WO2019204625A1

WO2019204625A1 - Halogen-free flame-retardant compositions for flexible polyurethane foams

Info

Publication number: WO2019204625A1
Application number: PCT/US2019/028151
Authority: WO
Inventors: Lawino Kagumba; Charles MANZI-NSHUTI; Ken Wei
Original assignee: Frx Polymers, Inc.
Priority date: 2018-04-18
Filing date: 2019-04-18
Publication date: 2019-10-24

Abstract

The present invention relates generally to the field of flame-retardant compositions, and in particular to halogen-free flame-retardant compositions, methods for making them, their use for flexible polyurethane foams. In particular, the compositions are made from two parts, wherein Part A includes at least one isocyanate and Part B includes at least one isocyanate reactive polyether polyol; and at least one additional component wherein at least one of Part A or Part B further comprises a phosphonate oligomer.

Description

HALOGEN-FREE FLAME-RETARDANT COMPOSITIONS FOR FLEXIBLE

POLYURETHANE FOAMS

REFERENCE TO RELATED APPLICATIONS

[0001] The present application claims benefit of priority to the filing date of U.S. Provisional Patent Application 62/659,502 filed April 18, 2018, entitled“HALOGEN-FREE FLAME-RETARDANT COMPOSITIONS FOR FLEXIBLE POLYURETHANE FOAMS” and U.S. Provisional Patent

Application 62/664,701 filed April 30, 2018, entitled“HALOGEN-FREE FLAME-RETARDANT COMPOSITIONS FOR FLEXIBLE POLYURETHANE FOAMS,” the contents of which are incorporated herein by reference in their entirety.

FIELD OF THE INVENTION

[0002] The present invention relates generally to the field of flame -retardant compositions, and in particular to halogen-free flame-retardant compositions for flexible polyurethane foams.

BACKGROUND

[0003] Flexible polyurethane foams can be used for a wide variety of applications, such as vehicle, construction, furniture, mattresses, insulation, protection, support, and the like, wherein the polyurethane is often required to have a number of specific properties, such as flame retardancy properties. In order to meet flame retardancy requirements, flexible polyurethane foams generally need to couple with flame retardant materials. The state-of-the-art approach to rendering flexible polyurethane foams flame retardant is to use additives such as halogen-based compounds or compounds containing aluminum and/or phosphorus. Use of the additives with certain polymers can have a deleterious effect on the processing characteristics and/or the mechanical performance of articles produced from them. In addition, some of these compounds are toxic, and can leach into the environment over time making their use less desirable. In some countries, certain halogenated additives are being phased-out of use because of environmental concerns.

[0004] Accordingly, there remains a critical need for flame -retardant flexible polyurethane foams that do not contain halogen.

SUMMARY

[0005] The present disclosure provides composition, method, and article of manufacture using halogen-free and flame -retardant materials for flexible polyurethane foams. [0006] Some embodiments pertain to a halogen-free composition comprising: Part A, at least one isocyanates selected from the group consisting of 4,4'-methyl diphenyl diisocyanate (MDI), polymeric MDI, or a combination thereof; and Part B, at least one isocyanate reactive polyether polyol, wherein one polyether polyol contains a content of ethylene oxide units of at least about 20% to about 100%, a phosphonate oligomer, and at least one additional component selected from the group consisting of blowing agent, surfactant, chain extender, catalyst, crosslinking agent, filler, cell opener, co-flame retardant, or any combinations thereof. In these embodiments, the composition can have a density ranging from about 80 kg/m³ to about -140 kg/m³. In these embodiment, the co-flame retardant can not comprise graphite. In these embodiments, the composition can be a polyurethane foam or a flexible polyurethane foam. In these embodiments, the co-flame retardant can be selected from the group consisting in , ammonium polyphosphate, melamine, melamine polyphosphate, melamine cyanurate, aluminum trihydrate, carbon nanotubes, silica or any combinations thereof. In these embodiments, the composition can lose a maximum of about 50% of its tensile strength after heat aging at least about 150 °C for about 7 days. In these embodiments, the composition can achieve FMVSS302 rating. In these embodiments, the composition can achieve a V-0 rating at about 0.5 inch according to Underwriter’s Laboratories Standard UL94 Flammability test before and after heat aging.

[0007] Some other embodiments pertain to a method for producing a flexible polyurethane foam comprising mixing and reacting Part A and Part B to form a foam, wherein Part A comprises at least one isocyanates selected from the group consisting of 4,4'-methyl diphenyl diisocyanate (MDI), polymeric MDI, or a combination thereof, and Part B comprises at least one isocyanate reactive polyether polyol, wherein one polyether polyol contains a content of ethylene oxide units of at least about 20% to about 100%, a phosphonate oligomer, and at least one additional component selected from the group consisting of blowing agent, surfactant, chain extender, catalyst, crosslinking agent, filler, cell opener, co-flame retardant, or any combinations thereof.

[0008] Some other embodiments pertain to a halogen-free flexible polyurethane foam for use in thermal applications including engine compartment of vehicle, underbody thermal part, or a combination thereof.

[0009] Embodiment 1: A halogen-free composition comprising:

Part A:

at least one isocyanate;

Part B:

(1) at least one isocyanate reactive polyether polyol; and

(2) at least one additional component selected from the group consisting of blowing agent, surfactant, chain extender, catalyst, crosslinking agent, filler, cell opener, co-flame retardant, or any combinations thereof,

wherein at least one of Part A or Part B further comprises a phosphonate oligomer.

[0010] Embodiment 2: A halogen-free composition comprising:

Part A:

at least one isocyanates selected from the group consisting of 4,4'-methyl diphenyl diisocyanate (MDI), polymeric MDI, or a combination thereof ;

Part B:

(1) at least one isocyanate reactive polyether polyol, wherein one of the polyether polyol contains a content of ethylene oxide units of at least about 20% to about 100%;

(2) a phosphonate oligomer; and

(3) at least one additional component selected from the group consisting of blowing agent, surfactant, chain extender, catalyst, crosslinking agent, filler, cell opener, co-flame retardant, or any combinations thereof.

[0011] Embodiment 3 : The halogen-free composition of embodiment 1 or 2, wherein one of the polyether polyol contains a content of ethylene oxide units of at least about 20% to about 100%

[0012] Embodiment 4: The halogen -free composition of embodiment 1 or 2, wherein the composition has a density ranging from about 80 kg/m³ to about 140 kg/m³.

[0013] Embodiment 5 : The halogen-free composition of claim 1 or 2, wherein the composition has a density ranging from about 20 kg/m³ to about 80 kg/m³.

[0014] Embodiment 6: The composition of embodiment 1 or 2, wherein the co-flame retardant does not comprise graphite.

[0015] Embodiment 7 : The composition of embodiment 1 or 2, wherein the composition is a polyurethane foam.

[0016] Embodiment 8: The composition of embodiment 7, wherein the polyurethane foam is a flexible polyurethane foam.

[0017] Embodiment 9: The composition of embodiment 1 or 2, wherein the co-flame retardant is selected from the group consisting in ammonium polyphosphate, melamine polyphosphate, melamine, melamine cyanurate, aluminum trihydrate, carbon nanotubes, silica, or any combinations thereof.

[0018] Embodiment 10: The composition of embodiment 7, wherein the composition loses a maximum of about 50% of its tensile strength after heat aging at least about 150 °C for about 7 days.

[0019] Embodiment 11 : The composition of embodiment 7, wherein the composition achieves FMVSS302 rating. [0020] Embodiment 12: The composition of embodiment 7, where the composition achieves a V-0 rating at about 0.5 inch according to Underwriter’s Laboratories Standard UL94 Flammability test before and after heat aging.

[0021] Embodiment 13: A method for producing a flexible polyurethane foam comprising the composition any of embodiments 1 to 12, wherein Part A and Part B are mixed and reacted to form a foam.

[0022] Embodiment 14: A halogen-free flexible polyurethane foam according to any of embodiments 1 to 12 for use in thermal applications including engine compartment of vehicle, underbody thermal part, or a combination thereof.

[0023] Embodiment 15: A halogen -free composition comprising:

Part A:

at least one isocyanate selected from the group consisting of 4,4'-methyl diphenyl diisocyanate (MDI), polymeric MDI, or a combination thereof ;

Part B:

(1) at least one isocyanate reactive polyether polyol, wherein one of the polyether polyol contains a content of ethylene oxide units of at least about 20% to about 100%; and

[0024] Embodiment 16: The halogen -free composition of embodiment 15, wherein one of the polyether polyol contains a content of ethylene oxide units of at least about 20% to about 100%.

BRIEF DESCRIPTION OF THE DRAWINGS

[0025] The foregoing and other objects and advantages of the invention will be appreciated more fully from the following further description, with reference to the accompanying drawings. The skilled person in the art will understand that the drawings, described below, are for illustration purposes only. The drawings are not intended to limit the scope of the applicant’s teachings in any way.

[0026] FIG. 1A shows an image of polyurethane foam composition, polyurethane with 5% expandable graphite;

[0027] FIG. 1B shows an image of polyurethane foam composition, polyurethane with 2.5% expandable graphite and 2.5% NOFIA OL1001; [0028] FIG. 1C shows an image of polyurethane foam composition polyurethane with 2.5% expandable graphite and 5% NOFIA OL1001; and

[0029] FIG. 2 shows a graph from the thermogravimetric analysis of pristine polyurethane foam (curve A) and polyurethane with 5.6% NOFIA OL1001 (curve B).

[0030] FIG. 3A shows a graph depicting Temperature at 50% mass loss.

[0031] FIG. 3B shows a graph depicting Residue at 400 °C.

DETAILED DESCRIPTION

[0032] The present disclosure is not limited to particular systems, devices, and methods described, as these may vary. The terminology used in the description is for the purpose of describing the particular versions or embodiments only, and is not intended to limit the scope.

[0033] As used in this document, the singular forms“a,”“an,” and“the” include plural references unless the context clearly dictates otherwise. Unless defined otherwise, all technical and scientific terms used herein have the same meanings as commonly understood by one of ordinary skill in the art. Nothing in this disclosure is to be construed as an admission that the embodiments described in this disclosure are not entitled to antedate such disclosure by virtue of prior invention. As used in this document, the term “comprising” means“including, but not limited to.”

[0034] The following terms shall have, for the purposes of this application, the respective meanings set forth below.

[0035] “Optional” or“optionally” means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event occurs and instances where it does not.

[0036] “Substantially no” means that the subsequently described event may occur at most about less than 10 % of the time or the subsequently described component may be at most about less than 10 % of the total composition, in some embodiments, and in others, at most about less than 5 %, and in still others at most about less than 1 %.

[0037] The term“alkyl” or“alkyl group” refers to a branched or unbranched hydrocarbon or group of 1 to 20 carbon atoms, such as but not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t- butyl, octyl, decyl, tetradecyl, hexadecyl, eicosyl, tetracosyl and the like. “Cycloalkyl” or“cycloalkyl groups” are branched or unbranched hydrocarbons in which all or some of the carbons are arranged in a ring such as but not limited to cyclopentyl, cyclohexyl, methylcyclohexyl and the like. The term“lower alkyl” includes an alkyl group of 1 to 10 carbon atoms. [0038] The term“aryl” or“aryl group” refers to monovalent aromatic hydrocarbon radicals or groups consisting of one or more fused rings in which at least one ring is aromatic in nature. Aryls may include but are not limited to phenyl, napthyl, biphenyl ring systems and the like. The aryl group may be unsubstituted or substituted with a variety of substituents including but not limited to alkyl, alkenyl, halide, benzylic, alkyl or aromatic ether, nitro, cyano and the like and combinations thereof.

[0039] “Substituent” refers to a molecular group that replaces a hydrogen in a compound and may include but are not limited to trifluoromethyl, nitro, cyano, Ci_₂o alkyl, aromatic or aryl, halide (F, Cl, Br, I), Ci_2o alkyl ether, Ci_₂o alkyl ester, benzyl halide, benzyl ether, aromatic or aryl ether, hydroxy, alkoxy, amino, alkylamino (-NHR’), dialkylamino (-NR’R”) or other groups which do not interfere with the formation of the intended product.

[0040] As defined herein, an“arylol” or an“arylol group” is an aryl group with a hydroxyl, OH substituent on the aryl ring. Non-limiting examples of an arylol are phenol, naphthol, and the like. A wide variety of arlyols may be used in the embodiments of the invention and are commercially available.

[0041] The term“alkanol” or“alkanol group” refers to a compound including an alkyl of 1 to 20 carbon atoms or more having at least one hydroxyl group substituent. Examples of alkanols include but are not limited to methanol, ethanol, 1- and 2-propanol, 1,1- dimethylethanol, hexanol, octanol and the like. Alkanol groups may be optionally substituted with substituents as described above.

[0042] The term“alkenol” or“alkenol group” refers to a compound including an alkene 2 to 20 carbon atoms or more having at least one hydroxyl group substituent. The hydroxyl may be arranged in either isomeric configuration (cis or trans). Alkenols may be further substituted with one or more substituents as described above and may be used in place of alkenols in some embodiments of the invention. Alkenols are known to those skilled in the art and many are readily available commercially.

[0043] As used herein, the term“about” means plus or minus 10% of the numerical value of the number with which it is being used. Therefore, about 50% means in the range of 45%-55%.

[0044] The terms "flame retardant", "flame resistant", "fire resistant" or "fire resistance", as used herein, mean that the polymer exhibits a limiting oxygen index (LOI) of at least 27. The LOI of a material is indicative of its ability to bum once ignited. The test for LOI is performed according to a procedure set forth by the American Society for Test Methods (ASTM). The test, ASTM D2863, provides quantitative information about a material's ability to bum or "ease of bum". If a polymeric material has an LOI of at least 27, it will, generally, bum only under very high applied heat. Fire resistance may also be tested both by measuring the 0₂ index in accordance with ASTM D 2863-70 and also by measuring the after-burning time in accordance with the UL test (Subject 94). In this test, the tested materials are given classifications of UL-94 VO, UL-94 VI and UL-94 V2 based on the results obtained with the ten test bars of a given thickness. Briefly, the criteria for each of these UL-94 V-classifications are as follows:

[0045] UL-94 VO: the total flaming combustion for each specimen after removal of the ignition flame should not exceed 10 seconds and the total flaming combustion for 5 specimens should not exceed 50 seconds. None of the test specimens should release any drips which ignite absorbent cotton wool.

[0046] UL-94 V 1 : the total flaming combustion for each specimen after removal of the ignition flame should not exceed 30 seconds and the total flaming combustion for 5 specimens should not exceed 250 seconds. None of the test specimens should release any drips which ignite absorbent cotton wool.

[0047] UL-94 V2: the total flaming combustion for each specimen after removal of the ignition flame should not exceed 30 seconds and the total flaming combustion for 5 specimens should not exceed 250 seconds. Test specimens may release flaming particles, which ignite absorbent cotton wool.

[0048] Fire resistance may also be tested by measuring after-burning time. These test methods provide a laboratory test procedure for measuring and comparing the surface flammability of materials when exposed to a prescribed level of radiant heat energy to measure the surface flammability of materials when exposed to fire. The test is conducted using small specimens that are representative, to the extent possible, of the material or assembly being evaluated. The rate at which flames travel along surfaces depends upon the physical and thermal properties of the material, product or assembly under test, the specimen mounting method and orientation, the type and level of fire or heat exposure, the availability of air, and properties of the surrounding enclosure. If different test conditions are substituted or the end- use conditions are changed, it may not always be possible by or from this test to predict changes in the fire-test-response characteristics measured. Therefore, the results are valid only for the fire test exposure conditions described in this procedure.

[0049] Both number average (M_n) and weight average molecular weight (M_w) as used herein, can be determined by gel permeation chromatography (GPC). GPC provides information about the molecular weight and molecular weight distribution of a polymer based on size exclusion chromatography.

Typically, the molecular weight of a polymer is based on the calibration of the chromatograph columns using known molecular weights of polystyrene standards. It is known that the molecular weight distribution of a polymer is important to properties such as thermo-oxidative stability (due to different amount of end groups), toughness, melt flow, and fire resistance, for example, low molecular weight polymers drip more when burned. [0050] Description general phosphonate structures

[0051] Embodiments of the invention are not limited by the type of phosphonate component included and may include, for example, polyphosphonates, branched polyphosphonates, or hyberbranched polyphosphonates, random or block copolyphosphonates, co-oligo(phosphonate ester)s, or co- oligo(phosphonate carbonate)s, phosphonate oligomers, branched phosphonate oligomers, or hyperbranched phosphonates, and in certain embodiments, the phosphonate component may have the structures described and claimed in U.S. Patent Nos. US7,645,850, US7, 816,486, US8,389,664, US8,563,638, US8,648,l63, US8,779,04l, US8,530,044, each of which is hereby incorporated by reference in its entirety.

[0052] Such phosphonate components may include repeating units derived from diaryl

alkylphosphonates or diaryl arylphosphonates. For example, in some embodiments, such phosphonate components include structural units illustrated by Formula I:

where Ar is an aromatic group and -O-Ar-O- may be derived from an aromatic dihydroxy compound or aromatic diol, R is a Ci_₂o alkyl, C2-20 alkene, C_2-20 alkyne, C_5-20 cycloalkyl, or C_6-20 aryl, and nl is an integer from 2 to about 200, 2 to about 100, 2 to about 75, 2 to about 50, 2 to about 20, 2 to about 10, or 2 to about 5, or any integer between these ranges.

[0053] The term“aromatic diol” is meant to encompass any aromatic or predominately aromatic compound with at least two associated hydroxyl substitutions of the formula (II):

wherein n2, p2, and q2 are each independently 0, 1, 2, 3, or 4; R^a is independently at each occurrence unsubstituted or substituted C_MO hydrocarbyl; and X^a is a single bond,— O— ,— S— ,— S(O)— ,— S(0)_2— ,— C(O)— , or a C 1-18 hydrocarbylene, which can be cyclic or acyclic, aromatic or nonaromatic, and can further comprise one or more heteroatoms selected from oxygen, nitrogen, sulfur, silicon, or phosphorus. As used herein, the term“hydrocarbyl”, whether used by itself, or as a prefix, suffix, or fragment of another term, refers to a residue that contains only carbon and hydrogen unless it is specifically identified as“substituted hydrocarbyl”. The hydrocarbyl residue can be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It can also contain combinations of aliphatic, aromatic, straight chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties. The term“substituted” means including at least one substituent such as a hydroxyl, amino, thiol, carboxyl, carboxylate, amide, nitrile, sulfide, disulfide, nitro, Cn₈ alkyl, Cn₈ alkoxyl, C₆_i₈ aryl, C₆_i₈ aryloxyl, C₇_i₈ alkylaryl, or C₇_i₈ alkylaryloxyl. The term“substituted” further permits inclusion of halogens (i.e., F, Cl, Br, I).

[0054] Some illustrative examples of specific dihydroxy compounds include the following: bisphenol compounds such as 4,4'-dihydroxybiphenyl, l,4-dihydroxynaphthalene, l,5-dihydroxynaphthalene, 1,6- dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, bis(4- hydroxyphenyl)methane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)diphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane, bis(4-hydroxy- 3 ,5 -dibromophenyl)methane, bis(4-hydroxy-3 -methylphenyl)methane, bis(4-hydroxy-3 - chlorophenyl)methane, bis(4-hydroxyphenyl)-l-naphthylmethane, l,2-bis(4-hydroxyphenyl)ethane, 1,1- bis(4-hydroxyphenyl)-l-phenylethane, 2,2-bis(4-hydroxyphenyl)propane (“bisphenol A” or“BPA”), 2- (4-hydroxyphenyl)-2-(3-hydroxyphenyl)propane, 1 , 1 -bis(4-hydroxyphenyl)cyclopentane, 1 , 1 -bis(4- hydroxyphenyl)cyclohexane, 1 , 1 -bis(4-hydroxy-3 -methylphenyl)cyclohexane, 1 , 1 -bis-(4- hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1, l-bis(4-hydroxyphenyl)isobutene, 1, l-bis(4- hydroxyphenyl)cyclododecane, trans-2,3 -bis(4-hydroxyphenyl)-2 -butene, 2,2-bis(4- hydroxyphenyl)adamantane, alpha, alpha' -bis(4-hydroxyphenyl)toluene, bis(4-hydroxyphenyl)acetonitrile, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3-ethyl-4-hydroxyphenyl)propane, 2,2-bis(3-n- propyl-4-hydroxyphenyl)propane, 2,2-bis(3-isopropyl-4-hydroxyphenyl)propane, 2, 2-bis(3 -sec-butyl -4- hydroxyphenyl)propane, 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4- hydroxyphenyl)propane, 2,2-bis(3-allyl-4-hydroxyphenyl)propane, 2,2-bis(3-methoxy-4- hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3- chlorophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 4,4'-dihydroxybenzophenone, bis(4-hydroxy-3,5-dimethylphenyl)ketone, bis(4-hydroxy-3,5-dichlorophenyl)ketone, 3,3-bis(4- hydroxyphenyl)-2-butanone, l,6-bis(4-hydroxyphenyl)-l,6-hexanedione, ethylene glycol bis(4- hydroxyphenyl)ether, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl) sulfide, bis(4- hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfone, 9,9-bis(4-hydroxyphenyl)fluorene, 2,7- dihydroxypyrene, 6,6'-dihydroxy-3,3,3',3'-tetramethylspiro(bis)indane (“spirobiindane bisphenol”), phenolphthalein and phenolphthalein derivatives, 3,3-bis(4-hydroxyphenyl)phthalimide, 2,6- dihydroxydibenzo-p-dioxin, 2,6-dihydroxythianthrene, 2,7-dihydroxyphenoxathin, 2,7-dihydroxy-9, 10- dimethylphenazine, 3,6-dihydroxydibenzofiiran, 3,6-dihydroxydibenzothiophene, and 2,7- dihydroxycarbazole; resorcinol, substituted resorcinol compounds such as 5-methyl resorcinol, 5-ethyl resorcinol, 5-propyl resorcinol, 5-butyl resorcinol, 5-t-butyl resorcinol, 5-phenyl resorcinol, 5-cumyl resorcinol, or the like; catechol; hydroquinone; substituted hydroquinones such as 2-methyl

hydroquinone, 2-ethyl hydroquinone, 2-propyl hydroquinone, 2-butyl hydroquinone, 2-t-butyl hydroquinone, 2-phenyl hydroquinone, 2-cumyl hydroquinone, 2,3,5,6-tetramethyl hydroquinone, 2,3,5,6-tetra-t-butyl hydroquinone, chlorohydroquinone, acetoxyhydroquinone, and nitrohydroquinone.

[0055] In particular embodiments, the Ar may be derived from bisphenol A and R may be a methyl group providing polyphosphonates, phosphonate copolymers, random and block co-oligo(phosphonate carbonate)s and co-oligo(phosphonate ester)s, and oligomeric phosphonates that may have structures such as, but not limited to, structures of Formulae III:

(III).

[0056] In some embodiments, a single aromatic diol may be used, and in other embodiments, various combinations of such aromatic diols may be incorporated into the polymer. The phosphorous content of phosphonate component may be controlled by the molecular weight (MW) of the aromatic diol used in the oligomeric phosphonates, polyphosphonates, or copolyphosphonates. A lower molecular weight aromatic diol may produce an oligomeric phosphonate, polyphosphonate, or copolyphosphonate with a higher phosphorus content. An aromatic diol, such as resorcinol, hydroquinone, or a combination thereof or similar low molecular weight aromatic diols may be used to make oligomeric phosphonates or polyphosphonates with high phosphorous content. The phosphorus content, expressed in terms of the weight percentage, of the phosphonate oligomers, phosphonates, or copolyphosphonates may be in the range from about 2 wt. % to about 18 wt. %, about 4 wt. % to about 16 wt. %, about 6 wt. % to about 14 wt. %, about 8 wt. % to about 12 wt. %, or a value between any of these ranges. In some embodiments, phosphonate oligomers, polyphosphonates, or copolyphosphonates prepared from bisphenol A or hydroquinone may have phosphorus contents of 10.5 wt. % and 18 wt. %, respectively.

[0057] Description polyphosphonates

[0058] In certain embodiments, the phosphonate component may be a polyphosphonate containing long chains of the structural unit of Formula I. In some embodiments, the polyphosphonates may have a weight average molecular weight (Mw) according polystyrene standards of about 10,000 g/mole to about 100,000 g/mole as determined by GPC, and in other embodiments, the polyphosphonates may have an Mw of from about 12,000 to about 80,000 g/mole as determined by GPC. The number average molecular weight (Mn) in such embodiments may be from about 5,000 g/mole to about 50,000 g/mole, or from about 8,000 g/mole to about 15,000 g/mole, and in certain embodiments the Mn may be greater than about 9,000 g/mole. The molecular weight distribution (i.e., Mw/Mn) of such polyphosphonates may be from about 2 to about 10 in some embodiments and from about 2 to about 5 in other embodiments.

[0059] In certain embodiments, the phosphonate component may be a polyphosphonate containing branched structures of the structural unit of Formula I. In some cases, a branching agent (i.e. tri or tetrahydroxy aromatic compound) may be added or it may be generated in-situ via a reaction of bisphenol A and an appropriate catalyst. In some embodiments, the branched polyphosphonates may have a molecular weight distribution (i.e., Mw/Mn) of from about 2 to about 10 in some embodiments and from about 2.3 to about 3.2 in other embodiments.

[0060] Description phosphonate copolymers

[0061] In some embodiments, the phosphonate component may be copolymers containing carbonate linkages [i.e., copoly(phosphonate carbonate)] or ester linkages [i.e., copoly(phosphonate esters)].

[0062] For example, copoly (phosphonate carbonate)s may include repeating units derived from at least 20 mole percent high purity diaryl alkylphosphonate or optionally substituted diaryl

alkylphosphonate, one or more diaryl carbonate, and one or more aromatic dihydroxy compounds, wherein the mole percent of the high purity diaryl alkylphosphonate is based on the total amount of transesterification components, i.e., total diaryl alkylphosphonate and total diaryl carbonate. As indicated by the term“random” the monomers of the copoly(phosphonate carbonate)s of various embodiments may be incorporated into polymer chain randomly. Therefore, the polymer chain may include alternating phosphonate and carbonate monomers linked by one or more aromatic dihydroxide and/or various segments in which several phosphonate or several carbonate monomers form phosphonate or carbonate segments. Additionally, the length of various phosphonate or carbonate segments may vary within individual copoly (phosphonate carbonate)s.

[0063] The phosphonate and carbonate content of the copoly(phosphonate carbonate)s may vary among embodiments, and embodiments are not limited by the phosphonate and/or carbonate content or range of phosphonate and/or carbonate content. For example, in some embodiments, the

copoly(phosphonate carbonate)s may have a phosphorus content of from about 1% to about 20% by weight of the total copoly(phosphonate carbonate), and in other embodiments, the phosphorous content of the copoly(phosphonate carbonate)s of the invention may be from about 2% to about 10% by weight of the total polymer. [0064] In other embodiments, the copoly(phosphonate carbonate)s or copoly(phosphonate ester)s, may have structures such as, but not limited to, those structures of Formulae IV and V, respectively:

V

and combinations thereof, where Ar¹ and Ar² are each, independently, an aromatic group and -O-Ar'-O- and -0-Ar²-0- may be derived from a dihydroxy compound as described by structure (II). In Formula IV and V, R is a Ci_₂o alkyl, C2-20 alkene, C_2-20 alkyne, C_5-20 cycloalkyl, or C_6-20 aryl. R¹ may be a Ci_₂₀ alkylene or cycloalkylene, such as methylene, ethylene, propylene, butylene, pentylene, and the like, and in particular embodiments, R¹ can be derived from aliphatic diols such as, but not limited to, 1,4- cyclohexyldimethanol, 1, 4-butane diol, 1, 3-propane diol, ethylene diol, ethylene glycol, and the like and combinations thereof. R² is, independently, a Ci_₂₀ alkylene, C_2-20 alkylenylene, C_2-20 alkylynylene, C_5-20 cycloalkylene, or C_6-20 arylene. In certain embodiments, R² can be derived from adipic acid, dimethyl terephthabc acid, terephthalic acid, isophthabc acid, naphthalene dicarboxylic acid and the like or derivatives thereof or combinations thereof. In certain embodiments, R² may be an aromatic group such as naphthalene, phenylene, biphenylene, propane-2, 2-diyldibenzylene, and in some embodiments, R² can be derived from, for example, dimethyl terephthalate, dimethyl isophthalate, dimethyl naphthalate, and the like and combinations thereof. Thus, R² may be, for example, naphthalene, phenyl, both of which may be substituted at any position on the rings.

[0065] Such copoly(phosphonate carbonates) or copoly(phosphonate esters) may be block copoly(phosphonate carbonates) or copoly(phosphonate esters) in which each m4, n4, and p5 is greater than about 1, and the copolymers contain distinct repeating phosphonate and carbonate blocks or phosphonate and ester blocks. In other embodiments, the copoly(phosphonate carbonates) or copoly(phosphonate esters) can be random copolymers in which each m4, n4, and p5 are each, independently, an integer from 1 to about 200, 1 to about 100, 1 to about 75, 1 to about 50, 1 to about 20, 1 to about 10, or 1 to about 5, or any integer between these ranges. [0066] In particular embodiments, the Ar¹ and Ar² may be derived from bisphenol A and R may be a methyl group providing random and block co(phosphonate carbonate)s and co(phosphonate ester)s that may have structures such as, but not limited to, structures of Formulae VI and VII:

and combinations thereof, where each of m4, n4, p5, and R¹ and R² are defined as described above.

[0067] The copoly(phosphonate carbonate)s of various embodiments exhibit both a high molecular weight and a narrow molecular weight distribution (i.e., low polydispersity). For example, in some embodiments, the copoly(phosphonate carbonate)s may have a weight average molecular weight (Mw) of about 10,000 g/mole to about 100,000 g/mole as determined by GPC, and in other embodiments, the copoly(phosphonate carbonate)s may have a Mw of from about 12,000 to about 80,000 g/mole as determined by GPC. The number average molecular weight (Mn) in such embodiments may be from about 5,000 g/mole to about 50,000 g/mole, or from about 8,000 g/mole to about 15,000 g/mole, and in certain embodiments the Mn may be greater than about 9,000 g/mole. The narrow molecular weight distribution (i.e., Mw/Mn) of such copoly(phosphonate carbonate)s may be from about 2 to about 7 in some embodiments and from about 2 to about 5 in other embodiments.

[0068] Additional description phosphonate oligomers

[0069] In some embodiments, the molecular weight (weight average molecular weight as determined by gel permeation chromatography based on polystyrene calibration) range of the oligophosphonates, random or block co-oligo(phosphonate ester)s and co-oligo(phosphonate carbonate)s may be from about 500 g/mole to about 18,000 g/mole or any value within this range. In other embodiments, the molecular weight range may be from about 1,500 g/mole to about 15,000 g/mole, about 3,000 g/mole to about 10,000 g/mole, or any value within these ranges. In still other embodiments, the molecular weight range may be from about 700 g/mole to about 9,000 g/mole, about 1,000 g/mole to about 8,000 g/mole, about 3,000 g/mole to about 4,000 g/mole, or any value within these ranges. [0070] The oligomeric phosphonates can have about 60% to about 100% of the total of oligomeric phosphonates have two or more reactive end-groups. In other embodiments, about 75% to about 99% of the total of oligomeric phosphonates have two or more reactive end-groups. In some embodiments, the reactive end-groups may be, for example, epoxy, vinyl, vinyl ester, isopropenyl, isocyanate, or combinations thereof, and in certain embodiments, about 80% to about 100% of the total oligomeric phosphonates may have two or more hydroxyl end groups. In various embodiments, the oligomeric phosphonates or portions thereof may include oligophosphonate, random co-oligo(phosphonate ester), block co-oligo(phosphonate ester), random co-oligo(phosphonate carbonate), block co-oligo(phosphonate carbonate), or combinations thereof. In some embodiments, the oligomeric phosphonates may include linear oligomeric phosphonates, branched oligomeric phosphonates, or a combination thereof, and in other embodiments, such oligomeric phosphonates may further include hyperbranched

oligophosphonates .

[0071] Description of compositions and polymer compositions

[0072] Some embodiments provide a halogen-free composition comprising: Part A: at least one isocyanate; Part B: (1) at least one isocyanate reactive polyether polyol, wherein one of the polyether polyol contains a content of ethylene oxide units of at least about 20% to about 100%; and (2) at least one additional component selected from the group consisting of blowing agent, surfactant, chain extender, catalyst, crosslinking agent, filler, cell opener, co-flame retardant, or any combinations thereof, wherein at least one of Part A or Part B further comprises a phosphonate oligomer.

[0073] Some embodiments provide a halogen-free composition comprising Part A: at least one isocyanates selected from the group consisting of 4,4'-methyl diphenyl diisocyanate (MDI), polymeric MDI, or a combination thereof, and Part B: (1) at least one isocyanate reactive polyether polyol, wherein one of the polyether polyol contains a content of ethylene oxide units of at least about 20% to about 100%; and (2) at least one additional component selected from the group consisting of blowing agent, surfactant, chain extender, catalyst, crosslinking agent, filler, cell opener, co-flame retardant, or any combinations thereof, wherein at least one of Part A or Part B further comprises a phosphonate oligomer.

[0074] Some embodiments, a halogen-free composition comprising: Part A, at least one isocyanate selected from the group consisting of 4,4'-methyl diphenyl diisocyanate (MDI), polymeric MDI, or a combination thereof; and Part B, at least one isocyanate reactive polyether polyol, a phosphonate oligomer, and at least one additional component selected from the group consisting of blowing agent, surfactant, chain extender, catalyst, crosslinking agent, filler, cell opener, co-flame retardant, or any combinations thereof. In some embodiments, a halogen-free composition comprising: Part A, at least one isocyanate selected from the group consisting of 4,4'-methyl diphenyl diisocyanate (MDI), polymeric MDI, or a combination thereof and a phosphonate oligomer, and Part B, at least one isocyanate reactive polyether polyol and at least one additional component selected from the group consisting of blowing agent, surfactant, chain extender, catalyst, crosslinking agent, filler, cell opener, co-flame retardant, or any combinations thereof.

[0075] In these embodiments, the polyether polyol can contain a content of ethylene oxide unit of about 20% to about 100%, or about 20% to about 90%, or about 20% to about 80%, or about 20% to about 70%, or about 20% to about 60%, or about 20% to about 50%, or about 20% to about 40%, or about 20% to about 30%. In these embodiments, the polyether polyol can contain a content of ethylene oxide units of at least about 20%, or at least about 30%, or at least about 40%, or at least about 50%, or at least about 60%, or at least about 70%, or at least about 80%, or at least about 90%.

[0076] In these embodiments, the composition can have a density ranging from about 40 kg/m³ to about 200 kg/m , or from about 40 kg/m to about 180 kg/m , or from about 40 kg/m to about 160 kg/m , or from about 40 kg/m³ to about 140 kg/m³. In these embodiments, the composition can have a density ranging from about 50 kg/m³ to about 180 kg/m³, or from about 60 kg/m³ to about 160 kg/m³, or from about 70 kg/m³ to about 140 kg/m³. In some embodiments, the composition can have a density ranging from about 80 kg/m³ to about 140 kg/m³.

[0077] In these embodiments, the co-flame retardant cannot comprise graphite. In these

embodiments, the composition can be a polyurethane foam or a flexible polyurethane foam. In some embodiments, the composition is substantially free of graphite. In some embodiments, the composition is free of graphite.

[0078] In these embodiments, the co-flame retardant can be selected from the group consisting in ammonium polyphosphate, melamine , melamine polyphosphate, melamine cyanurate, aluminum trihydrate, silica, carbon nanotubes, or any combinations thereof.

[0079] In these embodiments, the composition can lose a maximum of about 5% of its tensile strength after heat aging at least about 150 °C for about 7 days, or a maximum of about 10% of its tensile strength after heat aging at least about 150 °C for about 7 days, or a maximum of about 15% of its tensile strength after heat aging at least about 150 °C for about 7 days, or a maximum of about 20% of its tensile strength after heat aging at least about 150 °C for about 7 days, or a maximum of about 25% of its tensile strength after heat aging at least about 150 °C for about 7 days, or a maximum of about 30% of its tensile strength after heat aging at least about 150 °C for about 7 days, or a maximum of about 35% of its tensile strength after heat aging at least about 150 °C for about 7 days or a maximum of about 40% of its tensile strength after heat aging at least about 150 °C for about 7 days, or a maximum of about 45% of its tensile strength after heat aging at least about 150 °C for about 7 days. In some embodiment, the composition can lose a maximum of about 50% of its tensile strength after heat aging at least about 150 °C for about 7 days.

[0080] In these embodiments, the composition can achieve FMVSS302 rating. In these

embodiments, the composition can achieve a V-0 rating at about 0.5 inch according to Underwriter’s Laboratories Standard UL94 Flammability test before and after heat aging.

[0081] Some other embodiments pertain to a method for producing a flexible polyurethane foam comprising mixing and reacting Part A and Part B to form a foam, wherein Part A: at least one isocyanate; Part B: (1) at least one isocyanate reactive polyether polyol, wherein one of the polyether polyol contains a content of ethylene oxide units of at least about 20% to about 100%; and (2) at least one additional component selected from the group consisting of blowing agent, surfactant, chain extender, catalyst, crosslinking agent, filler, cell opener, co-flame retardant, or any combinations thereof, wherein at least one of Part A or Part B further comprises a phosphonate oligomer.

[0082] Some other embodiments pertain to a method for producing a flexible polyurethane foam comprising mixing and reacting Part A and Part B to form a foam, wherein Part A: at least one isocyanates selected from the group consisting of 4,4'-methyl diphenyl diisocyanate (MDI), polymeric MDI, or a combination thereof, and Part B: (1) at least one isocyanate reactive polyether polyol, wherein one of the polyether polyol contains a content of ethylene oxide units of at least about 20% to about 100%; and (2) at least one additional component selected from the group consisting of blowing agent, surfactant, chain extender, catalyst, crosslinking agent, filler, cell opener, co-flame retardant, or any combinations thereof, wherein at least one of Part A or Part B further comprises a phosphonate oligomer.

[0083] Some other embodiments pertain to a method for producing a flexible polyurethane foam comprising mixing and reacting Part A and Part B to form a foam, wherein Part A comprises at least one isocyanates selected from the group consisting of 4,4'-methyl diphenyl diisocyanate (MDI), polymeric MDI, or a combination thereof, and Part B comprises at least one isocyanate reactive polyether polyol, wherein one polyether polyol contains a content of ethylene oxide units of at least about 20% to about 100%, a phosphonate oligomer, and at least one additional component selected from the group consisting of blowing agent, surfactant, chain extender, catalyst, crosslinking agent, filler, cell opener, co-flame retardant, or any combinations thereof.

[0084] Some other embodiments pertain to a method for producing a flexible polyurethane foam comprising mixing and reacting Part A and Part B to form a foam, wherein Part A comprises a phosphonate oligomer, and at least one isocyanates selected from the group consisting of 4,4'-methyl diphenyl diisocyanate (MDI), polymeric MDI, or a combination thereof, and Part B comprises at least one isocyanate reactive polyether polyol, wherein one polyether polyol contains a content of ethylene oxide units of at least about 20% to about 100%, and at least one additional component selected from the group consisting of blowing agent, surfactant, chain extender, catalyst, crosslinking agent, filler, cell opener, co flame retardant, or any combinations thereof.

[0085] Some other embodiments pertain to a halogen-free flexible polyurethane foam for use in thermal applications including engine compartment of vehicle, underbody thermal part, or a combination thereof.

[0086] The term "polymer composition", as used herein, refers to a composition that comprises at least one of the present invention and at least one other polymer, oligomer, or monomer mixture. The other polymer, oligomer, or monomer mixture may include those that comprise, or are partially comprised of, or are comprised of monomers intended to produce the following polymer families including but not limited to a polycarbonate, polyacrylate, polyacrylonitrile, polyester, polyether, polyamide, polystyrene, polyurethane, polyurea, polyurethane urea, polyepoxy, poly(acrylonitrile butadiene styrene), polyimide, polyarylate, poly(arylene ether), polyethylene, polypropylene, polyphenylene sulfide, poly(vinyl ester), polyvinyl chloride, bismaleimide polymer, polyanhydride, liquid crystalline polymer, cellulose polymer, benzoxazine resin, another polyphosphonate, or a combination of any two or more of these. The other polymer, oligomer, or monomer may contain functional groups that will react chemically.

[0087] Any epoxy resin can be used for the purpose(s) of the invention provided that the resin contains at least one glycidyl group, alicyclic epoxy group, or a similar epoxy group (i.e., oxirane or ethoxyline group). Preferable is an epoxy resin having two or more epoxy groups. Such a component can be represented by novolac-type epoxy resin, cresol-novolac epoxy resin, triphenolalkane-type epoxy resin, aralkyl-type epoxy resin, aralkyl-type epoxy resin having a biphenyl skeleton, biphenyl-type epoxy resin, dicyclopentadiene-type epoxy resin, heterocyclic -type epoxy resin, epoxy resin containing a naphthalene ring, a bisphenol-A type epoxy resin, a methylene dianiline type epoxy resin, a bisphenol-F type epoxy compound, stilbene-type epoxy resin, trimethylol-propane type epoxy resin, terpene-modified epoxy resin, linear aliphatic epoxy resin obtained by oxidizing olefin bonds with peracetic acid or a similar peracid, alicyclic epoxy resin, or sulfur-containing epoxy resin. The substrate may also be composed of two or more epoxy resins of the aforementioned types. Preferable epoxy resins are those derived from bisphenol A or methylene dianiline. Preferable for use are aralkyl -type epoxy resins with a biphenyl structure, a bisphenol A structure or a methylene dianiline structure. The epoxy resin is typically commercially available, though this is not a requirement for applicability. The epoxy may also contain as a component a benzoxazine compound, oligomer or resin.

[0088] It is contemplated that the polymer compositions of the present invention may comprise other components, such as but not limited to other flame retardants, chopped or continuous glass, metal, carbon based, or ceramic fibers; fillers, surfactants, mold release agents, organic binders, polymeric binders, crosslinking agents, coupling agents, anti-dripping agents, colorants, inks, dyes, antioxidants or other stabilizers, or any combination thereof.

[0089] Some embodiments can be used as coatings on plastics, metals, ceramic, or wood products or they can be used to fabricate articles, such as free-standing films and extruded sheets, fibers, foams, molded articles, adhesives, filaments, and fiber reinforced composites. These articles may be well-suited for applications requiring fire resistance.

[0090] Some embodiments and polymer compositions including them exhibit outstanding flame resistance and good melt processability. Such improvements make these materials useful in applications in the automotive and electronic sectors that require outstanding fire retardancy, high temperature performance, and melt processability.

EXAMPLES

[0091] To further elucidate various aspects of the invention, the following working examples are provided. The examples are provided only for illustrative purposes and are not intended necessarily to present optimal practice of the invention and/or optimal results that may be obtained by practicing the invention.

[0092] Materials

[0093] Polyurethane compositions provided as examples are prepared using the following raw materials:

[0094] (A) Flame retardant additives: Phosphonate oligomer (NOFIA OL1001) was obtained from

FRX Polymers and can be used in either granulate form or powder form (typically <50 pm particle size). Expandable graphite (ExG) (Nyagraph 35) was obtained from Nyacol Nano Technologies. Halloysite nanotubes (Dragonite APA) was obtained from Applied Mineral Inc. Ammonium polyphosphate (APP) was obtained from Clariant and Melamine polyphosphate (Melapur 200) was obtained from BASF. Melamine, 99%, was purchased from Sigma Aldrich. Aerosil R8200, a hydrophobic silica, was obtained from Evonik.

[0095] (B) Polyols: Voranol CP6001 was obtained from DOW. Jeffol G-31-28 was obtained from

Huntsman. Poly-G 55-56 was obtained from Monument Chemicals. Pluronic F108 and Pluronic L62LF were obtained from BASF.

[0096] (C) Isocyanate: Suprasec 9634, modified monomeric 4,4' methyl diphenyl diisocyanate (MDI) was obtained from Huntsman and MDI based prepolymer Voralux HE 150 from Dow.

[0097] (D) Surfactants: Tegostab B4113 was obtained from Evonik.

[0098] (E) Chain extender: Diethylene glycol was obtained from Sigma Aldrich. [0099] (F) Catalysts: Niax Al, Fomrez Catalyst UL-22, Fomrez Catalyst UL-32, and Fomrez Catalyst

UL-54 were obtained from Momentive. Dabco 33LV was obtained from Evonik. K-KAT XC-B221 was obtained from King Industries Specialties Chemicals. Di-n-butyltin dilaurate was purchased from Sigma Aldrich.

[0100] (G) Water: tap water (Chelmsford, MA city water) was used.

[0101] Methods

[0102] Polyol side preparation: NOFIA OL1001 was incorporated into the polyol side of the formulation using two methods. (1) Pre-dissolving NOFIA OL1001 powder in a polyether polyol typically with >30% ethylene oxide content such as the polyether polyol Poly-G 55-56; 2000 MW.

Complete dissolution was achieved by mixing at 80-90 °C for 4- 5 hours. A chain extender, surfactants, catalysts, co-FR fillers, and water were then added and mixed until a homogeneous mixture is achieved (20-30 °C). Polyether polyol (6000 MW), Voranol CP6001, or Jeffol G-31-28 was then added and mixed until a homogeneous mixture is achieved. (2) Mixing the NOFIA OL1001 powder into the primary polyether polyol (6000 MW), such as Voranol CP6001, or Jeffol G-31-28 containing the surfactants, chain extender, blowing agent and catalyst. The powder is mixed until a homogenous dispersion is achieved with no visible aggregates.

[0103] Foam Preparation: To initiate the foaming reaction, the required amount of isocyanate was metered into the polyol side containing all the ingredients described above. Finally, the mixture was poured into a mold where the complete foaming reaction occurred. The foam was allowed to fully react at room temperature for 1 day.

[0104] Quantification of the amount of the phosphonate oligomer that had reacted into the polyurethane backbone was tested following the procedure provided here: a small foam sample (0.5 to 1.0 g) was placed in a scintilation vial containing THF (15-20 g). The vial was placed on a wrist shaker and allowed to mix (24-48 hours; room temperature , 20-30 °C). The mixture was then filtered to remove solid particles and undissolved moieties. Finally, the filtrate was analyzed using HPLC to quantify the unreacted Nofia OLlOOlphosphonate oligomer.

[0105] Thermal stability of the polyurethane foam formulations was evaluated by Thermogravimetric analysis (TGA) in air. The samples were heated at a ramp rate of 10 °C/min from 25 °C to 800 °C.

[0106] Compositions disclosed below, i.e., Examples 1-8, show the versatility of compositions that can be prepared using phosphonate oligomers as flame retardant compounds.

[0107] Example 1 [0108] Several polyurethane formulations containing 5% oligomeric phosphonate (NOFIA OL1001) were prepared to investigate the effect of the catalyst system on the reaction/ incorporation of NOFIA OL1001 into the polyurethane foam systems. Table 1-1 provides the recipe for foam formulations prepared using a single catalyst and Table 1-2 provides the recipes for foam formulations prepared using a blend of dibutyltin dilaurate plus a second catalyst.

[0109] Independent of the catalyst system, the results show that above 85% of NOFIA OL1001 is incorporated in the polyurethane backbone. Majority of the examples show >95% reaction is achieved, with the highest conversion (99 - 100%) achieved when Dabco 33LV is used (with or without DBTDL). Blends of DBTDL plus a second catalyst (see Table 1-2) were observed to slightly improve the conversion ofNOFIA OL1001. For example, while 90% conversion of NOFIA OL1001 was achieved using Dabco 33LV alone (Table 1-1 Example l-B), the replacement of 0.09 parts of Dabco 33LV with DBTDL improved the conversion ofNOFIA OL1001 to 99% (Table 1-2, Example l-AA). In terms of the kinetics of the foaming reaction, amine catalysts (Niax-Al and Dabco 33LV) were observed to be more effective as compared to their Tin counterparts: Cream time was short (within 0-1 min after charging the isocyanate); the Tin catalysts (Fomrez catalyst series) were slow to react (foam rise kicks off within 2-5 minutes); and no foam rise was observed when the Bismuth catalyst was used.

TABLE 1-1

TABLE 1-1

TABLE 1-2

[0110] Example 2

[0111] Example 2 discloses the impact of blending NOFIA OL1001 with co-FR additives on the foaming process and the density values of polyurethane foam formulations. Table 2-1 provides formulation recipes with loading levels of NOFIA OF 1001 ranging between 0-10%. The loading of the co-FR, Dragonite APA Halloysite nanotubes (HNT), or Melamine polyphosphate (MP) was 1%.

Comparable example C2-1 is the baseline formulation with no NOFIA OF1001 or other co-FR additives. The viscosity of the formulation mixtures prior to charging the isocyanate to initiate the foaming process remained low, making the process appealing. Comparable final density values were observed for the resulting foam formulations (within experimental error, between 110 - 135 kg/m³). TABLE 2-1

[0112] Typically, the NOFIA OLlOOl is first dissolved in PolyG-55-56, which is then added to the polyether polyol (Jeffol G31-28; 6000 MW). The presence of NOFIA OL1001 in the recipes also improves the dispersion of other co-FR additives that can be used along NOFIA OLlOOl . In Table 2-2, the recipes of formulations containing expandable graphite (ExG) or a combination of ExG and NOFIA OLlOO l are provided. ExG is insoluble in the polyols and quickly settles down during the sample preparation process if agitation is not maintained. As shown in Figure 1, however, NOFIA OLlOOl helps to disperse ExG in the final foam formulation: dark spots indicate areas where aggregates or

agglomerates of ExG are observed in the polyurethane foam containing 0% NOFIA OLlOOl (Figure 1A). The dispersion of ExG improves when 2.5% NOFIA OLlOOl is added (Figure 1B) and when the loading level of NOFIA OF1001 is further increased to 5%, uniform dispersion of the ExG without aggregation is obtained, which is an indication that the presence of NOFIA OF 1001 in the formulation aids in the dispersion of ExG in the final foam.

TABLE 2-2

[0113] Example 3

[0114] Example 3 discloses the impact of polyols and NOFIA OL1001 on the thermal stability of the foam formulation. The ratio of the polyol (Voranol CP6001; 6000 MW) to the polyol (PolyG-55-56; 2000 MW) was varied. In Table 3, comparative example 3-C1 and example 3-1 the ratio is set at 75 to 25 and, in comparative example 3-C2 and example 3-2, the ratio is set at 70 to 30 (Voranol CP6001 to PolyG-55- 56). Poly-G 55-56 is used as the solubilizing polyol for NOFIA OF1001. The resulting foam density of these formulations was 140 kg/m³. The data shows that the incorporation of NOFIA OF1001 at 5.6wt% in the final foam increases the thermal stability of the foam formulations; both the onset degradation temperature and the temperature at 50% mass loss are higher relative to the comparative samples (i.e., samples Cl and C2). For example 3-1, when comparing with comparative sample Cl, the temperature at 50% degradation increases by almost 40 °C. This trend holds when the ratio of Voranol CP6001 to Poly G 55-56 is varied in example 3-2. All formulations did not exhibit any shrinkage on storage (RT, 30 days) indicating the incorporation of NOFIA OL1001 into the polyurethane backbone did not have a negative impact on the foam properties. Figure 2 provides the TGA curves showing higher thermal resistance for the polyurethane foam containing NOFIA OL1001 (, dotted line B (example 3-1) versus the pristine PU foam (solid curve A, example 3-C1).

TABLE 3-1

[0115] Heat Aging of Foams at 150°C for 7 days

[0116] Table 3-2 shows formulations used to prepare foam samples with 5% and 10% NOFIA OL1001 in the final foam. The comparative example 3C-2 shows foam samples containing no NOFIA OL1001. TABLE 3-2

[0117] The samples were placed in an oven at l50°C for 7 days. The samples were analyzed by TGA before and after heating aging. The results are summarized Figure 3. Samples containing 5% and 10% NOFIA OL1001 have better thermal stability and heat aging properties versus the control sample with no NOFIA OL1001. The temperature at 50wt% mass loss for the control foam is l5°C lower than the 10% NOFIA OL1001 sample and drops by l0°C after the heat aging test, but for the NOFIA OL1001 containing samples, the temperature increases (5% sample) or remains the same (10% sample) after heat aging. The char at 400°C for the 5% and 10% NOFIA OL1001 samples are higher than the control before and after heat aging foam. The results show improved thermal stability of foams containing NOFIA OL1001.

[0118] Example 4 discloses the synergistic effects of a combination of melamine and NOFIA OL1001 and silica on the fire behavior properties of the foams in UL94 test. The total loading levels of the fire retardants in the final foam was set at 30 - 35%. The comparative example 4-C1 containing melamine only, at 35% loading in the final foam, achieved a V-2 rating. By replacing 6% Melamine with NOFIA OL1001 (example 4-B), a V-0 is achieved. The incorporation of silica was observed to improve upon the fire performance of the foam, especially dripping, is mitigated. Silica is particularly effective when used in combination with melamine and NOFIA OL1001. No self-extinguishing (NR) was observed for the foam containing 29.5% melamine and 0.5% silica without NOFIA OL1001. Increasing the loading of silica from 0.5% to 1.0% (example 4-D) improves the FR rating to no rating (NR) to V-2. Replacing part of the melamine (8.3%) with NOFIA OL1001 (example 4-E and 4-D) improved the rating to V-l. Incorporation of a EO-PEO copolymer, as Pluronic L62LF was observed to further enhance the FR properties (example 4-G) and V-0 was achieved.

TABLE 4

[0119] Example 5

Table 5 discloses the fire properties of the foam formulations prepared using a premix of NOFIA

OLlOOl/Isocyanate/Polyol to simplify the process. A modification was made to the standard experimental protocol and a prepolymer of isocyanate, NOFIA OL1001 and Polyol at a ratio of 70/15/15

(Isocyanate/NOFIA OLlOOl/Polyol) was prepared first. In example 5 -A, melamine, surfactants, catalysts and silica were then charged into the beaker containing Jeffol G-31-28 and the premix of

Isocyanate/NOFIA OLlOOl/PolyG-55-56 charged last to initiate the foaming process. In example 5-B, an extra surfactant, Pluronic L62LF, is also used. Both foam prepared using the modified process achieved V-0 in the UF-94 test and the density values achieved ranged between 110 and 125 kg/m³. The comparative examples 5 -Cl containing melamine at 29% and silica at 1% loading, failed to achieve V0.

TABLE 5

[0120] Example 6

Table 6 shows examples of compositions used to make foams that achieve VO at density at 70-80 kg/m³ . Comparative example (6-C1) shows the formulation with melamine only, without the NOFIA OL1001 does not self extinguish (no rating NR). The addition of 9.3% NOFIA OF1001 in example 6-A shows the foam self-extinguishes, but fails due to some burning drips. Example 6-B shows the foam containing the addition of 3 php silica to melamine and NOFIA OF1001 achieves V0 rating. TABLE 6

[0121] Example 7

[0122] Table 7 shows an example of a composition used to make 0.5 inch foams that are able to achieve V0 at density of 190 kg/m³ (0.5 inch thickness) with combination of melamine, NOFIA OL1001 and silica.

TABLE 7

[0123] Example 8

[0124] Table 8 shows examples of compositions used to make flexible polyurethane foams of 40 kg/m³ density containing NOFIA OL1001. The NOFIA OF 1001 was used in powder form and dispersed into the Specflex NF766 polyol. The combination of two silicon surfactants (Dow Coming 1280 additive and Tegostab B4113) was tested to determine the best foam cell structure when NOFIA OF 1001 incorporated into the low density foam. Visual observation of a cross-section of the foams showed the samples prepared with the highest loading of the Dow Coming 1280 additive (Example 8-D) had the best consistency in cell structure. Analysis of the foams determined 90-94% of NOFIA OF 1001 had reacted into the foam. Foams with 6php NOFIA OF1001 and 6php melamine pass the flame test FMVSS302. TABLE 8

[0125] Those skilled in the art will know or be able to ascertain using no more than routine experimentation, many equivalents to the embodiments and practices described herein. Accordingly, it will be understood that the invention is not to be limited to the embodiments disclosed herein, but is to be understood from the following claims, which are to be interpreted as broadly as allowed under the law.

[0126] The section headings used herein are for organizational purposes only and are not to be construed as limiting. While the applicant’s teachings are described in conjunction with various embodiments, it is not intended that the applicant’s teachings be limited to such embodiments. On the contrary, the applicant’s teachings encompass various alternatives, modifications, and equivalents, as will be appreciated by those of skill in the art.

Claims

What is claimed is:

1. A halogen-free composition comprising:

Part A:

at least one isocyanate;

Part B:

(1) at least one isocyanate reactive polyether polyol; and

2. A halogen-free composition comprising:

Part A:

Part B:

(2) a phosphonate oligomer; and

3. The halogen-free composition of claim 1 or 2, wherein one of the polyether polyol contains a content of ethylene oxide units of at least about 20% to about 100%

4. The halogen-free composition of claim 1 or 2, wherein the composition has a density ranging from about 80 kg/m³ to about 140 kg/m³.

5. The halogen-free composition of claim 1 or 2, wherein the composition has a density ranging from about 20 kg/m³ to about 80 kg/m³.

6. The composition of claim 1 or 2, wherein the co-flame retardant does not comprise graphite.

7. The composition of claim 1 or 2, wherein the composition is a polyurethane foam.

8. The composition of claim 7, wherein the polyurethane foam is a flexible polyurethane foam.

9. The composition of claim 1 or 2, wherein the co-flame retardant is selected from the group consisting in ammonium polyphosphate, melamine polyphosphate, melamine, melamine cyanurate, aluminum trihydrate, carbon nanotubes, silica, or any combinations thereof.

10. The composition of claim 7, wherein the composition loses a maximum of about 50% of its tensile strength after heat aging at least about 150 °C for about 7 days.

11. The composition of claim 7, wherein the composition achieves FMVSS302 rating.

12. The composition of claim 7, where the composition achieves a V-0 rating at about 0.5 inch

according to Underwriter’s Laboratories Standard UL94 Flammability test before and after heat aging.

13. A method for producing a flexible polyurethane foam comprising the composition any of claims 1 to 12, wherein Part A and Part B are mixed and reacted to form a foam.

14. A halogen-free flexible polyurethane foam according to any of claims 1 to 12 for use in thermal applications including engine compartment of vehicle, underbody thermal part, or a combination thereof.

15. A halogen-free composition comprising:

Part A:

Part B:

16. The halogen-free composition of claim 14, wherein one of the polyether polyol contains a content of ethylene oxide units of at least about 20% to about 100%