WO2016120203A1 - Thermoplastic compositions, multi-polymer compositions, methods of manufacture thereof, and composites prepared therefrom - Google Patents

Abstract

A thermoplastic composition including, based on the total weight of the composition, 20 to 90 wt.%, preferably 25 to 70 wt.%, more preferably 30 to 50 wt.% of a thermoplastic polymer, and 10 to 70 wt.%, preferably 20 to 60 wt.%, more preferably 35 to 55 wt.% of a polymerizable monomer solvent that is liquid at a temperature in a range of -10 to 120 °C, and includes an aryl acrylate compound having the structure (AA) wherein Z is hydrogen or methyl or ethyl or substituted or unsubstituted aryl, and A is an unsubstituted or substituted C6-C20 aryl, preferably an unsubstituted or monosubstituted C6-C20 aryl, and wherein the thermoplastic polymer is dissolved in the polymerizable monomer solvent at a temperature of less than or equal to 100°C, preferably 45 to 80°C, more preferably 60 to 70°C.

Description

THERMOPLASTIC COMPOSITIONS, MULTI-POLYMER COMPOSITIONS, METHODS OF MANUFACTURE THEREOF, AND COMPOSITES PREPARED

THEREFROM

BACKGROUND

[0001] Polyarylene ethers are a class of thermoplastic polymers with excellent mechanical and electrical properties, heat resistance, flame retardancy, low moisture absorption, and dimensional stability. As such, polyarylene ethers are widely used in automobile interiors, and electrical as well as electronic applications.

[0002] Polyarylene ethers can be very difficult to process by conventional methods (e.g., injection molding) as a result of their high melt viscosities and their high processing temperature relative to their oxidative degradation temperature. Consequently, polyarylene ethers are commonly blended with compatible polymers including polystyrene, polyamides, polyolefins, rubber-modified styrene polymers, and mixtures of polystyrene and

polycarbonate. Improvements in processing of the aforementioned blends of polyarylene ethers are often offset by a loss of mechanical strength (e.g., flexural modulus, flexural strength) and thermal properties (e.g., heat distortion temperature).

[0003] There has been extensive research and development surrounding the use of a reactive solvent in combination with a polyarylene ether. For example, epoxy resins have been investigated as a reactive solvent for the polyarylene ethers, where the polyarylene ether is first dissolved in an epoxy resin to form a solution. An article can be shaped from the solution and article subsequently cured at elevated temperatures. The properties of the article are largely determined by the polyarylene ether, however the use of an epoxy resin as the reactive solvent is not practical in a continuous melt process like injection molding because the epoxy resin needs a curing agent to set. The curing agent will, over time, accumulate in the injection molding barrel, thereby fouling the machine. Furthermore, the cure and subsequent phase separation occurs at a minimum temperature of 150°C, which is impractical in a molder environment.

[0004] Accordingly, there remains a need in the art for a polyarylene ether compositions including a polymerizable monomer as a reactive solvent that would solve the above-described processing problems while not adversely affecting the physical properties of the polyarylene ether. BRIEF DESCRIPTION

[0005] A thermoplastic composition comprises, based on the total weight of the composition, 20 to 90 wt.%, preferably 25 to 70 wt.%, more preferably 30 to 50 wt.% of a thermoplastic polymer; and 10 to 70 wt.%, preferably 20 to 60 wt.%, more preferably 35 to 55 wt.% of a polymerizable monomer solvent that is liquid at a temperature in a range of - 10 to 120 °C, and comprising, consisting essentially of, or consisting of an aryl acrylate compound having the structure

wherein Z is hydrogen, C1-C6 alkyl, or substituted or unsubstituted aryl, preferably hydrogen or methyl, and A is an unsubstituted or substituted C6-C20 aryl, preferably an unsubstituted or monosubstituted C6-C20 aryl; wherein the thermoplastic polymer is dissolved in the polymerizable monomer solvent at a temperature of less than or equal to 100°C, preferably 45 to 80°C, more preferably 60 to 70°C.

[0006] A method of manufacturing a thermoplastic composition comprises combining the components of the thermoplastic composition; and heating the combined components to a temperature of less than or equal to 130°C, or 70 to 120°C, or 80 to 1 10°C or 90 to 100° for a time effective to dissolve the thermoplastic polymer in the polymerizable monomer solvent.

[0007] A thermoplastic composition manufactured by the above-described method represents another aspect of the disclosure.

[0008] Another embodiment is a composite preform comprising the thermoplastic composition, and a reinforcing agent.

[0009] A method of making a composite preform comprises contacting a reinforcing agent with the thermoplastic composition, and optionally shaping the contacted reinforcing agent, preferably by molding.

[0010] A composite preform prepared by the above-described method is also disclosed.

[0011] A B-staged composite preform prepared by the method is also disclosed.

[0012] Another embodiment is a multi-polymer composition comprising, based on the total weight of the composition, 20 to 90 wt.%, preferably 25 to 70 wt.%, more preferably 30 to 50 wt.% of a thermoplastic polymer; and 10 to 70 wt.%, preferably 20 to 60 wt.%, more preferably 35 to 55 wt.% of a thermoset polymer comprising, consisting essentially of, or consisting of aryl acrylate compound units having the structure

wherein Z is hydrogen, C1-C6 alkyl, or substituted or unsubstituted aryl, preferably hydrogen or methyl, and A is an unsubstituted or substituted C6-C20 aryl, preferably an unsubstituted or monosubstituted C6-C20 aryl; wherein the thermoplastic polymer and the thermoset polymer form a miscible blend.

[0013] A method of making a multi-polymer composition comprises polymerizing the polymerizable monomer solvent of the thermoplastic composition to form a miscible blend comprising, based on the total weight of the composition, 20 to 90 wt.%, preferably 25 to 70 wt.%, more preferably 30 to 50 wt.% of a thermoplastic polymer; and 10 to 70 wt.%, preferably 20 to 60 wt.%, more preferably 35 to 55 wt.% of a thermoset polymer comprising, consisting essentially of, or consisting of aryl acrylate compound units having the structure

wherein Z is hydrogen, C1-C6 alkyl, or substituted or unsubstituted aryl, preferably hydrogen or methyl, and A is an unsubstituted or substituted C6-C20 aryl, preferably an unsubstituted or monosubstituted C6-C20 aryl.

[0014] A multi-polymer composition prepared by the above method represents another aspect of the disclosure.

[0015] Another embodiment is an article comprising the multi-polymer composition.

[0016] The above described and other features are exemplified by the following detailed description.

DETAILED DESCRIPTION

[0017] The inventors hereof have advantageously discovered that a thermoplastic composition comprising a thermoplastic polymer and a polymerizable monomer solvent that is a liquid at a temperature in a range of -10 to 120°C can be used to provide a miscible blend comprising the thermoplastic polymer and a thermoset polymer derived from the

polymerizable monomer solvent by heating the composition to a temperature of less than or equal to 120°C. The compositions are also useful in providing composite preforms and other articles. The use of the polymerizable monomer solvent precludes the use of additional solvent, which allows for a solvent removal step to be avoided completely during the preparation of the composites and articles. Furthermore, volatile impurities which can affect the properties of the composition, are greatly reduced.

[0018] The thermoplastic composition comprises a thermoplastic polymer.

Thermoplastic polymers are typically high molecular weight polymers. Examples of thermoplastic polymers that can be used include polyacetals, polyacrylics, polycarbonates, polystyrenes, polyolefins, polyesters, polyamides, polyaramides, polyamideimides, polyarylates, polyphenylene ethers, polyurethanes, epoxies, phenolics, silicones,

polyarylsulfones, polyethersulfones, polyphenylene sulfides, polysulfones, polyimides, polyetherimides, polysiloxane-polyimides, polysiloxanepolycarbonates,

polytetrafluoroethylenes, polyetherketones, polyetheretherketones, polyetherketoneketones, polybenzoxazoles, polyoxadiazoles, polybenzothiazinophenothiazines, polybenzothiazoles, polypyrazinoquinoxalines, polypyromellitimides, polyquinoxalines, polybenzimidazoles, polyoxindoles, polyoxoisoindolines, polydioxoisoindolines, polytriazines, polypyridazines, polypiperazines, polypyridines, polypiperidines, polytriazoles, polypyrazoles,

polycarboranes, polyoxabicyclononanes, polydibenzofurans, polyphthalides, polyacetals, polyanhydrides, polyvinyl ethers, polyvinyl thioethers, polyvinyl alcohols, polyvinyl ketones, polyvinyl halides, polyvinyl nitriles, polyvinyl esters, polysulfonates, polysulfides, polythioesters, polysulfones, polysulfonamides, polyureas, polyphosphazenes, polysilazanes, polypropylenes, polyethylenes, polyethylene terephthalates, polyvinylidene fluorides, polysiloxanes, or the like, or a combination comprising at least one of the foregoing thermoplastic polymers. In some preferred embodiments, the thermoplastic polymer is a poly(Ci-C4 alkyl)ene, a polyarylene ether, a polycarbonate, a polyetherimide, a

polyetheretherketone, a polyester, a poly(Ci-C6 alkyl) (meth)acrylate, a polyimide, a poly(phenylsulfone), a polystyrene, a poly(vinyl chloride), or a combination comprising at least one of the foregoing.

[0019] In an embodiment, the thermoplastic polymer comprises a polyphenylene ether. Polyphenylene ethers include those comprising repeating units having the structure

wherein each occurrence of Z¹ is independently halogen, unsubstituted or substituted C1-C12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1-C12 hydrocarbylthio, C1-C12 hydrocarbyloxy, or C2-C12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; and each occurrence of Z² is independently hydrogen, halogen, unsubstituted or substituted C1-C12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1-C12 hydrocarbylthio, C1-C12 hydrocarbyloxy, or C2-C12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms. 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. The 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. However, when the hydrocarbyl residue is described as substituted, it may, optionally, contain heteroatoms over and above the carbon and hydrogen members of the substituent residue. Thus, when specifically described as substituted, the hydrocarbyl residue can also contain one or more carbonyl groups, amino groups, hydroxyl groups, or the like, or it can contain heteroatoms within the backbone of the hydrocarbyl residue. As one example, Z¹ can be a di-n-butylaminomethyl group formed by reaction of a terminal

3,5-dimethyl-l,4-phenyl group with the di-n-butylamine component of an oxidative polymerization catalyst.

[0020] The polyphenylene ether can comprise molecules having

aminoalkyl-containing end group(s), typically located in a position ortho to the hydroxyl group. Also frequently present are tetramethyldiphenoquinone (TMDQ) end groups, typically obtained from 2,6-dimethylphenol-containing reaction mixtures in which tetramethyldiphenoquinone by-product is present.

[0021 ] The polyphenylene ether can be in the form of a homopolymer, a random copolymer, a graft copolymer, an ionomer, or a block copolymer. In some embodiments, the polyphenylene ether comprises 2,6-dimethyl-l,4-phenylene ether units optionally in combination with 2,3,6-trimethyl-l,4-phenylene ether units. In some embodiments, the polyphenylene ether consists of poly(2,6-dimethyl-l,4-phenylene ether). In some embodiments, the polyphenylene ether comprises less than or equal to 5 mole percent, or less than or equal to 3 mole percent, or less than or equal to 1 mole percent of end groups that react with the polymerizable monomer composition. Preferably, the polyphenylene ether is devoid of end groups that react with the polymerizable monomer. In some embodiments, the polyphenylene ether can be devoid of end groups that can physically interact with the polymerizable monomer by acting as a compatibilizer. Thus, the polyphenylene ethers used herein can exclude the reaction products of polyarylene ethers and functionalizing agents, such as acid-functionalized polyarylene ethers, anhydride-functionalized polyarylene ethers, (meth)acrylate-functionalized polyarylene ethers, vinyl-functionalized polyarylene ethers, allyl-functionalized polyarylene ethers, alkynyl-functionalized polyarylene ethers, and the like.

[0022] In some embodiments, the polyphenylene ether comprises a polyphenylene ether-polysiloxane block copolymer. As used herein, the term "polyphenylene ether- polysiloxane block copolymer" refers to a block copolymer comprising at least one polyphenylene ether block and at least one polysiloxane block.

[0023] In some embodiments, the polyphenylene ether-polysiloxane block copolymer is prepared by an oxidative copolymerization method. In this method, the polyphenylene ether-polysiloxane block copolymer is the product of a process comprising oxidatively copolymerizing a monomer mixture comprising a monohydric phenol and a

hydroxyaryl-terminated polysiloxane. In some embodiments, the monomer mixture comprises 70 to 99 parts by weight of the monohydric phenol and 1 to 30 parts by weight of the hydroxyaryl-terminated polysiloxane, based on the total weight of the monohydric phenol and the hydroxyaryl-terminated polysiloxane. The hydroxyaryl-diterminated polysiloxane can comprise a plurality of repeating units having the structure

wherein each occurrence of R⁸ is independently hydrogen, C1-C12 hydrocarbyl or C1-C12 halohydrocarbyl; and two terminal units having the structure

wherein Y is hydrogen, C1-C12 hydrocarbyl, C1-C12 hydrocarbyloxy, or halogen, and wherein each occurrence of R⁹ is independently hydrogen, C1-C12 hydrocarbyl or C1-C12

halohydrocarbyl. In a very specific embodiment, each occurrence of R⁸ and R⁹ is methyl, and Y is methoxy.

[0024] In some embodiments, the monohydric phenol comprises 2,6-dimethylphenol, and the hydroxyaryl-terminated polysiloxane has the structure

wherein n is, on average, 5 to 100, specifically 30 to 60.

[0025] The oxidative copolymerization method produces polyphenylene

ether-polysiloxane block copolymer as the desired product and polyphenylene ether (without an incorporated polysiloxane block) as a by-product. It is not necessary to separate the polyphenylene ether from the polyphenylene ether-polysiloxane block copolymer. The polyphenylene ether-polysiloxane block copolymer can thus be utilized as a "reaction product" that includes both the polyphenylene ether and the polyphenylene

ether-polysiloxane block copolymer. Certain isolation procedures, such as precipitation from isopropanol, make it possible to assure that the reaction product is essentially free of residual hydroxyaryl-terminated polysiloxane starting material. In other words, these isolation procedures assure that the polysiloxane content of the reaction product is essentially all in the form of polyphenylene ether-polysiloxane block copolymer.

[0026] The polyarylene ether can be prepared by the oxidative coupling of monohydroxyaromatic compounds such as 2,6-xylenol and/or 2,3,6-trimethylphenol.

Catalyst systems are generally employed for such coupling. They can contain heavy metal compounds such as copper, manganese or cobalt compounds, usually in combination with one or more ligands such as a secondary amine, tertiary amine, halide or combination comprising at least one of the foregoing.

[0027] In some embodiments, the polyphenylene ether has an intrinsic viscosity of 0.2 to 1 deciliter per gram measured by Ubbelohde viscometer at 25°C in chloroform. Within this range, the polyphenylene ether intrinsic viscosity can be 0.3 to 0.6 deciliter per gram. When the polyarylene ether is a poly(2,6-dimethyl-l,4-phenylene ether), the intrinsic viscosity range of about 0.3 to about 0.6 deciliter per gram can correspond to a number average molecular weight range of about 16,000 to about 25,000 g/mol (16,000 to about 25,000 Daltons (Da)).

[0028] In some embodiments, the polyphenylene ether is a poly(2,6-dimethyl-l,4- phenylene ether). In some embodiments, the polyphenylene ether has, on average, 0.7 to 1.1 hydroxyl groups per molecule.

[0029] The amount of thermoplastic polymer present in the thermoplastic

composition is 20 to 90 weight percent (wt.%), preferably 25 to 70 wt.%, more preferably 30 to 50 wt.%, based on the total weight of the thermoplastic composition.

[0030] In addition to the thermoplastic polymer, the thermoplastic composition also comprises a polymerizable monomer solvent. The polymerizable monomer solvent is preferably a liquid at a temperature in a range of -10 to 120°C.

[0031] The polymerizable monomer solvent comprises, consists essentially of, or consists of an aryl acrylate compound, which as used herein has the structure

wherein Z is hydrogen, C1-C6 alkyl, or substituted or unsubstituted aryl, and A is an unsubstituted or substituted C6-C20 aryl. In some embodiments, Z is hydrogen, C1-C6 alkyl, or unsubstiuted aryl, and A is an unsubstituted or monosubstituted C6-C20 aryl. In other embodiments, Z is hydrogen, methyl, ethyl, or unsubstiuted aryl, and A is an unsubstituted or C6-C20 aryl monosubstituted with a halogen, cyano, nitro, or C1-C4 alkyl. The aryl acrylate can be phenyl (meth)acrylate, preferably phenyl acrylate wherein Z is hydrogen and A is phenyl. A combination comprising more than one of the foregoing aryl acrylate compounds can be used.

[0032] The thermoplastic polymer is dissolved in the polymerizable monomer solvent at a temperature of less than or equal to 120°C, or less than or equal to 100°C, preferably 15 to 120°C, or 20 to 100°C, or 45 to 80°C, or 60 to 70°C.

[0033] In an embodiment, the polymerizable monomer solvent optionally further comprises a copolymerizable monomer different from the aryl acrylate compound. The polymerizable monomer different from the aryl acrylate compound co-dissolves with the aryl acrylate compound and the thermoplastic polymer and can be an ethylenically unsaturated compound. The polymerizable monomer different from the aryl acrylate compound can comprise an allyl- or vinyl-substituted aromatic compound (e.g., styrene), a (C1-C12 alkyl) (meth)acrylate, (meth)acrylonitrile, a (C1-C6 alkyl) fumarate ester, a fumarate anhydride, a vinylidene halide, a vinyl carboxylate, a (C1-C12 alkyl) vinyl ketone, or a combination comprising at least one of the foregoing. The polymerizable monomer different from the aryl acrylate compound can be, for example, styrene, 2,4-dichlorostyrene, p-methoxystyrene, p- methylstyrene, p-phenylstyrene, p-divinylbenzene, p-chloromethoxystyrene, alpha- methylstyrene, o-methyl-alpha-methylstyrene, m-methyl-a-methylstyrene, p-methyl-alpha- methylstyrene p-methoxy-a-methylstyrene, acrylonitrile, methacrylonitrile, fumaric acid, maleic acid, vinyl ketone, maleic anhydride, acrylic acid, methacrylic acid, vinylidene chloride, maleate ester, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, vinyl chloride, vinyl acetate, divinyl benzene, ethylene oxide, isobutene, alkyl vinyl ether, anetholle, indene, coumarone, benzofuran, 1 ,2-dihydronaphthalene, acenaphthylene, isoprene, chloroprene, trioxane, 1,3-dioxolane, propylene oxide, β-propiolactone, vinyl biphenyl, 1, 1-diphenyl- ethylene, 1-vinylnaphthalene, 2-vinylnaphthalene, 2-vinyl-pyridine, 4-vinylpyridine, 2,3- dimethylbutadiene, ethylene, propylene, allyltrimethylsilane, 3-butenyl-trimethylsilane, vinyl carbazone, Ν,Ν-diphenylacrylamide, and combinations comprising at least one of the foregoing.

[0034] In other embodiments, however, the thermoplastic composition has less than or equal to 5 wt.%, or less than or equal to 3 wt.%, or less than or equal to 1 wt.% of a copolymerizable allyl- or vinyl-substituted aromatic compound based on the total weight of the thermoplastic composition. Preferably, the thermoplastic composition is devoid of an allyl or vinyl-substituted aromatic compound. Exemplary allyl or vinyl-substitute aromatic compounds can include, for example, styrene, C1-C6 alkyl styrenes, halogenated styrenes, vinyl naphthalene, and the like.

[0035] In still other embodiments, the thermoplastic composition has less than or equal to 5 wt.%, less than or equal to 3 wt.%, or less than or equal to 1 wt.% of any additional monomer copolymerizable with the aryl acrylate compound, based on the total weight of the thermoplastic composition. Preferably, the thermoplastic composition is devoid of any additional monomer copolymerizable with the aryl acrylate compound.

[0036] In some embodiments, the thermoplastic composition has less than or equal to 5 wt.%, or less than or equal to 3 wt.%, or less than or equal to 1 wt.% of a monomer having two or more unsaturated groups, based on the total weight of the thermoplastic composition. Preferably, the thermoplastic composition is devoid of a monomer having two or more unsaturated groups. Exemplary monomers having two or more unsaturated groups can include, for example, divinyl benzene, trivinyl benzene, pentaerythritol tetra(meth)acrylate, 1, 1,1-trimethylolpropane triacrylate, or a combination comprising at least one of the foregoing

[0037] The polymerizable monomer solvent is present in the thermoplastic composition in an amount of 10 to 70 wt.%, preferably 20 to 60 wt.%, more preferably 35 to 55 wt.%, based on the weight of the total thermoplastic composition.

[0038] The thermoplastic composition can optionally further comprise a

polymerization initiator, preferably a free radical polymerization initiator. Free radical polymerization initiators can include photoinitiators and thermal initiators, and can include, for example, diazo compounds, peroxides, and the like. The polymerization initiator is preferably a thermal initiator having an activation temperature of 50 to 100°C, preferably 60 to 90°C. Exemplary free radical polymerization initiators include 2,2'-azobis(4-methoxy-2,4- dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile),

phenylethyl)azodiphenylmethane, 2,2'-azobisisobutyronitrile, dimethyl 2,2'- azobisisobutyrate, diethyl 2,2'-azobisisobutyrate, l, l '-azobis(l-cyclohexanecarbonitrile), 2,2'- azobis(2-methylbutyronitrile), 2,2'-azobis(2,4,4-trimethylpentane), 2-phenylazo-2,4- dimethyl-4-methoxyvaleronitrile, 2,2'-azobis(2-methylpropane), diacyl peroxides (e.g., such as dilauroyl peroxide, benzoyl peroxide, didecanoyl peroxide, succinoyl peroxide), organic hydroperoxides (e.g., cumyl hydroperoxide and tert-amyl hydroperoxide), dialkyl peroxydicarbonates (e.g., diethyl peroxydicarbonate, diisopropyl peroxydicarbonate, dimyristyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, di(2- ethylhexyl)peroxydicarbonate, di(4-tert-butyl)cyclohexyl peroxydicarbonate and dicetyl peroxydicarbonate), peresters (e.g., tert-amyl perpivalate, tert-butyl perpivalate, tert-amyl peroxyneodecanoate, tert-butyl peroxyneodecanoate and cumyl peroxyneodecanoate), and the like, and combinations comprising at least one of the foregoing. In some embodiments, the free radical polymerization initiator comprises benzoyl peroxide (BPO).

[0039] Before curing, the thermoplastic composition has less than or equal to 5 wt.%, preferably less than or equal to 3 wt.%, preferably less than or equal to 1 wt.% of a polymer comprising units derived from the polymerizable monomer solvent. Preferably, the thermoplastic composition before curing is devoid of a polymer comprising repeating units derived from the polymerizable monomer solvent. For example, when the polymerizable monomer solvent is phenyl acrylate, the thermoplastic composition can be devoid of a poly(phenyl acrylate).

[0040] In an advantageous feature, the thermoplastic composition generally comprises less than or equal to 10 wt.% of a non-reactive solvent, or less than or equal to 5 wt.% of a non-reactive solvent, or less than or equal to 1 wt.% of a non-reactive solvent, or less than or equal to 0.5 wt.% of a non-reactive solvent. More preferably, the composition is devoid of a non-reactive solvent, or a non-reactive solvent is excluded from the composition. Non-reactive solvents do not polymerize or copolymerize with the aryl acrylate compounds or other copolymerizable solvents. Such solvents include, for example, benzene, xylenes, chlorobenzenes, dimethyl sufoxide, acetone, chlorinated hydrocarbons (e.g., methylene chloride, 1, 1,1 -trichloroethane, perchloroethane, chloroform, dicholorobenzene,

trichlorobenzene, carbon tetrachloride, and the like, or a combination thereof),

dimethylformamide, and the like.

[0041] The thermoplastic composition can, optionally, further comprise one or more additives, for example, stabilizers, mold release agents, processing aids, flame retardants, drip retardants, nucleating agents, UV blockers, dyes, pigments, antioxidants, anti-static agents, blowing agents, mineral oil, metal deactivators, antiblocking agents, nanoclays, electrically conductive agents, and combinations thereof.

[0042] The thermoplastic composition comprising the thermoplastic polymer and the polymerizable monomer solvent can have a viscosity of 0.05 to 500 Pa.s (50 to 500,000 centipoise (cP)), alternatively 0.5 to 500 Pa.s (500 to 500,000 centipoise (cP)) at a temperature of less than or equal to 120°C. The viscosity of the thermoplastic composition can be dependent on the relative amount of each component present in the thermoplastic composition (e.g., percent solids content).

[0043] A method of manufacturing the above-described thermoplastic composition represents another aspect of the disclosure. In some embodiments, the thermoplastic composition is prepared by combining the thermoplastic polymer and the polymerizable monomer solvent, and any optional components, and heating the combined components to a temperature of less than or equal to 130°C, or 70 to 120°C, or 80 to 110°C or 80 to 100°C, or 80 to 90°C. The combined components can be heated for a time effective to dissolve the thermoplastic polymer in the polymerizable monomer solvent, for example, 1 to 30 minutes, or 5 to 20 minutes, or 10 to 15 minutes.

[0044] Another embodiment is a composite preform comprising the thermoplastic composition and a reinforcing agent. The reinforcing agents can be provided in the form of a reinforcing particulate, a fiber, a fabric, a porous material, or a combination comprising at least one of the foregoing. A fabric can be, for example, a woven or non- woven glass or carbon fabric. For example, a suitable fabric can comprise non-woven fabrics or woven fabrics comprising any of the following glass types: E, D, S, R, or a combination comprising at least one of the foregoing. Also suitable is NE type glass available from NittoBoseki Co., Fukushima, Japan. Suitable glass styles include, but are not limited to, 106, 1080, 21 12, 21 13, 21 16, and 7628, wherein the term glass style is known to those skilled in the art and refers to the size of glass fibers and number of fibers in a bundle. In other embodiments fabrics can comprise such materials as aramid such as KEVLAR® aramid available from DuPont, aramid/glass hybrid, or ceramic. In addition, woven fabrics of cellulose fibers can also be used. Fabrics can have a thickness from 5 to 200 micrometers, specifically 10 to 50 micrometers, and more specifically 10 to 40 micrometers. A reinforcing fiber can include single crystal fibers or "whiskers" such as silicon carbide, alumina, boron carbide, iron, nickel, copper, or the like, and fibers (including continuous and chopped fibers) such as asbestos, carbon fibers, glass fibers, such as E, A, C, ECR, R, S, D, or NE glasses, or the like. Reinforcing organic fibrous fillers formed from organic polymers capable of forming fibers such as poly(ether ketone), polyimide, polybenzoxazole, poly(phenylene sulfide), polyesters, polyethylene, aromatic polyamides, aromatic polyimides, polyetherimides,

polytetrafluoroethylene, acrylic polymers, poly(vinyl alcohol) or the like can also be used. Monofilament or multifilament fibers can also be used individually or in combination with other types of fiber, though, for example, co-weaving or core/sheath, side-by-side, orange- type or matrix and fibril constructions, or by other methods known to one skilled in the art of fiber manufacture. Co-woven structures include glass fiber-carbon fiber, carbon fiber- aromatic polyimide (aramid) fiber, and aromatic polyimide fiberglass fiber or the like.

Fibrous agents can be supplied in the form of, for example, rovings, woven fibrous reinforcements, such as 0-90 degree fabrics or the like; non-woven fibrous reinforcements such as continuous strand mat, chopped strand mat, tissues, papers and felts or the like; or three-dimensional reinforcements such as braids. As used herein, a "porous material" can be any material having any size pores or openings that may or may not be interconnected. The reinforcing agent can include a combination comprising at least one of the foregoing reinforcing agents.

[0045] In an embodiment, the composite comprises a fabric reinforcing agent impregnated with the thermoplastic composition. The fabric reinforcing agent can be a fabric comprising glass fibers, carbon fibers, aromatic polyamide fibers, or a combination comprising at least one of the foregoing fibers.

[0046] In another embodiment, the composite preform can be a B-staged preform comprising a reinforcing agent and the thermoplastic composition, wherein the thermoplastic composition further comprises a thermoset polymer comprising, consisting essentially of, or consisting of repeating units derived from partially polymerizing the polymerizable monomer solvent. Partially polymerizing the polymerizable solvent can refer to the conversion of 5 to 90 %, for example 10 to 80 wt.%, for example 20 to 70 wt.%, for example, 30 to 60 wt.% of the polymerizable monomer solvent to the corresponding polymer. The thermoset polymer derived from the polymerizable monomer solvent can have the structure

wherein Z is hydrogen, C1-C6 alkyl, or substituted or unsubstiuted aryl, and A is an unsubstituted or substituted C6-C20 aryl. In some embodiments, Z is hydrogen, C1-C6 alkyl, or unsubstiuted aryl, and A is an unsubstituted or monosubstituted C6-C20 aryl. In other embodiments, Z is hydrogen, methyl, ethyl, or unsubstituted aryl, and A is an unsubstituted or C6-C20 aryl monosubstituted with a halogen, cyano, nitro, or C1-C4 alkyl. Preferably, A is phenyl and Z is hydrogen. The reinforcing agent can be a fabric reinforcing agent impregnated with the thermoplastic composition comprising the thermoset polymer.

[0047] The composite preform can be prepared by a method comprising contacting the reinforcing agent with the thermoplastic composition at a temperature effective for the thermoplastic composition to wet the reinforcing agent. The contacting the reinforcing agent with the thermoplastic composition can comprise dipping or coating the reinforcing agent with the thermoplastic composition to impregnate the reinforcing agent with the composition. The method further optionally comprises the step of shaping the contacted reinforcing agent. Shaping the contacted reinforcing agent can be, for example, by molding. The temperature effective for the thermoplastic composition to wet the reinforcing agent can be less than or equal to 130°C, preferably 70 to 130°C, more preferably 80 to 1 10°C, even more preferably 90 to 100°C. The method advantageously excludes a solvent removal step.

[0048] The method can further optionally comprise a step of partially polymerizing the polymerizable monomer solvent to form a B-staged preform composite. Partially polymerizing the polymerizable monomer can be by heating the preform, exposing the preform to ultraviolet radiation, infrared radiation, microwave radiation, any other suitable radiation technique, or a combination comprising at least one of the foregoing, preferably at a temperature of less than or equal to 200°C. In an embodiment, the partially polymerizing comprises heating the preform to a temperature less than or equal to 180°C, preferably 70 to 120°C, more preferably 75 to 110°C, even more preferably 80 to 100°C, even more preferably, 90 to 100°C. In a preferred embodiment, the thermoplastic polymer comprises less than or equal to 5 mole percent, or less than or equal to 3 mole percent, or less than or equal to 1 mole percent of covalent links between the thermoplastic polymer and the polymerized monomer, based on total moles of the thermoplastic polymer. The mole percent of covalent links can be determined by nuclear magnetic resonance (NMR) spectroscopy, infrared spectroscopy, and the like.

[0049] A multi-polymer composition represents another aspect of the present disclosure. The multi-polymer composition comprises a thermoplastic polymer and a thermoset polymer. The thermoplastic polymer can be any of the aforementioned thermoplastic polymers, and can preferably be a polyphenylene ether. The thermoplastic polymer can be present in the multi-polymer composition in an amount of 20 to 90 wt.%, preferably 25 to 70 wt.%, more preferably 30 to 50 wt.%, based on the total weight of the composition.

[0050] The thermoset polymer included in the multi-polymer composition as used herein comprises, or consists essentially of, or consists of an aryl acrylate compound having units of the structure

wherein Z is hydrogen, C1-C6 alkyl, or substituted or unsubstiuted aryl, and A is an unsubstituted or substituted C6-C20 aryl. In some embodiments, Z is hydrogen, C1-C6 alkyl, or unsubstiuted aryl, and A is an unsubstituted or monosubstituted C6-C20 aryl. In other embodiments, Z is hydrogen, methyl, ethyl, or unsubstiuted aryl, and A is an unsubstituted or C6-C20 aryl monosubstituted with a halogen, cyano, nitro, or C1-C4 alkyl. Preferably, A is phenyl and Z is hydrogen. It is to be understood that the term "thermoset," when referring to the second included in the multi-polymer composition, is used for convenience to refer to the polymerization product of the polymerizable monomer solvent. Such polymers may also have thermoplastic characteristics.

[0051 ] The thermoplastic polymer and the thermoset polymer of the multi-polymer composition preferably form a miscible blend. The term "miscible blend" describes a polymer blend having a single glass transition temperature (Tg) and a monophasic resin morphology as determined by transmission electron microscopy at a magnification of fifteen thousand (15,000). The term "polymer blend" as used herein means a macroscopically homogeneous mixture of two or more different polymers. In some embodiments, the thermoplastic polymer and the thermoset polymer form an interpenetrating polymer network.

[0052] In some embodiments, the multi-polymer composition comprises less than or equal to 10 wt.% of a solvent, or less than or equal to 5 wt.% of a solvent, or less than or equal to 1 wt.% of a solvent, or less than or equal to 0.5 wt.% of a solvent. The composition can be devoid of a solvent, wherein a solvent is excluded from the composition. The multi- polymer composition can further comprise less than or equal to 5 mole percent, or less than or equal to 3 mole percent, or less than or equal to 1 mole percent of covalent links between the thermoplastic polymer and the polymerized monomer, based on total moles of the thermoplastic polymer.

[0053] The multi-polymer composition can have less than or equal to 5 wt.%, less than or equal to 3 wt.%, or less than or equal to 1 wt.% of a copolymerizable allyl- or vinyl- substituted aromatic compound based on the total weight of the multi-polymer composition. Preferably, the multi-polymer composition is devoid of an allyl or vinyl-substituted aromatic compound. Exemplary allyl or vinyl-substitute aromatic compounds can include, for example, styrene, C1-C6 alkyl styrenes, halogenated styrenes, vinyl naphthalene, and the like.

[0054] In some embodiments, the multi-polymer composition has less than or equal to 5 wt.%, less than or equal to 3 wt.%, or less than or equal to 1 wt.% of a monomer having two or more unsaturated groups, based on the total weight of the multi-polymer composition. Preferably, the multi-polymer composition is devoid of a monomer having two or more unsaturated groups. Exemplary monomers having two or more unsaturated groups can include, for example, divinyl benzene, trivinyl benzene, pentaerythritol tetra(meth)acrylate, 1, 1,1-trimethylolpropane triacrylate, bisphenol A diacrylate, tri ethylene glycol diacrylate, polyethylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, hydrogenated dicyclopentadienyl diacrylate, pentaetythritol hexaacrylate, ethylene oxide- modified bisphenol A diacrylate, trisacryloxy isocyanurate, polyfunctional epoxy acrylate, polyfunctional urethane acrylate, methacrylates corresponding to these acrylates, diethylene glycol bisallyl carbonate, and the like, or a combination comprising at least one of the foregoing.

[0055] The multi-polymer composition can have less than or equal to 5 wt.%, less than or equal to 3 wt.%, or less than or equal to 1 wt.% of any polymer units different from the aryl acrylate compound units, based on the total weight of the multi-polymer

composition. Preferably, the multi-polymer composition is devoid of any polymer units different from the aryl acrylate compound units. [0056] The multi-polymer composition can optionally comprise a thermoset polymer further comprising a polymer different from the above-described thermoset polymer derived from the aryl acrylate compound. For example, the polymer different from the aryl acrylate compound can be derived from an allyl- or vinyl-substituted aromatic compound, a (C1-C12 alkyl) (meth)acrylate, (meth)acrylonitrile, a (C1-C6 alkyl) fumarate ester, a fumarate anhydride, a vinylidene halide, a vinyl carboxylate, a (C1-C12 alkyl) vinyl ketone or a combination comprising at least one of the foregoing. In general, however, the reactive monomers will copolymerize.

[0057] The multi-polymer composition can be prepared by a method comprising polymerizing the polymerizable monomer solvent of the thermoplastic polymer composition to form a miscible blend comprising the thermoplastic polymer, and the thermoset polymer. Polymerizing the polymerizable monomer solvent can be by, for example, heating, exposing the composition to ultraviolet radiation, infrared radiation, microwave radiation, any other suitable method of irradiation, or a combination comprising at least one of the foregoing, preferably at a temperature of less than or equal to 180°C. In some embodiments, polymerizing the polymerizable monomer solvent is by heating to a temperature less than or equal to 180°C, preferably 70 to 120°C, more preferably 75 to 100°C, even more preferably 80 to 90°C, preferably in a single stage. In some embodiments, the polymerizing can optionally be conducted in two or more stages. In an embodiment, the method of preparing the multi-polymer composition can advantageously exclude a solvent removal step.

[0058] In some embodiments, the multi-polymer composition can further comprise a reinforcing agent. When present, the reinforcing agent can be contacted by the thermoplastic composition before polymerizing the polymerizable monomer to wet the reinforcing agent. For example, the reinforcing agent can be coated or impregnated with the thermoplastic composition to form a prepreg. The reinforcing agent preferably comprises a reinforcing particulate, a fiber, a fabric, a porous material, or a combination comprising at least one of the foregoing. After contacting the reinforcing agent with the thermoplastic composition, a B- staged prepreg can be prepared by partially polymerizing the polymerizable monomer solvent. The monomer solvent can optionally be fully polymerized in one or more additional steps.

[0059] The multi-polymer compositions prepared according to the above methods can be useful in various articles. For example, an article comprising the multi-polymer composition can be an electronic component, for example, a printed wiring board, an automobile interior component, for example an instrument panel, an arm rest, a top cover, and a car bumper, or a structural component for industrial construction and automotive applications.

[0060] The thermoplastic compositions and multi-polymer compositions disclosed herein can be used to provide a miscible blend comprising the thermoplastic polymer and a thermoset polymer derived from the polymerizable monomer solvent by heating the composition to a temperature of less than or equal to 120°C. The compositions require low curing temperatures, and the methods disclosed herein advantageously do not require the presence of a solvent. Therefore, solvent and other volatile impurities are excluded from the compositions and articles prepared therefrom, leading to improved products having fewer defects arising from entrapped volatiles. Therefore, a substantial improvement in thermoplastic compositions is provided.

[0061] The invention is further illustrated by the following non-limiting examples.

EXAMPLES

Comparative Example 1

[0062] Bulk polymerization of phenyl acrylate was performed using benzoyl peroxide (BPO) as a free radical initiator. The polymerization was carried out at 80°C under an inert nitrogen atmosphere. Within 2 hours, the polymerization mixture transformed from a highly viscous material to a transparent, solid. ^lH nuclear magnetic resonance (NMR) spectroscopy was used to characterize the material, and it was found that after 2 hours, greater than or equal to 85% conversion of phenyl acrylate to poly(phenyl acrylate) was achieved. Higher conversions (e.g., about 100%) were obtained with longer reaction times. The spectrum shows the appearance of broad peaks from about 1.6 to 3.2 ppm, characteristic of a polyacrylate backbone, confirming the polymerization of phenyl acrylate under these conditions.

[0063] The poly(phenyl acrylate) obtained by the above-described procedure was further characterized in terms of the thermal properties using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The poly(phenyl acrylate) had a glass transition temperature (Tg) of 56± 2°C, with degradation of the sample observed starting at 350°C. Comparative Example 1 confirms the successful polymerization of phenyl acrylate in the bulk at a temperature of 80°C. The DSC thermogram of the poly(phenyl acrylate) shows the glass transition temperature (Tg) to be 57°C.

Example 1 [0064] Phenyl acrylate was polymerized in the presence of polyphenylene ether (PPE) having a molecular weight of 53,000 g/mol (53,000 Daltons). A solution of PPE and phenyl acrylate in a 1 : 1 weight ratio was prepared by first dissolving benzoyl peroxide in the phenyl acrylate monomer solvent in an amount of 1 wt.% based on the total weight of the PPE and the phenyl acrylate. Following dissolution of the BPO, PPE was added and the mixture was thoroughly mixed to achieve a homogenous solution. The solution was heated to 80°C to polymerize phenyl acrylate. The compositions were highly viscous solutions or semisolids, depending on the wt.% of each component included in the composition. Polymerization was monitored using NMR. Thermal analysis of the resulting compositions was also conducted. Phenyl acrylate monomer peaks were observed from about 6.0 to 6.8 ppm. Thermal analysis showed two glass transition temperatures (Tg) at 56-59°C corresponding to the poly(phenyl acrylate) crystallization, and at 1 10-120°C corresponding to the homogenous blend of poly(phenyl acrylate) and polyphenylene ether.

[0065] Without wishing to be bound by theory, the glass transition temperature for a blend of two homopolymers is theoretically a value that is between the Tg of each of the corresponding homopolymers. The theoretical Tg can be calculated according to the Gordon- Taylor equation shown as equation 1, below.

¹ (Eq. 1)

[0066] Using equation 1, the theoretical Tg for a 1 : 1 blend by weight of poly(phenyl acrylate) and polyphenylene ether is 110°C based on the Tg of poly(phenyl acrylate) and polyphenylene ether being 56° and 210°C, respectively. The theoretical value of 110°C correlates to the experimentally observed value of 1 10-120°C.

[0067] The compositions and methods of manufacture are further illustrated by the following embodiments, which are non-limiting.

[0068] Embodiment 1. A thermoplastic composition comprising, based on the total weight of the composition, 20 to 90 wt.%, preferably 25 to 70 wt.%, more preferably 30 to 50 wt.% of a thermoplastic polymer; and 10 to 70 wt.%, preferably 20 to 60 wt.%, more preferably 35 to 55 wt.% of a polymerizable monomer solvent that is liquid at a temperature in a range of -10 to 120 °C, and comprising, consisting essentially of, or consisting of an aryl acrylate compound having the structure

wherein Z is hydrogen, C1-C6 alkyl, or substituted or unsubstituted aryl, preferably hydrogen or methyl, and A is an unsubstituted or substituted C6-C20 aryl, preferably an unsubstituted or monosubstituted C6-C20 aryl; wherein the thermoplastic polymer is dissolved in the polymerizable monomer solvent at a temperature of less than or equal to 100°C, preferably 45 to 80°C, more preferably 60 to 70°C.

[0069] Embodiment 2. The thermoplastic composition of embodiment 1, wherein the composition comprises less than or equal to 10 wt.% of a nonreactive solvent, preferably less than or equal to 5 wt.% of a solvent, more preferably wherein the composition is devoid of a solvent.

[0070] Embodiment 3. The thermoplastic composition of any one or more of the preceding embodiments, having Brookfield viscosity of 0.05 to 500 Pa.s (50 to 500,000 centipoise (cp)) at a temperature of less than or equal to 100°C.

[0071] Embodiment 4. The thermoplastic composition of any one or more of the preceding embodiments, comprising less than or equal to 5 wt.%, preferably less than or equal to 3 wt.%, preferably less than or equal to 1 wt.% of a polymer comprising units derived from the polymerizable monomer solvent, preferably wherein the composition is devoid of a polymer comprising units derived from the polymerizable monomer solvent.

[0072] Embodiment 5. The thermoplastic composition of any one or more of the preceding embodiments, wherein the thermoplastic polymer comprises a poly (C1-C4 alkyl)ene, a polyarylene ether, a polycarbonate, a polyetherimide, a polyetheretherketone, a polyester, a poly(Ci-C6 alkyl) (meth)acrylate, a polyimide, a polyphenylsulfone, a polystyrene, a polyvinyl chloride, or a combination comprising at least one of the foregoing.

[0073] Embodiment 6. The thermoplastic composition of any one or more of the preceding embodiments, wherein the thermoplastic polymer comprises a polyphenylene ether comprising repeating units having the structure

wherein each occurrence of Z¹ is independently halogen, unsubstituted or substituted C1-C12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1-C12 hydrocarbylthio, C1-C12 hydrocarbyloxy, or C2-C12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atom, and each occurrence of Z² is independently hydrogen, halogen, unsubstituted or substituted C1-C12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1-C12 hydrocarbylthio, C1-C12 hydrocarbyloxy, or C2-C12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atom.

[0074] Embodiment 7. The thermoplastic composition of embodiment 6 wherein the polyphenylene ether is poly(2,6-dimethyl-l,4-phenylene ether).

[0075] Embodiment 8. The thermoplastic composition of embodiment 6 or 7, wherein the polyphenylene ether comprises less than or equal to 5 mole percent, less than or equal to 3 mole percent, or less than or equal to 1 mole percent of end groups that react with the polymerizable monomer composition, and preferably wherein the polyphenylene ether is devoid of polymerizable end groups that are reactive with the polymerizable monomer.

[0076] Embodiment 9. The thermoplastic composition of any one or more of the preceding embodiments, wherein the aryl acrylate is phenyl (C1-C6 alkyl)acrylate, preferably phenyl methacrylate or phenyl acrylate.

[0077] Embodiment 10. The thermoplastic composition of any one or more of the preceding embodiments, having less than or equal to 5 wt.%, less than or equal to 3 wt.%, or less than or equal to 1 wt.% of a copolymerizable allyl- or vinyl-substituted aromatic compound based on the total weight of the thermoplastic composition, preferably wherein the thermoplastic composition is devoid of an allyl or vinyl-substituted aromatic compound.

[0078] Embodiment 1 1. The thermoplastic composition of any one or more of the preceding embodiments, having less than or equal to 5 wt.%, less than or equal to 3 wt.%, or less than or equal to 1 wt.% of a monomer having two or more unsaturated groups, based on the total weight of the thermoplastic composition, preferably wherein the thermoplastic composition is devoid of a monomer having two or more unsaturated groups.

[0079] Embodiment 12. The thermoplastic composition of any one or more of the preceding embodiments, having less than or equal to 5 wt.%, less than or equal to 3 wt.%, or less than or equal to 1 wt.% of any additional monomer copolymerizable with the aryl acrylate compound, based on the total weight of the thermoplastic composition, preferably wherein the thermoplastic composition is devoid of any additional monomer copolymerizable with the aryl acrylate compound. [0080] Embodiment 13. The thermoplastic composition of any one or more of embodiments 1 to 12, wherein the polymerizable monomer solvent further comprises a polymerizable monomer different from the aryl acrylate compound.

[0081] Embodiment 14. The thermoplastic composition of embodiment 13, wherein the polymerizable monomer different from the aryl acrylate comprises an allyl- or vinyl- substituted aromatic compound, a (C1-C12 alkyl) (meth)acrylate, (meth)acrylonitrile, a (C1-C6 alkyl ) fumaratc ester, a fumaratc anhydride, a v iny!ideiic halide, a vinyl carboxyiate, a (Ci- C12 alkyl) vinyl ketone, or a combination comprising at least one of the foregoing, preferably an allyl- or vinyl-substituted aromatic compound, more preferably styrene.

[0082] Embodiment 15. The thermoplastic composition of any one or more of the preceding embodiments, further comprising a polymerization initiator, preferably a free radical polymerization initiator, most preferably a free radical polymerization initiator activatable and 50 to 100°C, more preferably 60 to 90°C.

[0083] Embodiment 16. A method of manufacturing a thermoplastic composition, the method comprising combining the components of the thermoplastic composition of any one or more of embodiments 1 to 15; and heating the combined components to a temperature of less than or equal to 130°C, or 70 to 120°C, or 80 to 1 10°C or 90 to 100° for a time effective to dissolve the thermoplastic polymer in the polymerizable monomer solvent.

[0084] Embodiment 17. A thermoplastic composition manufactured by the method of embodiment 16.

[0085] Embodiment 18. A composite preform, comprising, the thermoplastic composition of any one or more of embodiments 1 to 15 or 17; and a reinforcing agent.

[0086] Embodiment 19. The composite preform of embodiment 18, wherein the reinforcing agent comprises a reinforcing particulate, fiber, fabric, porous material, or a combination comprising at least one of the foregoing.

[0087] Embodiment 20. The composite preform of embodiment 19, comprising a fabric reinforcing agent impregnated with the thermoplastic composition, preferably a fabric comprising glass fibers, carbon fibers, aromatic polyamide fibers, or a combination comprising at least one of the foregoing fibers.

[0088] Embodiment 21. The composite preform of any one or more of embodiments 18 to 20, wherein the thermoplastic composition further comprises a thermoset polymer comprising, consisting essentially of, or consisting of units derived from partially

polymerizing the polymerizable monomer solvent, and having the structure

wherein Z is hydrogen, C1-C6 alkyl, or substituted or unsubstituted aryl, preferably hydrogen or methyl, and A is an unsubstituted or substituted C6-C20 aryl, preferably an unsubstituted or monosubstituted C6-C20 aryl.

[0089] Embodiment 22. The composite preform of embodiment 21, comprising a fabric reinforcing agent impregnated with the thermoplastic composition.

[0090] Embodiment 23. A method of making a composite preform, the method comprising contacting a reinforcing agent with the thermoplastic composition of any one or more of embodiments 1 to 15 at a temperature effective for the thermoplastic composition to wet the reinforcing agent; and optionally shaping the contacted reinforcing agent, preferably by molding.

[0091] Embodiment 24. The method of embodiment 23, wherein the contacting is at a temperature of less than or equal to 130°C, preferably 70 to 120°C, preferably 80 to 1 10°C, more preferably 90 to 100°C.

[0092] Embodiment 25. The method of embodiments 23 or 24, wherein the reinforcing agent comprises a reinforcing particulate, fiber, fabric, porous material, or a combination comprising at least one of the foregoing, preferably wherein the reinforcing agent is a fabric and the contacting comprises impregnating the fabric with the thermoplastic composition to form a prepreg, more preferably wherein the fabric comprises glass fibers, carbon fibers, aromatic polyamide fibers, or a combination comprising at least one of the foregoing fibers.

[0093] Embodiment 26. The method of any one or more of embodiments 23 to 25, wherein the method excludes a solvent removal step.

[0094] Embodiment 27. The method of any one or more of embodiments 23 to 26, further comprising partially polymerizing the monomer solvent to form a B-staged preform.

[0095] Embodiment 28. The method of embodiment 27, wherein the partially polymerizing comprises heating the preform, exposing the preform to radiation, for example ultraviolet radiation, infrared radiation, microwave radiation, e-beam irradiation, or a combination comprising at least one of the foregoing, preferably at a temperature of less than or equal to 200°C. [0096] Embodiment 29. The method of embodiment 28, wherein the partially polymerizing comprises heating the preform to a temperature less than or equal to 180°C, preferably 70 to 120°C, more preferably 80 to 1 10°C, even more preferably 90 to 100°C.

[0097] Embodiment 30. The method of any one or more of embodiments 27 to 29, wherein the thermoplastic composition comprises less than or equal to 5 mole percent, less than or equal to 3 mole percent, or less than or equal to 1 mole percent of covalent links between the thermoplastic polymer and the polymerized monomer, preferably as determined by nuclear magnetic resonance spectroscopy, infrared spectroscopy, or the like.

[0098] Embodiment 31. A composite preform prepared by the method of any one or more of embodiments 23 to 30.

[0099] Embodiment 32. A B-staged composite preform prepared by the method of any one or more of embodiments 27 to 31.

[0100] Embodiment 33. A multi -polymer composition comprising, based on the total weight of the composition, 20 to 90 wt.%, preferably 25 to 70 wt.%, more preferably 30 to 50 wt.% of a thermoplastic polymer; and 10 to 70 wt.%, preferably 20 to 60 wt.%, more preferably 35 to 55 wt.% of a thermoset polymer comprising, consisting essentially of, or consisting of aryl acrylate compound units having the structure

Wherein Z is hydrogen, C1-C6 alkyl, or substituted or unsubstituted aryl, preferably hydrogen or methyl, and A is an unsubstituted or substituted C6-C20 aryl, preferably an unsubstituted or monosubstituted C6-C20 aryl; wherein the thermoplastic polymer and the thermoset polymer form a miscible blend.

[0101] Embodiment 34. The multi-polymer composition of embodiment 33, wherein the thermoplastic polymer and the thermoset polymer are an interpenetrating polymer network.

[0102] Embodiment 35. The multi-polymer composition of embodiment 34, wherein the composition comprises less than or equal to 10 wt.% of a solvent, preferably less than or equal to 5 wt.% of a solvent, more preferably wherein the composition is devoid of a solvent.

[0103] Embodiment 36. The multi-polymer composition of embodiment 34 or 35, wherein the multi-polymer composition comprises less than or equal to 5 mole percent, less than or equal to 3 mole percent, or less than or equal to 1 mole percent of covalent links between the thermoplastic polymer and the polymerized monomer, as determined by nuclear magnetic resonance spectroscopy, infrared spectroscopy, or the like.

[0104] Embodiment 37. The multi-polymer composition of any one or more of embodiments 34 to 36, wherein the thermoplastic polymer comprises a poly (Ci-C₄ alkyl)ene, a polyarylene ether, a polycarbonate, a polyetherimide, a polyetheretherketone, a polyester, a poly(Ci-C6 alkyl) (meth)acrylate, a polyimide, a polyphenylsulfone, a polystyrene, a polyvinyl chloride, or a combination comprising at least one of the foregoing.

[0105] Embodiment 38. The thermoplastic composition embodiment 37, wherein the thermoplastic polymer comprises a polyphenylene ether comprising repeating units having the structure

wherein each occurrence of Z¹ is independently halogen, unsubstituted or substituted C1-C12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1-C12 hydrocarbylthio, C1-C12 hydrocarbyloxy, or C2-C12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atom, and each occurrence of Z² is independently hydrogen, halogen, unsubstituted or substituted C1-C12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1-C12 hydrocarbylthio, C1-C12 hydrocarbyloxy, or C2-C12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atom.

[0106] Embodiment 39. The multi-polymer composition of embodiment 38 wherein the polyphenylene ether is poly(2,6-dimethyl-l,4-phenylene ether).

[0107] Embodiment 40. The multi-polymer composition of any one or more of embodiments 34 to 39, wherein A is phenyl.

[0108] Embodiment 41. The multi-polymer thermoplastic composition of any one or more of embodiments 34 to 40, having less than or equal to 5 wt.%, less than or equal to 3 wt.%, or less than or equal to 1 wt.% of polymer units derived from a copolymerizable allyl- or vinyl-substituted aromatic compound based on the total weight of the thermoplastic composition, preferably wherein the thermoplastic composition is devoid of polymer units derived from an allyl or vinyl-substituted aromatic compound. [0109] Embodiment 42. The multi-polymer composition of any one or more of embodiments 33 to 41, having less than or equal to 5 wt.%, less than or equal to 3 wt.%, or less than or equal to 1 wt.% of polymer units derived from monomer having two or more unsaturated groups, based on the total weight of the thermoplastic composition, preferably wherein the thermoplastic composition is devoid of polymer units derived from a monomer having two or more unsaturated groups.

[01 10] Embodiment 43. The multi-polymer composition of any one or more of embodiments 33 to 42, having less than or equal to 5 wt.%, less than or equal to 3 wt.%, or less than or equal to 1 wt.% of any polymer units different from the aryl acrylate compound units, based on the total weight of the thermoplastic composition, preferably wherein the thermoplastic composition is devoid of any polymer units different from the aryl acrylate compound units.

[01 11] Embodiment 44. The multi-polymer composition of any one or more of embodiments 34 to 42, wherein the thermoset polymer further comprises a polymer unit different from the aryl acrylate compound units.

[01 12] Embodiment 45. The multi-polymer composition of embodiment 44, wherein the polymer unit different from the aryl acrylate compound is derived from an allyl- or vinyl- substituted aromatic compound, a (C1-C12 alkyl) (meth)acrylate, (meth)acrylonitrile, a (C1-C6 alkyl ) fumaratc ester, a fumaratc anhydride, a vinyl idene halide, a vinyl carboxylate, a (Ci- C12 alkyl) vinyl ketone, or a combination comprising at least one of the foregoing, preferably a substituted or unsubstituted vinyl benzene.

[01 13] Embodiment 46. A method of making a multi-polymer composition, the method comprising, polymerizing the polymerizable monomer solvent of the thermoplastic composition of any one or more of embodiments 1 to 15 to form a miscib!e blend comprising, based on the total weight of the composition, 20 to 90 wt.%, preferably 25 to 70 wt.%, more preferably 30 to 50 wt.% of a thermoplastic polymer; and 10 to 70 wt.%, preferably 20 to 60 wt.%, more preferably 35 to 5 wt.% of a thermoset polymer comprising, consisting essentially of, or consisting of aiyl acrylate compound units having the structure

wherein Z is hydrogen, C1-C6 alkyl, or substituted or unsubstituted aryl, preferably hydrogen or methyl, and A is an unsubstituted or substituted C6-C20 aryl, preferably an unsubstituted or monosubstituted C6-C20 aryl.

[01 14] Embodiment 47. The method of embodiment 46, wherein the thermoplastic polymer and the thermoset polymer are an interpenetrating polymer network.

[01 15] Embodiment 48. The method of embodiment 46 or 47, wherein the multi- polymer composition comprises less than or equal to 5 mole percent, less than or equal to 3 mole percent, or less than or equal to 1 mole percent of covalent links between the thermoplastic polymer and the polymerized monomer, as determined by nuclear magnetic resonance spectroscopy, infrared spectroscopy, or the like.

[01 16] Embodiment 49. The method of any one or more of embodiments 46 to 48, wherein the polymerizing comprises heating, exposing the preform to ultraviolet radiation, infrared radiation, microwave radiation e-beam irradiation, or a combination comprising at least one of the foregoing, preferably at a temperature of less than or equal to 200°C.

[01 17] Embodiment 50. The method of embodiment 49, wherein the polymerizing comprises heating to a temperature less than or equal to 180°C, preferably 70 to 120°C, more preferably 80 to 1 10°C, even more preferably 90 to 100°C.

[01 18] Embodiment 51. The method of any one or more of embodiments to 46 to 50, wherein the polymerizing is conducted in two or more stages, preferably in single stage.

[01 19] Embodiment 52. The method of any one or more of embodiments to 46 to 51, wherein the method excludes a solvent removal step.

[0120] Embodiment 53. The method of any one or more of embodiments 46 to 50, further comprising contacting the thermoplastic composition with a reinforcing agent before the polymerizing to wet the reinforcing agent, preferably wherein the reinforcing agent comprises a reinforcing particulate, fiber, fabric, porous material, or a combination comprising at least one of the foregoing.

[0121] Embodiment 54. The method of embodiment 53, wherein the reinforcing agent is a fabric, and the contacting comprises impregnating the fabric with the thermoplastic composition to form a prepreg.

[0122] Embodiment 55. The method of embodiment 54, further comprising partially polymerizing the monomer solvent of the prepreg to form a B-staged prepreg before fully polymerizing the monomer solvent.

[0123] Embodiment 56. A multi-polymer composition prepared by the method of any one or more of embodiments 46 to 55. [0124] Embodiment 57. An article comprising the multi-polymer composition of embodiment 56.

[0125] All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other. The terms "a" and "an" and "the" herein do not denote a limitation of quantity, and are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Reference throughout the specification to "one embodiment", "another embodiment", "an embodiment", and so forth, means that a particular element (e.g., feature, structure, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments.

[0126] "Combination" is inclusive of blends, mixtures, alloys, reaction products, and the like. As used herein, the term "alkyl" means a branched or straight chain, saturated, monovalent hydrocarbon group, e.g., methyl, ethyl, i-propyl, and n-butyl. "Alkylene" means a straight or branched chain, saturated, divalent hydrocarbon group (e.g., methylene (-CH2-) or propylene (-(CH₂)₃-)). "Alkenyl" and "alkenylene" mean a monovalent or divalent, respectively, straight or branched chain hydrocarbon group having at least one carbon-carbon double bond (e.g., ethenyl (-HC=CH₂) or propenylene (-HC(CH₃)=CH₂-). "Alkynyl" means a straight or branched chain, monovalent hydrocarbon group having at least one carbon- carbon triple bond (e.g., ethynyl). "Alkoxy" means an alkyl group linked via an oxygen (i.e., alkyl-O-), for example methoxy, ethoxy, and sec-butyloxy. "Cycloalkyl" means a monovalent cyclic hydrocarbon group of the formula -CnEkn-x and -C_nH2n-2x- wherein x is the number of cyclization(s). "Aryl" means a monovalent, monocyclic or polycyclic aromatic group (e.g., phenyl or naphthyl). The prefix "halo" means a group or compound including one more halogen (F, CI, Br, or I) substituents, which can be the same or different. The prefix "hetero" means a group or compound that includes at least one ring member that is a heteroatom (e.g., 1, 2, or 3 heteroatoms, wherein each heteroatom is independently N, O, S, or P.

[0127] "Substituted" as used herein means that the compound or group is substituted with at least one (e.g., 1, 2, 3, or 4) substituents instead of hydrogen, where each substituent is independently nitro (-NO2), cyano (-CN), hydroxy (-OH), halogen, thiol (-SH), thiocyano (-SCN), Ci-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, Ci-6 haloalkyl, C1-9 alkoxy, Ci-6 haloalkoxy, C₃- 12 cycloalkyl, Cs-is cycloalkenyl, C6-12 aryl, C7-13 arylalkylene (e.g, benzyl), C7-12 alkylarylene (e.g, toluyl), C4-12 heterocycloalkyl, C3-12 heteroaryl, Ci-6 alkyl sulfonyl (-S(=0)2-alkyl), C6-12 arylsulfonyl (-S(=0)2-aryl), or tosyl (CH3C6H4SO2-), provided that the substituted atom's normal valence is not exceeded, and that the substitution does not significantly adversely affect the manufacture, stability, or desired property of the compound. When a compound is substituted, the indicated number of carbon atoms is the total number of carbon atoms in the group, including those of the substituent(s).

Claims

1. A thermoplastic composition comprising, based on the total weight of the composition,

20 to 90 wt.%, preferably 25 to 70 wt.%, more preferably 30 to 50 wt.% of a thermoplastic polymer; and

10 to 70 wt.%, preferably 20 to 60 wt.%, more preferably 35 to 55 wt.% of a polymerizable monomer solvent that is liquid at a temperature in a range of -10 to 120 °C, and comprising, consisting essentially of, or consisting of an aryl acrylate compound having the structure

wherein

Z is hydrogen, C1-C6 alkyl, or substituted or unsubstituted aryl, preferably hydrogen or methyl, and

A is an unsubstituted or substituted C6-C20 aryl, preferably an unsubstituted or monosubstituted C6-C20 aryl;

wherein the thermoplastic polymer is dissolved in the polymerizable monomer solvent at a temperature of less than or equal to 100°C, preferably 45 to 80°C, more preferably 60 to 70°C.

2. The thermoplastic composition of claim 1 wherein the polymerizable monomer solvent comprises an aryl acrylate compound having the structure

wherein

Z is hydrogen, C1-C6 alkyl, or substituted or unsubstituted aryl, preferably hydrogen or methyl, and

A is an unsubstituted or substituted C6-C20 aryl, preferably an unsubstituted or monosubstituted C6-C20 aryl.

3. The thermoplastic composition of any one or more of the preceding claims, wherein the composition comprises less than or equal to 10 wt.% of a nonreactive solvent, preferably less than or equal to 5 wt.% of a solvent, more preferably wherein the composition is devoid of a solvent.

4. The thermoplastic composition of any one or more of the preceding claims, comprising less than or equal to 5 wt.%, preferably less than or equal to 3 wt.%, preferably less than or equal to 1 wt.% of a polymer comprising units derived from the polymerizable monomer solvent, preferably wherein the composition is devoid of a polymer comprising units derived from the polymerizable monomer solvent.

5. The thermoplastic composition of any one or more of the preceding claims, wherein the thermoplastic polymer comprises a poly (Ci-C₄ alkyl)ene, a polyarylene ether, a polycarbonate, a polyetherimide, a polyetheretherketone, a polyester, a poly(Ci-C6 alkyl) (meth)acrylate, a polyimide, a polyetherimide, a polyphenylsulfone, a polystyrene, a polyvinyl chloride, or a combination comprising at least one of the foregoing.

6. The thermoplastic composition of any one or more of the preceding claims, wherein the thermoplastic polymer comprises a polyphenylene ether comprising repeating units having the structure

wherein

each occurrence of Z¹ is independently halogen, unsubstituted or substituted C1-C12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1-C12 hydrocarbylthio, C1-C12 hydrocarbyloxy, or C2-C12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atom, and

each occurrence of Z² is independently hydrogen, halogen, unsubstituted or substituted C1-C12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1-C12 hydrocarbylthio, C1-C12 hydrocarbyloxy, or C2-C12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atom.

7. The thermoplastic composition of claim 6 wherein the polypheny lene ether is poly(2,6-dimethyl-l,4-phenylene ether).

8. The thermoplastic composition of any one or more of the preceding claims, wherein the aryl acrylate is phenyl (Ci-C6 alkyl)acrylate, preferably phenyl methacrylate or phenyl acrylate.

9. A method of manufacturing a thermoplastic composition, the method comprising

combining the components of the thermoplastic composition of any one or more of claims 1 to 8; and

heating the combined components to a temperature of less than or equal to 130°C, or 70 to 120°C, or 80 to 110°C or 90 to 100° for a time effective to dissolve the thermoplastic polymer in the polymerizable monomer solvent.

10. A composite preform comprising the thermoplastic composition of any one or more of claims 1 to 8; and a reinforcing agent wherein the reinforcing agent comprises a reinforcing particulate, fiber, fabric, porous material, or a combination comprising at least one of the foregoing.

1 1. The composite preform of claim 10, comprising a fabric reinforcing agent impregnated with the thermoplastic composition, preferably a fabric comprising glass fibers, carbon fibers, aromatic polyamide fibers, or a combination comprising at least one of the foregoing fibers.

12. The composite preform of claim 1 1, comprising a fabric reinforcing agent impregnated with the thermoplastic composition.

13. A multi-polymer composition comprising, based on the total weight of the composition, 20 to 90 wt.%, preferably 25 to 70 wt.%, more preferably 30 to 50 wt.% of a thermoplastic polymer according to any one of claims 1-8; and 10 to 70 wt.%, preferably 20 to 60 wt.%, more preferably 35 to 55 wt.% of a thermoset polymer comprising, consisting essentially of, or consisting of aryl acrylate compound units having the structure

wherein

Z is hydrogen, C1-C6 alkyl, or substituted or unsubstituted aryl, preferably hydrogen or methyl, and

A is an unsubstituted or substituted C6-C20 aryl, preferably an unsubstituted or monosubstituted C6-C20 aryl;

wherein the thermoplastic polymer and the thermoset polymer form a miscible blend.

14. A multi-polymer composition according to claim 13 wherein the thermoset mer comprises aryl acrylate compound units having the structure

wherein

Z is hydrogen, C1-C6 alkyl, or substituted or unsubstituted aryl, preferably hydrogen or methyl, and

A is an unsubstituted or substituted C6-C20 aryl, preferably an unsubstituted or monosubstituted C6-C20 aryl.

An article comprising the multi-polymer composition of any one of claims 13

14.