Field of the Invention

[0001] The present invention relates generally to phosphorus-containing secondary amine compounds and polymers and coating compositions comprising the same.

Background of the Invention

[0002] Amine compounds are widely used for curing polyurea and polyurethane-polyurea hybrid polymer systems. In polyurea curing, the amine functionality reacts with an isocyanate functionality to yield urea linkages. In polyurethane-polyurea hybrids, a fast-reacting amine functionality, such as a primary amine, will react preferentially with the isocyanate to produce a polyurea portion, while a slow-reacting hydroxyl functionality will react with isocyanate functionality to produce a polyurethane portion, typically with the help of a catalyst. The two reactions give rise to a mixture, or hybrid, of polyurea and polyurethane. Catalysts typically used in polyurethane-urea nonfoaming systems include metal based compounds and a few tertiary amines which promote only a gelling reaction between hydroxyl functionality and isocyanate functionality.

[0003] Primary amines react very quickly with isocyanates to form urea linkages. This can be undesirable in some applications because the reaction may proceed faster than desired. For example, the reaction may progress substantially before components are mixed well, resulting in substandard properties, or the reaction may progress before components can be transferred to a suitable reaction location or molded into a suitable shape. It can also be undesirable in applications that need a measured reaction rate to avoid excessive heat release or in applications that need processing time. Secondary amines generally react more slowly than primary amines, but may still produce a reaction rate that is too fast for some applications. Thus, there is a need for amines having a moderate reaction speed for use in certain polymerization processes.

[0004] It is also desirable that certain polymers have flame retardant properties. This can be achieved with the addition of flame retardants to polymer materials to enhance their flame retardancy. There exist two main approaches to achieve flame retardancy: the additive and the reactive approach. The reactive approach has the advantage that the additive is chemically incorporated into the polymer structure, so it does not migrate to the surface of the matrix either during high temperature processing or burning. Increased focus on the health and environmental compatibility of flame retardants has resulted in a greater desire for use of halogen-free additives, such as organophosphorus reactive flame retardants and phosphorus-containing chemicals that provide the flame retardant effect and can be incorporated into the polymer component. Furthermore, the need for fire-retardant building materials, such as rigid polyurethane foam insulation, has led to the development of many new phosphorus-containing polyethers and polyesters.

[0005] Phosphorus-containing polyols can provide improved flame retardancy. A conventional phosphorus-containing polyol is defined as a polyol containing at least one phosphorus-containing group. It is typically a polymeric or oligomeric polyol. This polyol may be selected from, for example, polyester polyols. The main disadvantage of the use of phosphorus-containing polyols, however, is the lack of hydrolytic stability of these chemicals. Hydrolysis of phosphorus- containing polyols can result in loss of properties in polyurethanes. Therefore, there is a need for hydrolytically stable phosphorus-containing fire retardants. SUMMARY OF THE INVENTION

[0006] Embodiments described herein generally relate to a phosphorus- containing secondary amine compound comprising the reaction product of a polyamine compound, a carbonyl compound, and a phosphorus-containing compound.

[0007] In one embodiment, a phosphorus-containing primary amine may be formed by reducing the phosphorus-containing secondary amine compound and an acrylonitrile.

[0008] In a further embodiment, a polymer is provided comprising the reaction product of an isocyanate compound, the phosphorus-containing secondary amine compound, and, optionally, a polyol compound and one or more additives, wherein the polymer comprises a urea moiety, a urethane moiety, or combinations thereof.

[0009] In a further embodiment, a coating composition is provided comprising the reaction product of an isocyanate compound, the phosphorus-containing secondary amine compound, and, optionally, a polyol compound and one or more additives, wherein the coating composition comprises a urea moiety, a urethane moiety, or combinations thereof.

[0010] In a further embodiment, a polyurethane composition is provided comprising the reaction product of an isocyanate compound, the phosphorus- containing secondary amine compound, and, optionally, a polyol compound, wherein the polyurethane composition comprises a urea moiety, a urethane moiety, or combinations thereof. [0011] In a further embodiment, a polyurethane foam is provided comprising the reaction product of an isocyanate compound, the phosphorus-containing secondary amine compound, and, optionally, a polyol compound, wherein the polyurethane foam comprises a urea moiety, a urethane moiety, or combinations thereof.

[0012] In a further embodiment, a polyurethane elastomer is provided comprising the reaction product of an isocyanate compound, the phosphorus- containing secondary amine compound, and, optionally, a polyol compound, wherein the polyurethane elastomer comprises a urea moiety, a urethane moiety, or combinations thereof.

[0013] In a further embodiment, an epoxy composition is provided comprising the reaction product of an epoxy resin compound, the phosphorus-containing secondary amine compound, and, optionally one or more additives, wherein the epoxy composition comprises an epoxy.

[0014] In a further embodiment, an epoxy composition is provided comprising the reaction product of an epoxy resin compound, a phosphorus-containing primary amine compound, and, optionally one or more additives. The phosphorus-containing primary amine compound is formed by reacting a polyamine compound, a carbonyl compound, and a phosphorus-containing compound to form a phosphorus-containing secondary amine compound, reacting the phosphorus-containing secondary amine compound with acrylonitrile to form a reaction product, and reducing the reaction product. The epoxy composition comprises an epoxy. [0015] In another embodiment, the phosphorus-containing secondary amine described in this invention is further reacted with acrylonitrile then reduced to impart a primary amine functionality.

[0016] In yet another embodiment, a polymer is provided comprising the reaction product of an isocyanate compound, a phosphorus-containing secondary amine compound, and, optionally, a polyol compound, wherein the phosphorus-containing secondary amine compound is the reaction product of a polyamine compound, a carbonyl compound, and a phosphorus-containing compound, and wherein the polymer comprises a urea moiety, a urethane moiety, or combinations thereof. This results in the incorporation of the phosphorus containing amine into the polymer matrix.

[0017] In yet another embodiment, a coating composition is provided comprising the reaction product of an isocyanate compound, a phosphorus- containing secondary amine compound, and, optionally, a polyol compound, wherein the phosphorus-containing secondary amine compound is the reaction product of a polyamine compound, a carbonyl compound, and a phosphorus- containing compound, and wherein the coating composition comprises a urea moiety, a urethane moiety, or combinations thereof. This results in the incorporation of the phosphorus containing amine into the coating matrix.

[0018] In yet another embodiment, a foam composition is provided comprising the reaction product of an isocyanate compound, a phosphorus-containing secondary amine compound, and, optionally, a polyol compound, wherein the phosphorus-containing secondary amine compound is the reaction product of a polyamine compound, a carbonyl compound, and a phosphorus-containing compound, and wherein the foam composition comprises a urea moiety, a urethane moiety, or combinations thereof. This results in incorporation of the phosphorus containing amine into the polymer foam matrix.

[0019] In yet another embodiment, a polymer is provided comprising the reaction product of an epoxy resin with the phosphorus-containing secondary amine described in this invention which is further reacted with acrylonitrile then reduced to impart a primary amine functionality. This results in incorporation of the phosphorus containing amine into the polymer matrix.

[0020] In another embodiment, an olefin polymerizable compound is formed by reacting the phosphorus-containing secondary amine compound with an acrylate, wherein the olefin polymerizable compound has an amide linkage and a free olefinic group.

DETAILED DESCRIPTION OF THE INVENTION

[0021] The present invention relates generally to phosphorus-containing secondary amine compounds such as the aminophosphonate ("AP") compounds discussed below. AP compounds have been found surprisingly useful as reactive components for polyurea and poiyurethane-polyurea systems, and other related amine reactions. The secondary amine phosphates unexpectedly impart the right reaction speed along with improved hydrolytic stability and fire retardancy. The addition of phosphorus functionality in proximity of the secondary amine results in a secondary amine that has moderate reactivity in polymerization reactions. Furthermore, the addition of phosphorus offers flame retardation benefits as well as hydrolytic stability. The phosphorus-containing secondary amines of this invention do not contain ester linkages that anchor the phosphorus to the polymer matrix as do conventional phosphate ester polyols. Therefore, the phosphorus attachment to the polymer using the phosphorus- containing secondary amines of the present invention is hydrolytically stable.

[0022] AP compounds may be made by combined reaction of a carbonyl compound, an amine compound such as a polyamine compound, and a phosphorus containing compound. Accordingly, in certain embodiments, suitable aminophosphonate compounds may generally be produced according to Equation 1 :

[0023] In some embodiments, the AP compound comprises a moiety comprising the following general structure (A) below:

(A)

R ² OR ¹ — NR ⁴ C— P=0 R ³ OR ¹ wherein R ¹ , R ² , R ³ , and R ⁴ are each independently hydrogen or an organic group, such as an alkyl or aryl group. It should be noted that, in certain embodiments, the phosphorus-containing secondary amine compounds of the present invention may have any number of these moieties substituted on a hydrocarbon backbone. Higher functionality polyamines may form poly-AP compounds, up to thermodynamic limits. That is, in these particular compounds, the compounds comprise a plurality of moieties such as those depicted in structure (A) above. As will be understood by those skilled in the art, use of primary amines as a reactive ingredient (reagent) results in secondary AP compounds in which R ⁴ is hydrogen while the use of secondary amines as a reagent will result in tertiary AP compounds in which R ⁴ is a moiety other than hydrogen (e.g., an organic group such as an alkyl or aryl group).

[0024] The secondary amine functionals produced by such reactions have been found to be useful in various amine-mediated polymerization reactions. Amines, R ^a (NR ^b _x ) _y , for example, can be reacted with isocyanates, R ^c NCO, to form polyureas, [R ^a N(R ^b )CON(R ^b )] _n , wherein R ^a is an organic subsiituent such as a hydrocarbon chain, R ^b is hydrogen or an organic group, for example a hydrocarbon group, and R ^c is hydrogen or an organic group, for example a hydrocarbon group. If a mono-AP compound, such as the reaction product depicted in Equation 1 above, is used as an amine source for a polyurea or a polyurethane / urea polymer, the resulting polymer contains the structure [R ^a NHCON(PT)] _n , wherein PT is the phosphonate group -C(R ² R ³ )-P(OR ¹ ) ₂ =0.

[0025] In the above formulations, R ¹ may be an alkyl, alkenyl, alkynyi, or aryl group of about 1 -10 carbon atoms. R ² and R ³ can each be hydrogen or an alkyl, alkenyl, alkynyi, or aryl group having about 1-10 carbon atoms. In the aminophosphonate compounds described above R(AP) _X , R may be an alkyl, cycloalkyl, polyether, or aryl group, or a combination thereof.

[0026] The phosphorus-containing secondary amine compounds described above may be reacted with an isocyanate compound, a polyol compound, and optionally, one or more additives to form a polymer, a polyurethane composition, a polyurethane foam (such as spray foams), or a polyurethane elastomer comprising urea moieties and/or urethane moieties. Various additives may be incorporated into the reaction mixture (a polymer system, including but not limited to polyurethanes, polyureas, and epoxies) to impart specific desired properties. These additives include but are not limited to: colorants, UV stabilizers, plasticizers, surfactants, and anti-static agents.

[0027] Phosphites that are suitable for use in the present invention include, without limitation, organophosphites such as alkylphosphites, alkenylphosphites, alkynylphosphites, or arylphosphites. Examples are trimethyl phosphite, triethyl phosphite, tripropyl phosphite, triisopropyl phosphite, tributyl phosphite, triphenyl phosphite, triisodecyl phosphite, tris(t-butyl dimethylsilyl) phosphite, tris(1 ,1 ,1 ,3,3,3-hexafluoro-2-propyl) phosphite, tris(2,2,2-trifluoroethyl) phosphite, tris(2,4-di-t-butylphenyl) phosphite, tris(2-chloroethyl) phosphite, tris(nonylphenyl) phosphite, tris(tridecyl) phosphite, tris(trimethylsilyl) phosphite, tris(2-tolyl) phosphite, triisooctyl phosphite, triallyl phosphite, dimethyl phosphite, diethyl phosphite, bis(2-ethylhexyl) phosphite, dibenzyl phosphite, dibutyl phosphite, dilauryl phosphite, di-t-butyl phosphite, diphenyi phosphite, and mixtures and derivatives thereof.

[0028] Carbonyls that may be used in the present invention include, without limitation, ketones or aldehydes such as formaldehyde, paraformaldehyde, paraldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, hexaldehyde, nonanal, octanal, undecanal, dodecyl aldehyde, acrolein, methacrolein, furfural, benzaldehyde, substituted benzaldehyde, naphthaldehyde, substituted naphthaldehyde, phthaldialdehyde, tolualdehyde, crotonaldehyde, anisaldehyde, valeraldehyde, isovaleraldehyde, 4- (dimethylamino) benzaldehyde, 2-bromoacrolein, glutaraldehyde, 2- acetylbenzaldehyde, 2-methyl-2-pentenal, 2-methylbutyraldehyde, tiglic aldehyde, cinnamaldehyde, chloral hydrate, 2-tethylbutyraldehyde, 2- methylpentanal, 3,3-dimethylbutyraldehyde, 3-(dimethylamino)-2-methyl-2- propenal, 3-(methylthio) propionaldehyde, 3-(trimethylsilyl)-2-propynal, 3- methylcrotonaldehyde, bromomalonaldehyde, tribromoacetaldehyde, trimethylacetaldehyde, trifluoroacetaldehyde, citronellal, -naphthaldehyde, acetone, methyl phenyl ketone, methyl ethyl ketone, cyclohexanone, benzophenone, butyrophenone, hexanophenone, valerophenone, and mixtures and derivatives thereof.

[0029] Linear aliphatic amines that may be used in the present invention include, without limitation, Ν,Ν'-diisopropylethylenediamine, N,N'-di-sec-butyl- 1 ,2-diaminopropane, N,N'-di(3,3-dimethyl-2-butyl)-1 ,4,diamine-2-methylpentane, N,N'-di-sec-butyl-1 ,6-diaminohexane, N,N'-di(3-pentyl)-2,5-dimethyl-2,5- hexanediamine, N,N'-diisopropyl-1 ,7-diaminoheptane, N,N'-di-sec-butyl-1 ,8- diaminooctane, N,N'-di(2-pentyl)-1 , 10-diaminodecane, and N,N'-di(3-hexyl)-1 ,12- diaminododecane, Linear secondary aliphatic diamines that may be used in the present invention include, without limitation, N,N'-d-(3,3-dimethyl-2-butyl)-1 ,6- diaminohexane, ethylenediamine, 1 ,2-diaminopropane, 1 ,3-diaminopropane, 1 ,4- diaminobutane, 1 ,5-diaminopentane, 1 ,5-diamino-2-methylpentane, 1 ,6- diaminohexane, 2,5-dimethyl-2,5-hexanediamine, 1 ,7-diaminoheptane, 1 ,8- diaminooctane, 1 ,10-diaminodecane, 1 ,12-diaminododecane. Linear aliphatic primary diamines that may be used in the present invention include, without limitation, Ν,Ν'-didodecylethylenediamine, N,N'-didecyl-1 ,3-diaminopropane, N,N'-dinonyl-1 ,5-diaminopentane, N,N'-diheptyl-1 ,5-diamino-2-methylpentane, N,N'-di-n-butyl-1 ,6-diaminohexane, N,N'-di-n-propyl-2,5-dimethyl-2,5- hexanediamine, N,N'-di-n-propyl-1 ,7-diaminoheptane, N,N'-di-n-butyl-1 ,8- diaminooctane, N,N'-dipentyl-1 ,10-diaminodecane, N,N'-dihexyl-1 , 12- diaminododecane, Ν,Ν'-diisopropylidene-ethylenediamine, N,N'-di-sec- butylidene-1 ,2-diaminopropane, N,N'-di(2-butenylidene)-1 ,3-diaminopropane, N,N'-di(3,3-dimethyl-2-butylidene)-1 ,5-diamino-2-methylpentane, N,N'-di-sec- butylidene-1 ,6-diaminohexane, N,N'-di(3-pentylidene)-2,5-dimethyl-2,5- hexanediamine, N,N'-diisopropylidene-1 ,7-diaminoheptane, Ν,Ν'-di-sec- butylidene-1 ,8-diaminooctane, N,N'-di(2-pentylidene)-1 ,10-diaminodecane, Ν,Ν'- di(3-hexylidene)-1 ,12-diaminododecane, and mixtures thereof. [0030] Cyclic amines that are suitable for use in the present invention include, without limitation, N,N'-d(1-cyclopropylethyl)-1 ,5-diaminopentane, N,N'-di(4- hexyl)-1 ,2-diaminocyclohexane, N,N'-dicyclohexyl-1 ,3-dimethyl-3-pentyl-1 ,3- cyclohexanebis(methylamine), N,N'-di(3-methyl-2-cyclohexenyl)-1 ,2- diaminopropane, N,N'-di(2,5-dimethylcyclopentyl)-1 ,4-diaminobutane, Ν,Ν'- di(isophoryl)-1 ,5-diaminopentane, N,N'-di(methyl)-2,5-dimethyl-2,5- hexanediamine, N,N'-di(5-nonyl)-isophoronediamine, N,N'-di-(3,3-dimethyl-2- butyl)-3(4),8(9)-bis-(aminomethyl)-tricyclo[5.2.1 .0(2,6)]decane (also called Ν,Ν'- di-(3,3-dimethyl-2-butyl)-TCD diamine), N,N'-di-2-(4-methylpentyl)- isophoronediamine, 1 ,2-diaminocyclohexane, 1 ,3-diaminocyclohexane, 1 ,4- diaminocyclohexane, 2,4-diethyl-6-methyl-1 ,3-cyclohexanediamine, 4,6-diethyl-2- methyl-1 ,3-cyclohexanediamine, 1 ,3-cyclohexanebis(methylamine), 1 ,4- cyclohexanebis(methylamine), isophorone diamine, bis(p- aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, ,8- diamino-p-menthane, 3(4),8(9)-bis-(aminomethyl)-tricyclo[5.2.1.0(2,6)]decane (TCD diamine, also called octahydro-4,7-methanoinden-1 (2),5(6)-dimethanamine or octahydro-4,7-methano-1 H-indenedimethyl-amine), N,N'-dihexyl-1 ,2- diaminocyclohexane, N,N'-didecyl-1 ,3-diaminocyclohexane, N,N'-di-n-butyl- ,4- diaminocyclohexane, N,N'-dipentyl-1 ,3-cyclohexanebis(methylamine), Ν,Ν'- dinonyl-1 ,4-cyclohexanebis(methylamine)N,N'-di(undecyl)-1 ,2- diaminocyclohexane, Ν,Ν'-dihexylisophoronediamine, Ν,Ν'- dioctylisophoronediamine, Ν,Ν'-dipentyl-TCD diamine, N,N'-di(4-hexylidene)-1 ,2- diaminocyclohexane, N,N'-dicyclohexylidene-1 ,3-diaminocyclohexane, N,N'-di(1- cyclopropylethylidene)-1 ,5-diaminopentane, N,N'-di(1 -cyclobutylethylidene)-1 ,4- diaminocyclohexane, N,N'-di(2,4-dimethyl-3-pentylidene)-1 ,3- cyclohexanebis(methylamine), N,N'-di(1-penten-3-ylidene)-1 ,4- cyclohexanebis(methylamine), N,N'-di(3-methyl-2-cyclohexenylidene)-1 ,2- diaminopropane, N,N'-di(2,5-dimethylcyclopentylidene)-1 ,4-diaminobutane, Ν,Ν'- di(isophorylidene)-1 ,5-diaminopentane, N,N'-di(menthylidene)-2,5-dimethyl-2,4- hexanediamine, N,N'-di(undecylidene)-1 ,2-diaminocyclohexane, N,N'-di-2-(4- methylpentylidene)-isophoronediamine, N,N'-di(5-nonylidene)- isophoronediamine, and mixtures thereof.

[0031] Aromatic amines that may be used in the present invention include, without limitation, 1 ,2-phenylenediamine (phenylenediamine is also called benzenediamine), 1 ,3-phenylenediamine, 1 ,4-phenylenediamine, 4-ethyl-1 ,2- phenylenediamine, 2-isopropyl-1 ,3-phenylenediamine, 4-t-butyl-1 ,3- phenylenediamine, 2-pentyl-1 ,4-phenylenediamine, 4,5-dihexyl-1 ,2- phenylenediamine, 4-methyl-5-heptyl-1 ,3-phenylenediamine, 4,6-di-propyl- ,3- phenylenediamine, 2,5-dioctyl-1 ,4-phenylenediamine, 2,3-diethyl-1 ,4- phenylenediamine, 4,5,6-trihexyl-1 ,3-phenylenediamine, 2,2'- methylenebis(phenylamine) (phenylamine is also called benzeneamine), 2,3'- methylenebis-(phenylamine), 2,4'-methylenebis(phenylamine), 3,3'- methylenebis(phenylamine), 3,4'-methylenebis(phenylamine), 4,4'- methylenebis(phenylamine), 4,4'-(1 ,2-ethanediyl)bis(phenylamine), 3,4'-(1 ,3- propanediyl)bis(phenylamine), 2,2'-methylenebis(5-t-butyl-phenylamine), 3,3'- methylenebis(2-methylphenylamine), 3,3'-methylenebis(5-pentylphenylamine), 3,3'-methylenebis(6-isopropylphenylamine), 4,4'-methylenebis(2- methylphenylamine), 4,4'-methylenebis(3-sec-butylphenylamine), 4,4'-(1 ,2- ethanediyl)bis(2-methylphenylamine), 3,3'-methlyenebis(2,4- dipentylphenylamine), 3,3'-methylenebis(5,6-diisopropylphenylamine), 4,4'- methylenebis(2,3-di-sec-butylphenylamine), 4,4'-methylenebis(3,5-di-t- butylphenylamine), 3,6-di-n-butyl-1 ,2-phenylenediamine, 2,4,6-triethyl- ,3- phenylenediamine, 2,4-diethyl-6-methyl-1 ,3-phenylenediamine, 4,6-diethyl-2- methyl-1 ,3-phenylenediamine, 2,4-diisopropyl-6-methyl-1 ,3-phenylenediamine, 2- methyl-4,6-di-sec-butyl-1 ,3-phenylenediamine, 2-ethyl-4-isopropyl-6-methyl-1 ,3- phenylenediamine, 2,3,5-tri-n-propyl-1 ,4-phenylenediamine, 2,3-diethyl-5-sec- butyl-1 ,4-phenylenediamine, 3,4-dimethyl-5,6-diheptyl-1 ,2-phenylenediamine, 2,4,5,6-tetra-n-propyl-1 ,3-phenylenediamine, 2,3,5,6-tetraethyM ,4- phenylenediamine, 2,2'-methylenebis(6-n-propylphenylamine), 2,2'- methylenebis(3,6-di-n-propylphenylamine), 3,3'-methylenebis(2,6-di-n- butylphenylamine), 4,4'-methylenebis(2,6-diethylphenylamine), 4,4'- methylenebis(2,6-diisopropylphenylamine), 4,4'-methylenebis(2-isopropyl-6- methylephenylamine), 4,4'-(1 ,2-ethanediyl)bis(2,6-diethylenephenylamine), 4,4'- (1 ,2-ethanediyl)bis(2,6-diisopropylphenylamine), 2,2'-methylenebis(3,4,6- tripentylphenylamine), 3,3'-methylenebis(2,5,6-trihexylphenylamine), 4,4- methylenebis(2,3,6-trimethylphenylamine), 4,4'-methylenebis(2,3,4,6- tetramethylphenylamine), and mixtures thereof.

[0032] Polyether amines that are suitable for use in the present invention include, without limitation, polyether amines such as polyethylene oxide amine, polypropylene oxide amine, and poly-THF amine. Mixed polyether amines such as poly-(EO)(PO) amine, [-(EO)i-(PO) _r ] _k (NH ₂ )i, and mixed polyether amines with any mixture of EO, PO, and THF, may also be used. For example, such amines are produced by Huntsman under the tradename JEFFAMINE. The amine of 1 ,3-propanediol (PDO) oligomer, as well as mixed polymer amines with any mixture of EO, PO, THF, and PDO, may also be used.

[0033] As explained above, AP compounds are surprisingly useful as reactive components in polyurethane/polyurea systems. Secondary amines may be used in polyurethane-polyurea hybrid reactions as chain extenders. In a polyurethane- polyurea system, a secondary amine reacts with an isocyanate to form urea linkages, while a tertiary amine catalyzes reaction of the isocyanate with an alcohol to form a polyurethane. If x equivalents of a secondary amine and y equivalents of an alcohol are mixed with x+y equivalents of an isocyanate, with a catalytic amount of a tertiary amine, a polyurethane-polyurea blend results. Using AP compounds as secondary amines for such reactions adds phosphorus structures to the resulting polymers, improving fire resistance without compromising hydrolytic stability. The phosphorus-containing secondary amine compounds described above may be reacted with an isocyanate compound, a polyol compound, and optionally, one or more additives to form a phosphorus- containing polymer, a polyurethane composition, a polyurethane foam (such as spray foams), or a polyurethane elastomer comprising urea moieties and/or urethane moieties. Various additives may be incorporated into the reaction mixture (a polymer system, including but not limited to polyurethanes, polyureas, and epoxies) to impart specific desired properties. These additives include but are not limited to: colorants, UV stabilizers, plasticizers, surfactants, and antistatic agents.

[0034] Similar benefits exist for epoxy polymers, formed by reaction of epoxide monomers and amine hardeners. In one embodiment, bis- and tris-AP compounds may be substituted for standard amine hardeners to create cross- linked epoxy polymers with improved fire resistance due to phosphorus inclusion. The phosphorus-containing secondary amines of this invention may also be modified to impart primary amine functionality. Primary amines react more rapidly as epoxy hardeners (curatives) than do secondary amines. Modification of the secondary amine phosphate to impart primary amine functionality therefore has the benefit that it enables faster epoxy curing. This modification may be done, for example, by reacting the phosphorus-containing secondary amine with acrylonitrile and then reducing as shown in Equation 2:

The resulting phosphorus-containing species now contains a primary amine which can be used in epoxy polymers. This new phosphorus-containing primary amine compound offers the same flame retardant and hydrolytic stability benefits of the other phosphorus-containing secondary amines of the invention.

[0035] An epoxy composition may be formed by reacting an epoxy resin compound, the phosphorus-containing primary amine compound, and, optionally one or more additives. Various additives may be incorporated into the epoxy reaction mixture to impart specific desired properties. These additives include but are not limited to: colorants, UV stabilizers, plasticizers, surfactants, and anti-static agents.

[0036] In certain embodiments of the present invention, a trialkylphosphite may be reacted with a carbonyl and a diamine or triamine, as shown in Equations 3 and 4:

(V)

[0037] In Equations 3 and 4 above, the carbonyl may be an aldehyde or ketone, such as any of the compounds listed above. R1 may be an organic group, such as an alkyl or aryl group, which may contain a halogen. R2 and R3 may be hydrogen or an organic group, such as an alkyl or aryl group, which may contain a halogen. R may be an organic group, such as an alkyl, cycloalkyl, polyether, or aryl group. Any of the carbonyl compounds, phosphites, and amines listed above may be used to perform the reactions of Equations 3 and 4. The reaction products I, II, and III may react with isocyanate compounds to form linkages that incorporate the phosphonate groups into either polyurea or polyurethane/ureas including but not limited to coatings and foams. For example, Equation 5 shows how reaction product I may react with an isocyanate compound:

The products of the reaction shown by Equation 5 have advantageous properties, such as flame retardancy and hydrolytic stability of the flame retardant phosphorus-containing moiety. In addition to reaction with isocyanates, the phosphorus-containing amines of this invention can react with epoxy resins to form epoxy polymers resulting in the same flame retardant and hydrolytic stability advantages.

[0038] The following is a list of useful aminophosphonate precursors for polyurea, polyurethane, and epoxy reactions:



21

22









[0039] The secondary phosphorus-containing amine molecules of this invention can also be modified to impart a polymerizable olefinic group into the molecule such that it can be co-polymerized with other polymeric olefinic monomers such as, but not limited to acrylics, and maleic anhydride. The phosphorus-containing secondary amine compound may be reacted with an acrylate, such as, but not limited to methylmethacrylate or acrylic acid. Equation 6 shows an example of use of a methylmethacrylate to modify the secondary phosphorus-containing amine molecules of this invention (making an amide linkage) and impart a polymerizable olefinic group such that the new resulting molecule can be co-polymerized via olefin polymerization into, for example, but not limited to polystyrene or polyacrylates. The polymer formed by modifying the secondary phosphorus-containing amine molecule may have other olefin polymerizable groups such as, but not limited to, acrylates, itaconics, maleic anhydride, and styrene.

+

Methanol

EXAMPLES

Example 1 :

[0040] 170.4 g (1 mol) of isophorone diamine (IPDA) was charged into a 1000 ml three-neck flask and the flask was heated to 75 °C. 332.4 g (2 mol) triethyl phosphite and 60 g (2.0 mol formaldehyde) paraformaldehyde were added into the heated flask. After adding all the reactants, the reaction was run at 75 °C for 4 hours. The crude product was stripped under vacuum at 120 °C for 1 hour. The bottom product was a liquid with low viscosity, and had amine value of ~4.5 meg/g. The following is the reaction schematic drawing for this reaction.

[0041] The ethanol product was removed to yield a product having species I as the majority, with some species II and III present as well.

[0042] The product mixture l/ll/lll was reacted with Adiprene ^® LW-520, an H ¹² MDI based difunctional prepolymer at 5% NCO available from Chemtura Corp. of Middlebury, Connecticut, at room temperature and a 1 :1 isocyanate:amine molar ratio. For comparison, Polyclear ^® 136, an aliphatic secondary amine chain extender with -7.35 meg/g amine value from Hanson Group, LLC, of Alpharetta, Georgia, was also reacted with the Adiprene LW-520. It was found that the gel time for the product mixture of equation 4 is close to 10 minutes and the gel time for Polyclear 136 is around 2 minutes.

[0043] Desmophen ^® N3400, an HDI based isocyanate at 21 % NCO from Bayer Corp., was also used in cure speed/pot life characterization testing. When reacted with the Desmophen, the products of equation 4 above had a gel time of 1 minute and tack free time of 10 minutes. By comparison, the gel time for Polyclear 136, in combination with Desmophen, was too short to be measured with the same mixing and processing conditions.

Example 2:

[0044] In a second example, 210.3 g (1 mol) of 4,4'- methylenebis(cyclohexylamine) was charged to a 1000 ml three-neck flask and the flask heated to 75°C. 332.4 g (2 mol) triethyl phosphite and 60 g (2.0 mol formaldehyde) paraformaldehyde were added into the heated flask. After adding all the reactants, the reaction was run at 75 °C for 4 hours. The crude product was stripped under vacuum at 120 °C for 1 hour. The bottom product was a liquid with low viscosity. The following product was found to be the majority product:

Example 3:

[0045] In another example, 238.4 g (1 mol) of 4,4'-methylenebis(2-methyl cyclohexylamine) was charged to a 1000 ml three-neck flask and the flask heated to 75°C. 332.4 g (2 mol) triethyl phosphite and 60 g (2.0 mol formaldehyde) paraformaldehyde were added into the heated flask. After adding all the reactants, the reaction was run at 75 °C for 4 hours. The crude product was stripped under vacuum at 120 °C for 1 hour. The bottom product was a liquid with low viscosity. The following product was found to be the majority product:

Example 4:

[0046] Characteristics of polyurea coating materials made using secondary aminophosphonates are shown in Table 1. Performance using the isophorone based diaminophosphonate of Example 1 above was compared to various other amines. In each case, a prepolymer of 48% by weight isophorone diisocyanate (IPDI) and 52% by weight JEFFAMINE ^® SD-2001 amine (N,N ^* -bis(2- propy polyoxypropylenediamine having about 15.5% by weight isocyanate content was blended with an amine to form a polyurea. The various amines referred to in Table 1 are as follows:

Amine 1 : JEFFAMINE T-3000 amine (Glyceryl poly(oxypropylene) triamine)

Amine 2: JEFFAMINE T-403 amine (Trimethylolpropane polyoxypropylene triamine)

Amine 3: (N,N'-diisopropyl)-3-aminomethyl-3,5,5-trimethylcyclohexylam ine

Amine 4: 3-{3-[(2-cyanoethylamino)methyl]-3,5,5-trimethyl-cyclohexyla mino propionitrile

Amine 5: bis-(4-N-sec-butylaminocyclohexyl)-methane Flame resistance was tested by subjecting a .5" x 5" strip of each resin to a Bunsen burner flame for 10 seconds, approximately according to the UL94 flame resistance standard,

Table 1

Characteristics of a Polyurea Made from an Isophorone Based Diaminophosphonate Compared with those of Polyureas Made from

Non-phosphorus Containing Amines

[0047] Samples 1 , 2, and 4 were tested for flame resistance as described above. Sample 1 continued to burn and exhibited dripping, even after igniting flame was removed. Sample 2 charred on its surface, but did not allow flame to propagate, and did not drip. Sample 4 burned and dripped at a slower rate than sample 1. The results shown in Table 1 thus indicate a flame resistance benefit of using phosphorus containing amines of this invention versus other conventional amines used in polyurea systems.

[0048] The polyurea formulation from sample 2 containing the phosphorus- containing secondary amine of Example 1 also had a slower gel time when compared to the other formulations containing conventional amine systems. Moreover, the polyurea formulation from sample 2 had a slower gel time than the polyurea formulation of sample 4 made from a conventional non-phosphorus- containing secondary amine. The gel time is related to the speed of reaction of the amine with the isocyanate. Slower formulation systems are desired in many applications.

Example 5:

[0049] Table 2 shows results of a comparison similar to that shown in Table 1 , but using the diaminophosphonate of Example 2 above. The prepolymer used for the samples in Table 2 is a blend of 48.5% by weight IPDI and 51.5% by weight JEFFAMlNE SD-2001 amine with an isocyanate content of about 16% by weight.

Table 2

Characteristics of a Polyurea Made from a Dicyclohexylaminophosphonate

Compared with those of Polyureas Made from

Non-phosphorus Containing Amines

[0050] Sample 7 had higher gel times and tack free times than Samples 5, 6 and 8, indicative of a slower reaction between the isocyanate and the secondary aminophosphate. Moreover, the polyurea formulation of sample 7 even had a higher gel time and tack free time than the polyurea formulation of sample 8 made from a conventional non-phosphorus-containing secondary amine.

[0051] The polyurea products described above are typically used as coating agents. Because the secondary aminophosphonates described herein are less reactive overall than primary amines, a liquid reaction mixture of isocyanate and secondary aminophosphonate reacts slowly enough to allow time for application of the reaction mixture to a substrate before hardening. For example, a mixture of an isocyanate and a secondary aminophosphonate may be spin coated, ribbon coated, or spray coated onto a substrate to a desired thickness and allowed to cure and set. The coating thus formed is electrically, thermally, and vibrationally insulating, and shows improved flame resistance over polyureas made using some other amines. Substrates which may be coated with such mixtures include metals, cellulosic substrates, polymers, polyurethane or polyurea foams, wood, glasses, and the like.

Example 6:

[0052] 900 g (15 mol) of ethylenediamine was charged into a 12-L three-neck flask and the flask was heated to 75 °C. 4986 g (30 mol) triethyl phosphite and 1635.7 g (30 mol) 55% formaldehyde solution were added into the heated flask. After adding all of the reactants, the reaction was run at 75 °C for 1 hour. The crude product was stripped under vacuum at 100 °C for 2 hours. The bottom product was a liquid with low viscosity, and had amine value of ~5.5 meg/g.

[0053] Although this example uses ethylenediamine (EDA) as the amine, as explained above, other amines may be used, such as JEFFAMINE® D2000 and JEFFAMINE® D230, produced by Huntsman Corp.

Example 7:

[0054] Characteristics of 2.0 pcf spray foam materials made using secondary aminophosphonates are shown in Table 3. Physical properties of 2.0 pcf foams made using the secondary aminophosphates of Example 6 above were compared to those of a 2.0 pcf foam made using TCPP, a standard trichloropropylphosphate fire retardant available from Suspesta as Fyrol® PCF. In each case, a resin blend containing 44.38% by weight of B resin blend and 55.62% by weight of A Rubinate M (a polymeric MDI available from Huntsman) were combined to form a spray foam. The B resin blend consisted of the non- isocyanate side comprising the components as listed in Table 3 for each sample.

[0055] The resin blend was prepared as follows:

44.38 g of B resin blend were added (without mixing) to 55.62 g Rubinate M (PMDI) in a 1 quart unwaxed paper cup. The contents of the cup were mixed at 3600 rpm for 3 seconds. The foam was left to stand overnight and the resulting foam was observed. This was done to evaluate the stability of the foam.

[0056] The various components added to the resin blend and referred to in Table 3 are as follows:

Terol® 925 is an aromatic polyester polyol available from Oxid Chemical, Inc. JEFFOL®R 425-X is a mannich base polyol available from Huntsman Corp.

CARPOL GSP 280 is a sucrose glycerin EO/PO polyol available from E.R. Carpenter.

SILSTAB 2 00 is a silicone surfactant available from Siltech Corp.

TCPP is trichloropropylphosphate fire retardant available from Supresta as

Fyrol® PCF.

RB-79 is an aromatic bromine containing fire retardant available from Albermarle Corp.

JEFFCAT®ZF-10 is a tertiary amine catalyst available from Huntsman Corp. JEFFCAT®ZR-70 is a tertiary amine catalyst available from Huntsman Corp. JEFFCAT®ZR-50 is a tertiary amine catalyst available from Huntsman Corp. JEFFCAT®Z-1 10 is a tertiary amine catalyst available from Huntsman Corp. 245fa is 1 ,1 ,1 ,trifloroethane available from Honeywell Corp. Table 3

Characteristics of 2.0 pcf Spray Foams Made from Phosphorus-Containing Secondary Amines Compared with those of a 2.0 pcf Spray Foam Made from a

Non-Phosphorus Containing Amine

[0057] The results in Table 3 show that incorporation of secondary amine phosphates of this invention produce a polyurethane foam having physical properties sufficiently similar to those of a conventional polyurethane foam made using a standard fire retardant (in this case, TCPP) and no secondary amine, and having improved hydrolytic stability. The phosphorus-containing secondary amines of this invention do not contain ester linkages that anchor the phosphorus to the polymer matrix as do conventional phosphate ester polyols. Therefore, the phosphorus attachment to the polymer using the phosphorus-containing secondary amines of the present invention is hydrolytically stable.

Example 8:

[0058] Characteristics of 0.5 pcf spray foam materials made using secondary aminophosphonates are shown in Table 4. Physical properties of 0.5 pcf foams made using the secondary aminophosphates of Example 6 above were compared to those of a 0.5 pcf foam made using TCPP, a standard trichloropropylphosphate fire retardant available from Supresta as Fyrol® PCF. In each case, a resin blend containing 48% by weight of B resin blend and 52% by weight of A Rubinate M (a polymeric MDI available from Huntsman) were combined to form a spray foam. The B resin blend consisted of the non- isocyanate side comprising the components as listed in Table 4 for each sample.

[0059] The resin blend was prepared as follows:

42 g of B resin blend were added (without mixing) to 58 g Rubinate M (PMDI) in a 1 quart unwaxed paper cup. The contents of the cup were mixed at 3600 rpm for 3 seconds. The mixture was left to stand overnight and the resulting foam was observed.

[0060] The various components added to the resin blend and referred to in Table 4 are as follows:

JEFFOL G31 -35 is a flexible glycerin based PO/EO capped polyol OH # 35 available from Huntsman.

JEFFOL SD-441 is a sucrose/DEG base polyol OH# 441 available from Huntsman.

SURFONIG N-95 is a 9.5 mole ethoxylate of Nonylphenol available from Huntsman.

TCPP is trichloropropylphosphate fire retardant available from Supresta as Fyrol® PCF.

Silstab 2760 is a silicone surfactant available from Siltech.

JEFFCAT®ZF-20 is a tertiary amine catalyst available from Huntsman.

JEFFCAT®Z-130 is a tertiary amine catalyst available from Huntsman.

JEFFCAT®Z-1 10 is a tertiary amine catalyst available from Huntsman.

Table 4

Characteristics of 0.5 pcf Spray Foams Made from Phosphorus-Containing Secondary Amines Compared with those of a 0.5 pcf Spray Foam Made from a

Non-Phosphorus Containing Amine

JEFFOL®SD-441 10.0 10.0 10.0 5.0 5.0

(parts by weight)

Surfonic®N-95 (parts 14.0 14.0 14.0 14.0 14.0 14.0 14.0 14.0 14.0 by weight)

TCPP (parts by weight) 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0

Water (parts by weight) 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0

SILSTAB 2760 (parts 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 by weight)

JEFFCAT®ZF-20 0.9 0.9 0.9 0.9 0.9 0.9 0.9 0.9 0.9 (parts by weight)

JEFFCAT®Z-130 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 (parts by weight)

JEFFCAT®Z-110 4.0 4.0 4.0 4.0 4.0 4.0 4.0

(parts by weight)

JEFFAMINE D-2000 10.0 23.2 23.2 23.2 Phosphate (parts by

weight)

JEFFA INE®D-230 5.0 10.0 10.0 Phosphate (parts by

weight)

EDA Phosphate (parts 5.0 10.0 10.0 by weight)

Cream time, sec 4 3.7 2 4 2 4 2.5 1 .5 1.5

Top of cup, sec 5 8 5 7 5 4 5

Tack free time, sec 12 1 1 1 1 14 10 10 10 8 9 [0061] Top of cup measurements were not taken for Samples 33A and 33B. The 0.5 pcf foams were observed. Sample 33C had a sweet odor. Samples 33B and 33C were more open and showed less shrinkage than sample 33A, the only sample without a secondary amine phosphate. The foams from samples 33B and 33C made with the JEFFAMINE mannich condensate phosphates were surprisingly only a little faster in reactivity than sample 33A. The foams from Samples 35C and 35D made using secondary amine phosphates surprisingly resulted in good quality foams despite the absence of polyols. This is surprising and advantageous because the secondary amine phosphates make the reaction controllable such that a good urethane polymer is formed. If a primary amine were used, the reaction would be too fast and no urethane foam would result.

[0062] The results in Table 4 show that incorporation of secondary amine phosphates of this invention produce a polyurethane foam having physical properties sufficiently similar to those of a conventional polyurethane foam made using a standard fire retardant (in this case, TCPP) and no secondary amine, and having improved hydrolytic stability. The phosphorus-containing secondary amines of this invention do not contain ester linkages that anchor the phosphorus to the polymer matrix as do conventional phosphate ester polyols. Therefore, the phosphorus attachment to the polymer using the phosphorus-containing secondary amines of the present invention is hydrolytically stable.

Example 9:

[0063] Characteristics of 3.0 pcf spray foam materials made using secondary aminophosphonates are shown in Table 5. Physical properties of 3.0 pcf foams made using the secondary aminophosphonates of Example 6 above were compared to those of a 3.0 pcf foam made using TCPP, a standard trichloropropylphosphate fire retardant available from Supresta as Fyrol® PCF. In each case, a resin blend containing 44.38% by weight of B resin blend and 55.62% by weight of A Rubinate M (a polymeric MDI available from Huntsman) were combined to form a spray foam. The B resin blend consisted of the non- isocyanate side comprising the components as listed in Table 5 for each sample.

[0064] The resin blend was prepared as follows:

44.38 g of B resin blend were added (without mixing) to 55.62 g Rubinate M (polymeric MDI) in a 1 quart unwaxed paper cup. The contents of the cup were mixed at 3600 rpm for 3 seconds. The mixture was left to stand overnight and the resulting foam was observed.

[0065] The various components added to the resin blend and referred to in Table 5 are as follows:

JEFFOL®SG-522 is a sucrose/glycerin PO polyol available from Huntsman Corp. JEFFOL®G30-240 is a glycerin PO polyol available from Huntsman Corp.

JEFFOL®G30-650 is a glycerin PO polyol available from Huntsman Corp.

Surfonic®T-15 is a 15 mole ethoxylate of tallow amine available from Huntsman Corp.

JEFFCAT®ZR-50 is a low odor amine catalyst available from Huntsman Corp.

TEGOSTAB B 8404 is a silicone surfactant available from Evonik.

245fa is a1 ,1 ,1 , trichloroethane available from Honeywell Corp.

TCPP is trichloropropylphosphate fire retardant available from Supresta as

Fyrol® PCF. Table 5

Characteristics of 3.0 pcf Metal Panel Foams Made from Phosphorus-Containing Secondary Amines Compared with those of a 3.0 pcf Metal Panel Foam Made from a Non-Phosphorus Containing Amine

[0066] The results in Table 5 show that incorporation of secondary amine phosphates of this invention produce a polyurethane foam having physical properties sufficiently similar to those of a conventional polyurethane foam made using a standard fire retardant (in this case, TCPP) and no secondary amine, but having improved hydrolytic stability. The phosphorus-containing secondary amines of this invention do not contain ester linkages that anchor the phosphorus to the polymer matrix as do conventional phosphate ester polyols. Therefore, the phosphorus attachment to the polymer using the phosphorus-containing secondary amines of the present invention is hydrolytically stable.

[0067] The foregoing examples show that the secondary amine phosphates of the present invention unexpectedly impart the right reaction speed to achieve foams having desired physical properties along with improved hydrolytic stability and fire retardancy.

[0068] While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.