, bus seats, vehicle seat bottoms and back bolsters, armrests, support rings for run-flat tires, and other automotive interior components.

18. The use according to claim 15, wherein the bedding use is selected from the group consisting of mattress use and mattress top use.

19. The use according to claim 15, wherein the blocking application is a sound-insulating material.

20. The use according to claim 15, wherein the insulating material is a roof insulation material.

21. (a) General formula (II) or general formula (III): 【Chemistry 10】 【Chemistry 11】 (In the formula, each R １ and R ２ is independently selected from alkyl groups containing 1 to 4 carbon atoms, R is a divalent linear or branched alkyl group containing up to four carbon atoms, a divalent aralkyl group containing seven to thirteen carbon atoms, or a bond. X and Y are each independently divalent aryl groups containing 6 to 12 carbon atoms. however, In general formula (II), the subscript c is an integer from 1 to 5, the subscript d is 1, and In general formula (III), the subscript c is 1, and the subscript d is an integer between 1 and 26. Polyfunctional dialkylphosphine compounds; and (b) Monohydroxyl dialkyl phosphinate compounds A composition containing the following:

22. A polyurethane foam comprising the composition of claim 21.

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