Polyurethane-acrylic hybrid composition for flame retardant products

Abstract

Polyurethane acrylate hybrid compositions may contain a polyurethane phase and a polyacrylate phase, the polyurethane phase containing a reaction product of: an isocyanate component including one or more isocyanate compounds, and an isocyanate-reactive component comprising one or more poly ether polyols; and the poly(meth)acrylate phase comprising a reaction product of: one or more polyfunctional phospho(meth) acrylate monomers having an acrylate functionality in the range of 2 to 8, one or more initiators, wherein the one or more polyfunctional phospho(meth)acrylate monomers and initiators are independently present in at least one of the isocyanate component, the isocyanate-reactive component, or a third component that is introduced upon combination of the isocyanate component and isocyanate-reactive component.

Description

[0001]85609-US-PSP POLYURETHANE-ACRYLIC HYBRID COMPOSITION FOR FLAME RETARDANT PRODUCTS Field Embodiments relate to polyurethane acrylate hybrid compositions containing an interpenetrating network of polyurethane and phosphate-containing polyacrylate, and methods of using same. Introduction Polyurethane and polyurethane-containing elastomers find wide application in a number of fields where flame resistance (FR) properties are needed to ensure safety and reliability, particularly in electronic and electric vehicle (EV) applications, or for composites and structural components. Prior attempts to provide FR polyurethane foams have include the use of FR additives, such as halogenated, small molecule, and / or solid FR additives. However, the use of halogenated additives is a health and environmental risk, while small molecule FR additives plasticize polymer networks reducing mechanical properties such as glass transition temperature, stiffness, and modulus. FR additives that are not covalently bound to the polymer network may leach out the material during the lifetime of the materials, par especially at elevated temperatures. Thus, options for PU elastomer-based materials having high strength, high softening point (i.e., glass transition temperature), and low viscosity during application are limited, particularly in applications such as EV battery potting, gap filling, insulation layers, and / or pultruded composites. Summary Embodiments disclosed herein include polyurethane acrylate hybrid composition, containing a polyurethane phase and a polyacrylate phase, the polyurethane phase containing a reaction product of: an isocyanate component including one or more isocyanate compounds, and an isocyanate-reactive component comprising one or more polyether polyols; and the poly(meth)acrylate phase comprising a reaction product of: one or more polyfunctional phospho(meth)acrylate monomers having an acrylate functionality in the range of 2 to 8, one or more initiators, wherein the one or more polyfunctional phospho(meth)acrylate monomers and initiators are independently present in at least one of the isocyanate component, the isocyanate- reactive component, or a third component that is introduced upon combination of the isocyanate component and isocyanate-reactive component. In some cases, embodiments also include articles formed from polyurethane acrylate hybrid compositions, including articles having UL-94 ratings of V2 or better at a thickness of ≤10 mm. 85609-US-PSP In another aspect, embodiments disclosed herein include methods of preparing a polyurethane acrylate hybrid composition including, combining to form a mixture: an isocyanate component including one or more isocyanate compounds; an isocyanate-reactive component comprising one or more polyether polyols; and an optional third component; wherein one or more (meth)acrylate monomers having an acrylate functionality in the range of 2 to 8, and one or more initiators are, independently, present in at least one of the isocyanate component, the isocyanate- reactive component, or the optional third component; and reacting the mixture to form the polyurethane acrylate hybrid composition. In another aspect, embodiments disclosed herein include methods of preparing composite articles, include: disposing on a substrate or extruding through a die chamber, a polyurethane acrylic hybrid composition prepared by combining to form a mixture including: a polyurethane phase comprising a reaction product of:an isocyanate component including one or more isocyanate compounds, and an isocyanate-reactive component comprising one or more polyether polyols; a poly(meth)acrylate phase comprising a reaction product of: one or more polyfunctional phospho(meth)acrylate monomers having an acrylate functionality in the range of 2 to 8, one or more initiators, wherein the one or more polyfunctional phospho(meth)acrylate monomers and initiators are independently present in at least one of the isocyanate component, the isocyanate- reactive component, or a third component that is introduced upon combination of the isocyanate component and isocyanate-reactive component; and one or more fillers and / or one or more reinforcement materials. Detailed Description Embodiments relate to polyurethane (PU) acrylate hybrid compositions containing an interpenetrating network of polyurethane and polyacrylate phases, and having a UL-94 vertical burn performance of V2 or better at sample thickness of 10 mm or lower. PU acrylate hybrid compositions may include a polyacrylate network containing one or more polyfunctional phosphoacrylate monomers that provide FR performance and mechanical strength. Methods may include reacting an isocyanate component and an isocyanate-reactive component in the presence of an orthogonal polymerization of (meth)acrylate monomer(s) and initiator(s) to generate the PU acrylate hybrid composition. PU acrylate hybrid compositions may be used in a number of applications such as battery encapsulation or potting (completely or partially or layered with other materials) and / or in pultruded or molded composites. As used herein, use of “(meth)” in conjunction with various acrylate or acrylate species indicates that the scope of the specification covers both the acrylate and / or methacrylate variations of the referenced compound. 85609-US-PSP As used herein, the term “interpenetrating polymer network” (i.e, IPN) is intended to mean an entangled network of two (or more) polymer phases obtained by simultaneous and / or sequential polymerization and / or crosslinking of two or more types of monomers to generate a mixed polymer product having a single and / or multiple glass transition temperature range from two or more entangled but independent crosslinked networks. Interpenetrating networks are distinguishable from a mixture of preformed polymer networks as containing individual polymer phases that are at least partially interlaced on a molecular scale, but which are not covalently bonded to each other and cannot be separated without breaking and / or disruption and / or degradation. The IPN with two independent networks in same material is also referred as dual and / or double network in some literature. PU acrylate hybrid compositions may be prepared through the orthogonal polymerization of the respective PU and poly(meth)acrylate phases that develop in the same reacting blend. PU acrylate hybrid compositions may be generated by reacting an isocyanate component with an isocyanate-reactive component, while the acrylate phase is generated through the reaction of one or more (meth)acrylate monomers and a free radical initiator system. The (meth)acrylate monomers and free radical initiator may be disposed in the isocyanate and / or isocyanate-reactive component, or combined as a third component upon combination of the isocyanate and isocyanate- reactive components. The (meth)acrylate monomers and free radical initiator system may be combined in a single component or divided among one or more components. The PU phase within the PU acrylate hybrid composition may include an isocyanate component containing one or more isocyanate compounds, such as polymeric isocyanates, aromatic isocyanates, or carbodiimide-modified isocyanates. Isocyanate compounds may be monomeric, oligomeric, prepolymers, and the like. The isocyanate component can include, for example, one or more isocyanate and / or polyisocyanate compounds. Isocyanate components may include isocyanate compounds having a nominal functionality of ≥1.5, or ≥2.0. The isocyanate component may include an isocyanate compound having a number average molecular weight of 150 g / mol to 750 g / mol. In some cases, the isocyanate compound can have a number average molecular weight from a low value of 150 g / mol, 200 g / mol, 250 g / mol or 300 g / mol to an upper value of 350 g / mol, 400 g / mol, 450 g / mol, 500 g / mol or 750 g / mol. The number average molecular weight values reported herein are determined by end group analysis, gel permeation chromatography, and other methods as is known in the art. The isocyanate compound can be monomeric and / or polymeric, as are known in the art. The isocyanate component may include on or more of aliphatic polyisocyanate, cycloaliphatic polyisocyanate, aliphatic polyisocyanate, aromatic polyisocyanate, and the like. 85609-US-PSP Examples of isocyanates include, but are not limited to, polymethylene polyphenylisocyanate; toluene 2,4- / 2,6-diisocyanate (TDI); methylenediphenyl diisocyanate (MDI, including its isomers); polymeric and prepolymeric MDI; triisocyanatononane (TIN); naphthyl diisocyanate (NDI); 4,4’-diisocyanatodicyclohexyl-methane; 3-isocyanatomethyl-3,3,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI); tetramethylene diisocyanate; hexamethylene diisocyanate (HDI); 2-methyl-pentamethylene diisocyanate; 2,2,4-trimethylhexamethylene diisocyanate (THDI); dodecamethylene diisocyanate; 1,4-diisocyanatocyclohexane; 4,4’- diisocyanato-3,3’-dimethyl-dicyclohexylmethane; 4,4’-diisocyanato-2,2-dicyclohexylpropane; 3- isocyanatomethyl-1-methyl-1-isocyanatocyclohexane (MCI); 1,3 -diisooctylcyanato-4 - methylcyclohexane; 1,3 -diisocyanato-2-methylcyclohexane; and combinations thereof, among others. In addition to the isocyanates mentioned above, partially modified polyisocyanates including uretdione, isocyanurate, carbodiimide, uretonimine, allophanate or biuret structure, and combinations thereof, among others, may be utilized. Isocyanate compounds may include isocyanate prepolymers resulting from reaction of an isocyanate-reactive compound with a molar excess of an isocyanate compound or polymeric isocyanate compound under conditions that do not lead to gelation or solidification, the isocyanate prepolymers can have a higher average isocyanate equivalent weight of > 140 g / eq (indirectly calculated by isocyanate content measured using ASTM D5155 and then using 4200 divided by isocyanate content to get the isocyanate equivalent weight). Formation of isocyanate prepolymers is known in the art, and may include reacting (1) at least one isocyanate compound and (2) at least one polyol compound. Isocyanate prepolymers may be described by an isocyanate index, defined as the ratio of isocyanate groups to isocyanate-reactive groups (such as OH groups) multiplied by 100. Isocyanate prepolymers disclosed herein may have an isocyanate index, defined as the equivalents of isocyanate divided by the total equivalents of isocyanate-reactive hydrogen containing materials, multiplied by 100) in a range of from 20 to 350, 30 to 300, or 40 to 200. Isocyanate prepolymers may have an isocyanate (NCO) content by weight according to ASTM D5155 of 1% or more, 2.5% or more, or 5% or more, and at the same time, 40% or less, 35% or less, or 30% or less, or in a range of 1% to 40%. Examples of commercial isocyanates include, but are not limited to, polyisocyanates under the trade names VORANATE™, VORATRON™, PAPI , VORAFORCE™ and ISONATE available from Dow Chemical Company. PU acrylate hybrid compositions may include an isocyanate component at a percent by weight (wt%) ranging from 15 wt% to 80 wt%, 20 wt% to 80 wt%, or 20 wt% to 70 wt%. In some cases, the isocyanate component may be included in a range of 30 to 300 parts for every 100 of the isocyanate-reactive component. 85609-US-PSP Isocyanate-reactive components may include a polyol blend containing one or more polyether polyols, including mixtures of high and low molecular weight (MW) polyether polyols, one or more (meth)acrylate monomers, initiators, catalysts, surfactants, fillers, and other additives. Isocyanate-reactive components may include one or more polyether polyols prepared by polyaddition of alkylene oxides such as propylene oxide and / or ethylene oxide onto polyhydroxy functional starter compounds in the presence of catalysts known in the art. Polyether polyols may include a polyol functionalized with one or more equivalents of a C3 to C5 alcohol (or mixture of alcohols). Polyether polyols disclosed herein may include products obtained by the polymerization of a cyclic oxide, for example, ethylene oxide (“EO”), propylene oxide (“PO”), butylene oxide (“BO”), tetrahydrofuran, or epichlorohydrin. Polyether polyols may be produced by functionalizing a polyol with a polyether, or polymerizing a cyclic oxide in the presence of a polyol initiator having a functionality ranging from 2 to 8, or 2 to 5. As understood in the art, the initiator compound, or combination thereof, is generally selected based on desired functionality of the resulting polyether polyol. Polyether polyols may be formed with one or more polyol initiators such as neopentylglycol; 1,2-propylene glycol; trimethylolpropane; pentaerythritol; sorbitol; sucrose; glycerine; alkanediols, such as 1,6-hexanediol, 1,4- butanediol, 1,3-butane diol, 2,3- butanediol, 1,3-propanediol, 1,2-propanediol, 1,5-pentanediol, 2-methylpropane-1,3-diol, 1,4- cyclohexane diol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,5-hexanediol; ethylene glycol; diethylene glycol; triethylene glycol; 9(1)-hydroxymethyloctadecanol, 1,4- bishydroxymethylcyclohexane; hydrogenated bisphenol; 9,9(10,10)- bishydroxymethyloctadecanol; 1,2,6-hexanetriol; and combinations thereof. Polyether polyols may have a hydroxyl equivalent weight, defined as the weight average molecular weight of the polyol divided by the average number of hydroxyl groups or the average hydroxyl functionality of the molecule, in a range of 30 Da to 5000 Da, or 30 Da to 4000 Da. Isocyanate-reactive components may include one or more low MW polyether polyols having an average functionality of 2 to 8 or 2 to 5, and an average hydroxyl equivalent (was indirectly determined according to hydroxyl number measured according to ASTM D4274 D where hydroxyl equivalent weight equals to 56100 divided by hydroxyl number) of 450 Da or less, or in the range of 30 Da to 450 Da, or 30 Da to 400 Da. In some cases, low MW polyether polyols may have a number average molecular weight of 400 Da or less, or 200 Da or less. In some cases, the isocyanate-reactive component may include a low MW polyether polyol at a percent by weight ranging from 10 wt% to 90 wt%, or 20 wt% to 90 wt%. Isocyanate-reactive components may include one or more high MW polyether polyols having an average functionality in a range of 1 to 8 or 1 to 5, and an average hydroxyl equivalent 85609-US-PSP weight of 500 Da or more, or in the range of 500 Da to 10,000 Da, 500 Da to 8,500 Da, or 500 Da to 8,000Da. High MW polyether polyols may be prepared using the chemistries and polyol initiators as discussed above with respect to polyether polyols. High MW polyether polyols may have a primary hydroxyl content of greater than 40%, greater than 20%, or greater than 60%. Further, high MW polyether polyols may be capped with oligomers or polymers of ethylene oxide (EO-capped) that modify elongation properties and toughness when compared to rigid foams of similar density. EO-capped high MW polyether polyols may have an ethylene oxide (EO) content at a percent by weight (wt%) of 3 wt% to 80 wt%, 3 wt% to 50 wt%, or 3 wt% to 30 wt%. In some cases, high MW polyether polyols may include EO-capped polypropylene oxide having an EO content ranging from 3 wt% to 80 wt% or 3 wt% to 50 wt%, an average functionality ranging from 1 to 8, an average molecular weight ranging from 800 Da to 10,000 Da, and having greater than 40% or greater than 60% primary hydroxyl functional groups. Isocyanate-reactive components may include a high MW polyether polyol at a percent by weight (wt%) of the sum of all polyols in an isocyanate-reactive component ranging from 10 wt% to 90 wt%, or 20 wt% to 90 wt%. The weight ratio of high MW:low MW polyether polyols may be in the range of 5:1 to 1:5, 5:1 to 1:1, 4:1 to 1:4, 3:1 to 1:3, or 3:1 to 1:1. PU acrylate hybrid compositions may include a polyacrylate phase produced by the polymerization of one or more polyfunctional phosphor(meth)acrylate monomers. In some cases, polyfunctional phosphor(meth)acrylate monomers include phosphate compounds that are liquid at room temperature, resistant to hydrolysis, and are non-halogenated. Polyfunctional phosphor(meth)acrylate monomers may have 2 or more unsaturated hydrocarbon functional groups, such as acrylate, methacrylate, vinyl, allyl, alkenyl, and the like. Polyfunctional phosphor(meth)acrylate monomers may have a general formula of [R1O(R2O)m]nP(=O)(R3)3-n, where each R1is independently an acrylate, a C3 to C8 unsaturated carbonyl compound, or a C2 to C8 carbon chain containing at least one alkenyl group; m is 0 to 2; R2is a C2 to C5 carbon chain; n is 2 or 3, and R3is hydrogen, hydroxyl, or a C1 to C8 alkoxy. Polyfunctional phosphor(meth)acrylate monomers may include phosphate esters of an alcohol in which the alcohol also contains a polymerizable vinyl or olefinic group, such as diallyl hydrogen phosphate, divinyl phosphate, triallyl phosphate, and the like. Polyfunctional phosphor(meth)acrylate monomers may also include bis- or tri-(meth)acryloyloxyalkyl phosphates such as bis[2-(meth)acryloyloxyethyl] phosphate, 2-(meth)acryloyloxyethylphenyl acid phosphate, bis[3-(meth)acryloxypropyl]acid phosphate, 2-(meth)acryloyloxyethylphenyl 85609-US-PSP phosphonate, bis[2-acrylamido-2-methylpropane]phosphonic acid, bis[2-methylacrylamido-2- methylpropane]phosphonic acid, and the like. The isocyanate-reactive component may include one or more Polyfunctional phosphor(meth)acrylate monomers having an unsaturated double bond functionality ranging from 2 to 8, and number average molecular weights of 100 Da or more. The isocyanate-reactive component may include one or more polyfunctional phosphor(meth)acrylate monomers at a percent by weight (wt%) ranging from 1 wt% to 80 wt%, or 5 wt% to 75 wt%. In some cases, the one or more polyfunctional phosphor(meth)acrylate monomers may also be added to the isocyanate component, or to both the isocyanate component and the isocyanate-reactive components in various amounts such that the resulting composition has a percent by weight (wt%) of the monomers ranging from 0.5 wt% to 50 wt%. PU acrylate hybrid compositions may include an acrylate phase containing a fraction of one or more hydroxyalkyl (meth)acrylates, such as (meth)acrylate functionalized polyols and polyalkylene glycols (e.g., polyethylene glycol). Suitable hydroxyalkyl (meth)acrylates may include include hydroxy C1-10 alkyl (meth)acrylate monomers, such as hydroxyethyl acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate monomer, and the like. Suitable (meth)acrylate monomers include ethylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, nonanediol di(meth)acrylate, butylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate i.e., (PEG) di(meth)acrylate, dipropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, tris (2-hydroxyl-ethyl)isocyanurate triacrylate, ditrimethylolpropane tetra(meth)acrylate, and alkoxylated polyol derived di or polyacrylates, such as propoxylated neopentyl glycol diacrylate or propoxylated glycerol triacrylate, neopentyl glycol di(meth)acrylate, combinations of these, and the like. Preferred reactive diluents are diacrylates such as 1,6 hexanediol diacrylate, 1,9 nonanediol diacrylate, 1,4 butanediol acrylate, tricyclodecane dimethanol diacrylate, cyclohexane dimethanol diacrylate, cis / trans 1,3 / 1,4 cyclohexanedimethanol diacrylate, alkoxylated cyclohexane dimethanol diacrylates, tripropylene glycol diacrylate and the like. More preferred reactive diluents include propoxylated neopentyl glycol diacrylate, propoxylated glyceryl triacrylate and tripropylene glycol diacrylate, and the like. Isocyanate-reactive component may include one or more hydroxyalkyl (meth)acrylates at a percent by weight (wt%) in a range of 0 wt% to 60 wt%, or 1 wt% to 50 wt%. 85609-US-PSP PU acrylate hybrid compositions may include one or more initiators (e.g., free radical initiators) added to the isocyanate, isocyanate-reactive component, or as a third component introduced upon combination of the isocyanate and isocyanate-reactive components. The initiator includes but is not limited to peroxides, persulfides, peroxycarbonates, peroxyboric acid, quinones azo compounds or other suitable radical initiators that can initiate curing of a double bond-containing (meth)acrylate or vinyl compound. Initiators may be active, or activatable by redox, radical (thermal-initiation or photo-initiation), or combinations of any of those. Suitable initiators include azo compounds, such as 2,2-azobisisobutyronitrile (AIBN), and the like, or peroxides such as tert-butyl peroxybenzoate, butyl 4,4-di(tert-butylperoxy)valerate, di- tert butyl peroxide, di-tert-amyl peroxide, dicumyl peroxide, di(tert-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di(tert-butylperoxyl)hexane, tert-butyl cumyl peroxide, 2,5-dimethyl- 2,5-di(tert-butylperoxyl)hexyne-3, di-tert-butyl peroxide, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7- triperoxonane, isopropylcumyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumyl hydroperoxide, tert-butyl hydroperoxide, and the like, or ketones such as benzophenone, camphorquinone, thioxanthone, and the like. Examples of a commercially available initiators are LUPEROX®DI, LUPEROX®10, and LUPEROX®P from Arkema, IRGACURE ® 819, IRGACURE ® 651, and IRGACURE ® 819 from Ciba, among other commercially available radical initiator(s) and / or generator(s). Additionally, one or more photo-sensitive radical initiator undergoing either Norrish Type I or Norrish Type II mechanism can be used in either isocyanate and / or isocyanate-reactive component and / or as a separate component. Polyurethane acrylate hybrid compositions may include one or more initiators at a percent by weight (wt%) of the isocyanate and / or isocyanate-reactive components ranging from 0.1 wt% to 20 wt%, 0.1 wt% to 10 wt%, or 0.25 wt% to 10 wt%. In some cases, the initiator may be added to the isocyanate or isocyanate-reactive component at a percent by weight (wt%) ranging from 0.1 wt% to 20 wt%, 0.1 wt% to 10 wt%, or 0.25 wt% to 10 wt%. PU acrylate hybrid compositions may include a poly(meth)acrylate phase prepared from the one or more polyfunctional phosphor(meth)acrylate monomers, optional hydroxyalkyl (meth)acrylates, and initiator is present at a percent by weight (wt%) of the PU acrylate hybrid composition in a range of 0.25 wt% to 20 wt%, 0.25 wt% to 10 wt%, or 0.5 wt% to 10 wt%. Isocyanate-reactive components may include one or more polyester polyols produced by the reaction of one or more carboxylic diacids and polyols having an OH functionality 2 to 4. Suitable carboxylic acids may include aromatic diacids or anhydrides such as phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, methyl esters of phthalic, isophthalic, or terephthalic acid, dimethyl terephthalate, trimellitic anhydride, pyromellitic dianhydride, or 85609-US-PSP mixtures thereof; and C4 to C12 aliphatic diacids. Suitable polyols for the formation of polyesters include one or more alkylene glycols or polyalkylene glycols having a hydroxy functionality of 2 to 4, such as ethylene glycol, 1,2- or 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, glycerine, and the like. Example polyester polyols include polyesters of phthalic anhydride and diethylene glycol, and polyesters of a C4 to C12 diacid such as succinic acid or adipic acid and diethylene glycol. Polyester polyols may have an average hydroxyl number (OH number) as determined according to ASTM D4274-21 in a range of 100 mg KOH / g to 500 mg KOH / g, 150 mg KOH / g to 450 mg KOH / g, or 200 mg KOH / g to 450 mg KOH / g. Isocyanate-reactive components may include one or more polyester polyols at a percent by weight (wt%) ranging from 10 wt% to 40 wt%, from 15 wt% to 35 wt%, or from 15 wt% to 30 wt%. Isocyanate-reactive components may include one or more polyol crosslinkers having a hydroxyl functionality of at least 3 and a weight average molecular weight of 800 g / mol or less. Suitable polyol crosslinkers may include glycerol, diglycerol, triglycerol, trimethylolpropane, di(trimethylolpropane), pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, derivatives like alkoxylates, or combinations thereof. Isocyanate-reactive components may include one or more polyol crosslinkers at a percent by weight (wt%) of 1 wt% to 15 wt%, 1 wt% to 10 wt%, or 1 wt% to 5 wt%. Isocyanate-reactive components may include one or more catalysts for enhancing polyurethane polymerization to generate the PU acrylate hybrid composition. Catalysts may be used individually or as a catalyst package containing multiple catalysts, such as gelling catalysts, blowing catalysts, and trimerization catalysts. Gelling and blowing catalysts may be differentiated by a tendency to favor either the urethane (gel) reaction, in the case of the gelling catalyst, or the urea (blow) reaction, in the case of the blowing catalyst. A trimerization catalyst may be utilized to promote the isocyanurate forming reaction in the compositions. The catalyst package can also be added as a separate stream into the reaction mixture of isocyanate and isocyanate-reactive composition. Gelling catalysts include organometallic compounds, cyclic tertiary amines and / or long chain amines, e.g., that contain several nitrogen atoms and combinations thereof. Organometallic compounds include organotin compounds, such as tin(II) salts of organic carboxylic acids, e.g., tin(II) diacetate, tin(II) dioctanoate, tin(II) diethylhexanoate, and tin(II) dilaurate, and dialkyltin(IV) salts of organic carboxylic acids, e.g., dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate and dioctyltin diacetate. Bismuth salts of organic carboxylic acids may also be utilized as the gelling catalyst, such as, for example, bismuth octanoate. Cyclic tertiary amines 85609-US-PSP and / or long chain amines include dimethylbenzylamine, triethylenediamine, and combinations thereof. Examples of a commercially available gelling catalysts are POLYCAT®8, DABCO®33-LV, and DABCO®T-12 from Evonik, among other commercially available gelling catalysts. Blowing catalysts may include bis-(2-dimethylaminoethyl)ether; pentamethyldiethylenetriamine, triethylamine, tributyl amine, N,N-dimethylaminopropylamine, dimethylethanolamine, N,N,N′,N′-tetra-methylethylenediamine, and combinations thereof, among others. An example of a commercial blowing catalyst is POLYCAT®5, from Evonik, among other commercially available blowing catalysts. Trimerization catalysts may include any such catalysts known in the art. Examples of trimerization catalysts include N,N',N''-tris(3-dimethylaminopropyl) hexahydro-S-triazine; N,N- dimethylcyclo-hexylamine; 1,3,5-tris(N,N-dimethylaminopropyl)-s-hexahydrotriazine; [2,4,6-tris (dimethylaminomethyl) phenol]; potassium acetate, potassium octoate; tetraalkylammonium hydroxides such as tetramethylammonium hydroxide; alkali metal hydroxides such as sodium hydroxide; alkali metal alkoxides such as sodium methoxide and potassium isopropoxide; and alkali metal salts of long-chain fatty acids having 10 carbon atoms to 20 carbon atoms, and combinations thereof, among others. Some commercially available trimerization catalysts include, for example, DABCO®TMR-2, DABCO®TMR-20, DABCO®TMR-30, DABCO®TMR-7, DABCO®K 2097; DABCO®K15, POLYCAT®41, and POLYCAT®46, each from Evonik, among other commercially available trimerization catalysts. Catalysts may include a “latent catalyst” or “delayed catalyst,” which is defined as a catalyst compound that is of low catalytic activity or is relatively inactive at ambient temperatures, and which becomes more catalytically active, such as by disassociation, decoordination, ring opening, ionization, or tautomerization upon heating to effect catalysis of least one of the chemical reactions involved in making a PU foam. Ambient temperatures may range 15 °C to 32 °C, where room temperature is often around 23 °C. Latent / delayed catalysts can be gelling, blowing, and / or trimerization types of catalysts in terms of their function in the foaming process. The latent catalyst is often a subset of tertiary amine gelling catalysts (e.g., blocked tertiary amines based on 1,8-Diazabicyclo[5.4.0]undec-7- ene (DBU)) that include acid salts, phenolic salts, or complexes of a tertiary amine catalyst where the acid or phenolic is often a carboxylic acid or phenol species, but not limited to, such as formic acid, acetic acid, propionic acid, 2-ethylhexanoic acid, phenoxyacetic acid, gluconic acid, tataric acid, citric acid, phenol, nonylphenol, diisopropyl phenol, and the like; and mixtures thereof. Some useable commercially available latent catalysts include, for example, DABCO®TMR-30, 85609-US-PSP POLYCAT®SA2 LE, POLYCAT®SA-1 / 10, DABCO®8154, NIAX™ A-107, NIAX™C-31, NIAX™C-225, JEFFCAT™ ZF-54, JEFFCAT™ LED-204; and mixtures thereof. The catalyst or catalyst package may be present in the PU acrylate hybrid composition at a percent by weight (wt%) ranging from 0.1 wt% to 10 wt%, or 1 wt% to 7 wt%. In some cases, a catalyst package may be added to the isocyanate component and / or the isocyanate-reactive component in amount sufficient to provide the mixture with the corresponding weight percentages above. The PU acrylate hybrid composition may self-leveling, such that the composition is applied for EV battery encapsulation or potting product and settles into a flat level before reaching maximum cure with the final change in height post settling is < 25% of total height of the encapsulant. PU acrylate hybrid compositions may include one or more fillers and / or reinforcement materials including fiberglass, fiber, ceramics, silica, calcium carbonate, calcium oxide, kaolin, talc, mica, mullite, phlogopite, muscovite montmorillonite, smectite, bentonite, illite, chlorite, sepiolite, attapulgite, halloysite, vermiculite, laponite, rectorite, perlite, alumina, alumina trihydrate (ATH), hollow particulates (e.g., glass, ceramic, polymer), fly ash, Portland cement, concrete mixes or similar inorganic materials, and combinations thereof. In some cases, reinforcement materials include any one or more of short and or long glass fibers, short and or long carbon nanotubes, short and or long carbon fibers, short and or long polyester fibers, natural fibers, aramid fibers, nylon fibers, basalt fibers, boron fibers, silicon carbide fibers, asbestos fibers, whiskers, hard particles, metal fibers, surface-functionalized derivatives of thereof, and the like. Fillers and / or inorganic reinforcement materials may be surface functionalized with a treatment agent to modify hydrophobicity or hydrophilicity. Surface modification may include covalent and ionic attachment chemistries to attach functional groups, such as alkyl chains, siloxane, hydroxyl groups, amines, thiols, isocyanate, epoxies, acrylates, aromatics, hydrosilyl (i.e., SiH), and the like. Treatment agents may vary depending on the nature of the filler or inorganic reinforcement material. For example, silica surfaces may be modified with a silane treating agent to incorporate functional groups that react with, or modify the compatibility of, the filler the PU acrylate hybrid formulation. One or more fillers and / or reinforcement materials may be added at a percent by weight (wt%) of the composition ranging from 0 wt% to 85 wt%, or 5 wt% to 80 wt%, or 10 wt% to 75 wt%, or 10 wt% to 75. In some cases, fillers may be added to the isocyanate component and / or the isocyanate-reactive component in amount sufficient to provide the mixture with the corresponding weight percentages above. In some cases, articles may be formed from PU acrylate compositions, by combining isocyanate and isocyanate-reactive components, dispensing the 85609-US-PSP combined mixture on a reinforcement material, and processing the resulting composite by a suitable process (e.g., pultrusion, molding, etc.). PU acrylate hybrid compositions may include one or more silicone or organic defoamers added at a percent by weight (wt%) of the polyurethane acrylate hybrid composition in a range of 0.05 wt% to 5 wt%, 0.1 wt% to 1.5 wt%, or 0.1 wt% to 1 wt%. The isocyanate-reactive component may also contain one or more additives including blowing agents, surfactants, crosslinkers, plasticizers, fillers, smoke suppressants, fragrances, reinforcements, dyes, colorants, pigments, preservatives, odor masks, physical blowing agents, chemical blowing agents, secondary radical stabilizers / activators (such as N,N,4- trimethylaniline), flame retardants, including phosphate-based FR additives such as triethyl phosphate, 2-Hydroxyethyl methacrylate acid phosphate, and the like, internal mold release agents, biocides, antioxidants, UV stabilizers, antistatic agents, moisture scavenger, thixotropic agents, adhesion promoters, cell openers, and the like. While formulation components have been disclosed individually, it is envisioned that component elements (e.g., compounds in isocyanate or isocyanate-reactive components) may be included, excluded, or combined in any manner or subcombination utilizing the above mentioned concentration ranges and nested subranges. PU acrylate hybrid compositions may be formed generally by combining the isocyanate component and the isocyanate-reactive component to form a mixture by a suitable method (e.g., mixing, injection), while the compounds that form the (meth)acrylate phase (e.g., polyfunctional phospho(meth)acrylate monomers, hydroxyalkyl (meth)acrylates, initiator) are present, independently, or in the isocyanate or isocyanate-reactive component or both. The (meth)acrylate phase-forming compounds may also be added as a third component upon or during the mixing of the isocyanate and isocyanate-reactive components and before polyurethane formation. Polyurethane acrylate hybrid compositions may include a polyurethane phase and a polyacrylate phase, the polyurethane phase comprising a reaction product of: an isocyanate component including one or more isocyanate compounds, and an isocyanate-reactive component comprising one or more polyether polyols, catalyst, and optionally surfactant, defoamers, fillers, and stabilizers; and the poly(meth)acrylate phase comprising a reaction product of: one or more polyfunctional phospho(meth)acrylate monomers having an acrylate functionality in the range of 2 to 8, one or more initiators, wherein the one or more polyfunctional phospho(meth)acrylate monomers and initiators are independently present in at least one of the isocyanate component, the isocyanate-reactive component, or a third component that is introduced upon combination of the isocyanate component and isocyanate-reactive component. 85609-US-PSP PU acrylate hybrid compositions may be used in any suitable process for developing articles and composites, including molding, injection, vacuum infusion, pultrusion, and the like. In one method, PU acrylate hybrid compositions may be prepared by combining the isocyanate component, the isocyanate-reactive component, polyfunctional phospho(meth)acrylate monomers, optional hydroxyalkyl (meth)acrylates, and initiators to form a mixture; processing the mixture in a mold to produce a molded article; and demolding the molded article. Methods of preparing a polyurethane acrylate hybrid composition may include combining to form a reactive mixture: an isocyanate component including one or more isocyanate compounds; an isocyanate-reactive component comprising one or more polyether polyols; and an optional third component; where one or more polyfunctional phospho(meth)acrylate monomers, optional hydroxyalkyl (meth)acrylates, and initiators are, independently, present in one or more of the isocyanate component, the isocyanate-reactive component, or the optional third component; and reacting the mixture to form the polyurethane acrylate hybrid composition. The method of mixing and dispensing may include speedmixing, hand mixing, impeller mixing, low pressure mixing, high pressure mixing, impingement mixing, static dynamic mixing, or static mixing. PU acrylate hybrid compositions may be used to prepare a composite part. For the preparation of the composite part, a polyurethane-poly(meth)acrylate reactive composition is mixed with a reinforcement material or injected into the reinforcement material, e.g., by vacuum assisted resin transfer molding (VARTM) and / or resin transfer molding (RTM). In some cases, methods of preparing composite articles may include disposing on a substrate or extruding through a die chamber, a PU acrylic hybrid composition prepared by combining to form a mixture: an isocyanate component including one or more isocyanate compounds; an isocyanate-reactive component; and optional third component; where one or more polyfunctional phospho(meth)acrylate monomers, optional hydroxyalkyl (meth)acrylates, and initiators are, independently, present in one or more of the isocyanate component, the isocyanate-reactive component, or the optional third component; and curing the mixture to produce the composite article. Composite articles prepared using the inventive PU acrylate hybrid compositions may include one or more reinforcement materials at a percent by weight (wt%) in a range of 1 wt% to 90 wt%, 30 wt% to 90 wt%, 40 wt% to 85 wt%, or 40 wt% to 80 wt%. Composite articles prepared using the inventive PU acrylate hybrid compositions may further include one or more core materials that facilitates the molding and weight reduction of a composite material. Core materials may include polystyrene foams, polyester PET foams, 85609-US-PSP polyimide PMI foams, polyvinyl chloride foam, metal foams, celluloses, woods such as balsa wood, and the like. In some cases, methods of preparing composite articles include: disposing on a substrate or extruding through a die chamber, a polyurethane acrylic hybrid composition prepared by combining to form a mixture including: a polyurethane phase comprising a reaction product of:an isocyanate component including one or more isocyanate compounds, and an isocyanate-reactive component comprising one or more polyether polyols; a poly(meth)acrylate phase comprising a reaction product of: one or more polyfunctional phospho(meth)acrylate monomers having an acrylate functionality in the range of 2 to 8, one or more initiators, wherein the one or more polyfunctional phospho(meth)acrylate monomers and initiators are independently present in at least one of the isocyanate component, the isocyanate-reactive component, or a third component that is introduced upon combination of the isocyanate component and isocyanate-reactive component; and one or more fillers and / or one or more reinforcement materials. Composite articles may have a V2 or better rating in UL-94 vertical test at a thickness of ≤10 mm. PU acrylate hybrid compositions may produce articles and composites having excellent mechanical properties and a FR performance of UL 94 vertical burn rating of V2 or better, e.g., enhanced impact resistance and modulus, high thermal deformation temperature, high tensile and flexural strength, high resistance to fatigue, high ductility, and low shrinkage rate. Articles and composites may be used in automotive and / or stationary storage applications such as electric vehicle (i.e, EV) battery potting and / or encapsulation (completely or partially or layered with other materials). For example, polyurethane acrylate hybrid compositions may be used in EV battery assembly, where the composition is emplaced and self-levels before the target height is set by curing. Other applications include use as gap fillers, thermal barriers, and EV battery tray insulation layers, and enclosure composites manufactured using pultrusion or molding process. Articles and composites may also be used in the manufacture of wind generator blades, wind generator nacelle housings, watercraft propeller blades, hulls, interior and exterior automobile decorative parts, automobile bodies, radomes, machinery structural members, decorative parts and structural members for architectures and bridges, and the like. Composite articles prepared using the PU acrylate hybrid compositions disclosed herein may include one or more reinforcement materials at a percent by weight (wt%) in a range of 1 wt% to 90 wt%, 5 wt% to 90 wt%, 10 wt% to 80 wt%, 20 wt% to 80 wt%, or 25 wt% to 75 wt%. The amount of FR additive (i.e., polyfunctional phospho(meth)acrylate monomers, and other optional additives) can vary depending on factors such as the FR additive selected and 85609-US-PSP intended use of the polyurethane compositions to achieve the UL-94 vertical burn (and / or horizontal burn) performance of V2 or better, V1 or better, or V0. In some cases, the PU acrylate hybrid compositions may have a UL-94 of V2 or better, or V1 or better at a thickness of 10 mm or less. PU compositions may include one or more silicone or organic defoamers added at a percent by weight (wt%) of the polyurethane composition in a range of 0.05 wt% to 5 wt%, 0.1 wt% to 5 wt%, or 0.1 wt% to 4 wt%. While formulation components and properties have been disclosed individually, it is envisioned that component elements (e.g., compounds in isocyanate or isocyanate-reactive components) may be included, excluded, or combined in any manner or subcombination utilizing any of the above concentration ranges and nested subranges therein. Further, that the recited formulation properties may be similarly achieved through various combinations of the recited components within the recited ranges. The numerical ranges disclosed herein include all values from, and including, the lower and upper value and all values in between. Unless stated to the contrary, implicit from the context, or customary in the art, all parts and percentages are based on weight and all test methods are current as of the filing date of this disclosure. Examples The following examples are provided to illustrate the embodiments of the invention, but are not intended to limit the scope thereof. Table 1 provides the materials used in the following examples. Table 1: Materials used in the examples Com onent Descri tion Source - a , a 85609-US-PSP Comp. Methacrylate Additive HydroxyletTCI -2hyl methacrylateAmerica a In this example, inventive samples containing polyurethane acrylate hybrid compositions were assayed for physical properties over comparative examples containing PU alone, with a comparative phosphate additive, or a comparative methacrylate additive. Sample formulations are shown in Tables 2 and 3. Samples were prepared by blending formulation components by DAC 600.1 FVZ-K speedmixer in the proportions specified in Tables 3 and 4, with all units in grams unless otherwise specified. A and B side components were prepared separately and mixed. The mixture was poured into a mold and kept at 23°C until tack free. The plaques were then demolded, and the test specimen shapes were cut accordingly. The test specimens were then allowed to post cure at 100°C for 1 hour to ensure formation of the polyurethane and acrylate IPN. Table 2: Sample formulations for Example 1 CE1) 85609-US-PSP Total A + B 100 100 100 100 100 Weight % PU network in fin l m t ri l100 75 55 90 75 Component CE6 (%) CE 7 (%) IE1 (%) IE2 (%) Unless specified otherwise in the testing method, samples were generally prepared by mixing the respective components of the isocyanate-reactive component (Side B) using a DAC 600.1 FVZ-K speedmixer until evenly dispersed. The isocyanate component (Side A) was then combined such that the functional group index of OH groups to NCO groups is maintained to 100 and mixed. The mixture was poured into the appropriate mold (at 12.5 mm thickness or 3 mm thickness)and the mold was kept at 23°C until it turns tack-free on the surface. The test specimens for tensile strength (CE1-3 and IE1-2) and stress-strain (#6-8) were then post cured at 150 °C for 3 hours. This ensured complete cure of acrylate components in the formulations IE1-2. 85609-US-PSP Fire Resistance performance was determined using UL-94 vertical burn test (1): The solid materials prepared in a metal mold at 12.7 mm thickness was then cut to 10 mm thickness with 0.5 inch width and ≥ 10 cm length. The material strips were tested with a standard UL-94 vertical burn protocol and performance was categorized in appropriate category as per the UL guidance - V0, V1, V2, and Fail (defined as the sample being consumed to the sample clamp during and / or post the flame exposure). Glass transition temperature (2) and Storage modulus (3-5) were det3ermined according to dynamic mechanical analysis (DMA) to obtain glass transition temperature (Tg) with ASTM D5279-21 on an Advanced Rheometric Expansion System (ARES-G2, TA Instruments) equipped with liquid nitrogen environmental control and torsion rectangular fixtures. A rectangular sample was cut from the plaques prepared in metal molds, as per the procedure described above, at 2 mm thickness, and cut to dimensions of 45 mm length and 12.8 mm width. The sample length was lined up axial to the torsional axis, and the DMA was performed in torsional mode. The temperature was increased from -50 °C to 200 °C at a ramp rate of 3 °C / min. The frequency of testing was 1 Hz at 0.05% torsional strain, with an axial tensile force of 0.098 N applied to keep sample taut, and at a data collection interval of 30 sec per point. The temperature sweep was done twice to ensure complete cure of plaque and the properties from the second sweep was reported. The major output from the characterization identified were the storage modulus in shear modulus (G’), Loss modulus (G’’), and the peak of Tanδis assigned as the glass transition temperature (Tg). Ultimate tensile strength (6), Tensile modulus (7), Elongation at break (8) were all obtained using ASTM D1708 standard on MTS machine. The samples of 3 mm thickness were tested post molding and a minimum of 2 days of aging at ASTM conditions prior to testing. The microtensile samples were punched in a dog-bone shape. Table 4: Sample properties for Example 1 # P t it i E1 E2 E E4 E 85609-US-PSP 6 Ultimate tensile strength (MPa) ≥ 12 40.3 25 1.26 69.2Cannottest° C t # Property Criteria CE6 CE7 IE1 IE2 9 The results show that the control PU formulation (CE1) failed to show any rating during the UL-94 vertical burn test (property #1). CE2 and CE3included phosphate additive – 1 (TEP) at 25wt% and 45 wt%, respectively, to increase FR performance, but was accompanied by reduced mechanical and rheological performance. Additionally, the high loading of phosphate additive in CE3 appeared to increase brittleness, potentially due to the evaporation of the additive from the sample as the temperature increases during testing. Mechanical properties in CE3 were also impaired as evidenced by a significant reduction in glass transition temperature (property #2) to 54 °C and 87 °C (a 34% and 59 % decrease from CE1), and storage modulus (property #3-5). Particularly, storage modulus at the 75 °C was reduced 93% with respect to CE1. Comparative sample CE5 contained 10 wt% of polyfunctional phospho(meth)acrylate, which failed to achieve UL-94 flame resistance, while CE5 (containing 25 wt% monofunctional phosphor(meth)acrylate additive) showed high phase separation during cure, making it unsuitable for mechanical property testing. The use of dimethacrylates (CE6) and mono methacrylate (CE7) at 25 wt% in total formulation failed provide any flame resistance according to UL-94 tests. In inventive examples IE1 and IE2, respectively, the use of phosphate dimethacrylate at 25 wt% and 45 wt% demonstrated increased FR performance to V1 and V0, respectively over 85609-US-PSP CE1. While IE1 showed a similar FR performance to CE2 at same loading level of FR additive at 25 wt%, the mechanical properties of IE1 and IE2 were surprisingly superior to PU-based samples CE1 and CE5. Further, sample IE1 was homogenous in appearance and showed superior mechanical properties over CE5 containing phosphate monomethacrylate. This indicates that the polyfunctional (difunctional here) phosphates increase FR performance over monofunctional phosphates. Particulalry, increasing the concentration of polyfunctional phosphor(meth)acrylate to 10 wt% or more is shown to achieve V1 and V0 ratings. IE1 contained similar loading of FR additive of 25 wt% to CE2, however, the sample showed a 62 % increase (412 MPa more) in storage modulus at 25 °C (property #3) and up to 16 times increase at 75 °C (744 MPa more), which is attributed to the non-plasticizing nature of the phosphor(meth)acrylate additive forming an interpenetrating polymeric network. (i.e., IPN). Surprisingly, the IE1 demonstrated 1067 MPa (22% increase) of storage modulus G’ over PU control CE1 at 25°C and the tensile modulus increase of 55%. Thus, the phosphor(meth)acrylate additive improves FR performance as expected, but also reinforces polymer networks. Similarly, IE2 containing 45 wt% polyfunctional phosphor(methacrylate) further improved FR performance of the cured resin composition to V0 vertical burn rating, and improved tensile modulus (property #7) over CE1-CE3. While the foregoing is directed to exemplary embodiments, other and further embodiments may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.

Claims

85609-US-PSP Claims 1. A polyurethane acrylate hybrid composition, comprising a polyurethane phase and a polyacrylate phase, the polyurethane phase comprising a reaction product of: an isocyanate component including one or more isocyanate compounds, and an isocyanate-reactive component comprising one or more polyether polyols; and the poly(meth)acrylate phase comprising a reaction product of: one or more polyfunctional phospho(meth)acrylate monomers having an acrylate functionality in the range of 2 to 8, one or more initiators, wherein the one or more polyfunctional phospho(meth)acrylate monomers and initiators are independently present in at least one of the isocyanate component, the isocyanate-reactive component, or a third component that is introduced upon combination of the isocyanate component and isocyanate-reactive component.

2. The composition of claim 1, wherein the one or more polyfunctional phospho(meth)acrylate monomers have a general formula of [R1O(R2O)m]nP(=O)(R3)3-n, where each R1is independently a C3 to C8 unsaturated carbonylor C2 to C8 carbon chain containing at least one alkenyl group, acrylate, m is 0 to 2, R2is a C2 to C5 carbon chain, n is 2 or 3, and R3is hydrogen, hydroxyl, or a C1 to C8 alkoxy.

3. The composition of claim 1, wherein the polyurethane phase and the polyacrylate phase form an interpenetrating network.

4. The composition of claim 1, wherein the poly(meth)acrylate phase is present at a percent by weight (wt%) of the PU acrylate hybrid composition in a range of 5 wt% to 45 wt%.

5. The composition of claim 1, wherein the polyether polyol comprises: (i) at least one low molecular weight polyether polyol having an average functionality ranging from 2 to 8 and a hydroxyl equivalent weight in the range of 30 Da to 400 Da;85609-US-PSP (ii) at least one high molecular weight polyether polyol having an average functionality ranging from 2 to 8 and a hydroxyl equivalent weight in the range of 800 Da to 10,000 Da; 6. The composition of claim 1, wherein the polyether polyol comprises a mixture of a high MW polyether polyol and a low MW polyether polyol at a weight ratio of 5:1 to 1:

1.

7. The composition of claim 1, wherein the one or more polyether polyols have a hydroxyl equivalent weight ranging from 30 Da to 10,000 Da.

8. The composition of claim 1, further comprising a reinforcement material at a percent by weight (wt%) of 5 wt% to 80 wt%.

9. An article prepared from the polyurethane acrylate hybrid composition of claim 1.

10. The article of claim 9, wherein the article has a UL-94 rating of V2 or better at a thickness of ≤10 mm.

11. A method of preparing a polyurethane acrylate hybrid composition comprising, combining to form a mixture: an isocyanate component including one or more isocyanate compounds; an isocyanate-reactive component comprising one or more polyether polyols; and an optional third component; wherein one or more (meth)acrylate monomers having an acrylate functionality in the range of 2 to 8, and one or more initiators are, independently, present in at least one of the isocyanate component, the isocyanate-reactive component, or the optional third component; and reacting the mixture to form the polyurethane acrylate hybrid composition.

12. The method of claim 11, wherein the polyurethane acrylate hybrid composition is self- leveling prior to curing.

13. A method of preparing composite article, comprising: disposing on a substrate or extruding through a die chamber, a polyurethane acrylic hybrid composition prepared by combining to form a mixture comprising:85609-US-PSP a polyurethane phase comprising a reaction product of: an isocyanate component including one or more isocyanate compounds, and an isocyanate-reactive component comprising one or more polyether polyols; a poly(meth)acrylate phase comprising a reaction product of: one or more polyfunctional phospho(meth)acrylate monomers having an acrylate functionality in the range of 2 to 8, one or more initiators, wherein the one or more polyfunctional phospho(meth)acrylate monomers and initiators are independently present in at least one of the isocyanate component, the isocyanate-reactive component, or a third component that is introduced upon combination of the isocyanate component and isocyanate-reactive component; and one or more fillers and / or one or more reinforcement materials, wherein the composite article has a V2 or better rating in UL-94 vertical test at a thickness of ≤10 mm.

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