Patent Application
20190284340
This application claims priority to and the benefit of European Patent Application No. 18161688.9 filed in the European Patent Office on Mar. 14, 2018, and all the benefits accruing therefrom under 35 U.S.C. § 119, the entire content of which is incorporated herein by reference.
Phthalonitrile polymers constitute an important class of high-temperature materials, having a wide range of uses, such as composite matrices, adhesives, sealants, and semiconductors. Phthalonitrile (PN) and diphthalonitrile (DPN) monomers can provide heat-curable crosslinked polymers having superior flammability and high temperature properties, relative to other high temperature polymers. The PN and DPN compounds polymerize through the cyano groups to provide a crosslinked polymeric network with high thermal and oxidative stability, as well as a high modulus of elasticity.
DPN compounds include a spacer group that links the moieties having the phthalonitrile functionality. Aliphatic spacer groups are readily cured compared to DPN compounds having aromatic spacer groups. The cure temperature of DPN compounds having aromatic spacers can be higher than for aliphatic-spacer linked compounds. The relatively slow rate of polymerization for aromatic spacer-linked DPN compounds has been attributed to the rigidity of the linking structure, which can reduce the mobility of the cyano groups.
There accordingly remains a need for thermoset polymer products derived from DPN monomers having aromatic bridging groups, and methods of synthesizing DPN monomers, thermosetting composition, and thermoset polymer compositions.
Described herein is a 4,4′-(((3-oxo-isoindoline-1,1-diyl)bis(4,1-arylene))bis(oxy))diphthalonitrile compound of formula (1)
wherein each occurrence of R1 is independently a hydrogen, a phenyl, or a C1-6 alkyl, more preferably a hydrogen or a C1-3 alkyl; each occurrence of R2 and R3 is independently a hydrogen, a halogen, or a C1-25 hydrocarbyl, preferably a hydrogen or a C1-6 alkyl, more preferably a hydrogen or a C1-3 alkyl; and r, p, and q are each independently 0 to 4, preferably 0 or 1, more preferably 0.
Also provided is a method for the manufacture of the 4,4′-(((3-oxo-isoindoline-1,1-diyl)bis(4,1-arylene))bis(oxy))diphthalonitrile compound (1), wherein the method comprises contacting an inorganic base and a 3,3-bis(4-hydroxyaryl)-2-arylisoindolin-1-one of formula (2)
to provide a metal salt precursor, and reacting the metal salt precursor with 4-nitrophthalonitrile under conditions effective to provide the 4,4′-(((3-oxo-isoindoline-1,1-diyl)bis(4,1-arylene))bis(oxy))diphthalonitrile compound of formula (1), wherein each occurrence of R1 is independently a hydrogen, a phenyl, or a C1-6 alkyl, more preferably a hydrogen or a C1-3 alkyl; each occurrence of R2 and R3 is independently a hydrogen, a halogen, or a C1-25 hydrocarbyl, preferably a hydrogen or a C1-6 alkyl, more preferably a hydrogen or a C1-3 alkyl; and r, p, and q are each independently 0-4, more preferably 0 or 1, preferably 0.
In another aspect, a thermosetting composition comprises the 4,4′-(((3-oxo-isoindoline-1,1-diyl)bis(4,1-arylene))bis(oxy))diphthalonitrile compound and a curing agent.
In still another aspect, a thermoset polymer composition comprises the crosslinked product of the thermosetting composition.
Also provided is an article comprising the thermoset polymer composition, wherein the article is a composite, a foam, a fiber, a layer, a coating, an encapsulant, an adhesive, a sealant, a component, a prepreg, a casing, or a combination thereof.
The disclosure is further illustrated by the following detailed description, examples, and claims.
Described herein are aromatic diphthalonitrile (DPN) monomers and uses thereof. The aromatic DPN monomers have an aromatic spacer that can provide good thermo-oxidative resistance, and can be used to provide thermoset polymers with potentially well-defined melting points. For example, thermoset polymers including the aromatic spacer-linked DPN monomers can withstand high temperatures for extended periods of time without permanent damage. In particular, the resulting thermoset polymers can withstand temperatures of up 500° C., preferably 200 to 500° C., more preferably 200 to 400° C. The thermoset polymers derived from the aromatic DPN monomers can be superior in physical and chemical properties to epoxies, polyimides, and other polymers used as high temperature adhesives.
Disclosed herein is the DPN compound, 4,4′-(((3-oxo-isoindoline-1,1-diyl)bis(4,1-arylene))bis(oxy))diphthalonitrile, of formula (1)
wherein each occurrence of R1 is independently a hydrogen, a phenyl, or a C1-6 alkyl, preferably a hydrogen or a C1-3 alkyl. Each occurrence of R2 and R3 is independently a hydrogen, a halogen, or a C1-25 hydrocarbyl, preferably a hydrogen or a C1-6 alkyl, more preferably a hydrogen or a C1-3 alkyl. In formula (1), r, p, and q are each independently 0 to 4, preferably 0 or 1, more preferably 0. For example, R1 is a hydrogen or a C1-3 alkyl, and each occurrence of R2 and R3 is independently a hydrogen or a C1-6 alkyl. In another example, R1 is a hydrogen or a C1-3 alkyl, each occurrence of R2 and R3 is independently a hydrogen or a C1-3 alkyl, and r, p, and q are each 0.
The DPN compound can be a 4,4′-(((3-oxo-2-arylisoindoline-1,1-diyl)bis(4,1-phenylene))bis(oxy))diphthalonitrile of formula (1a)
wherein each occurrence of R1 and R2 is independently a hydrogen or a C1-3 alkyl. In formula (1a), r and p are each independently 0 or 1, preferably 0. Preferably, in formula (1a), each occurrence of R1 and R2 is independently a hydrogen or a C1-3 alkyl, and r and p are each 0. For example, the DPN compound can be a 4′-(((3-oxo-2-phenylisoindoline-1,1-diyl)bis(4,1-phenylene))bis(oxy))diphthalonitrile of formula (1b)
Also provided is a method for the manufacture of a thermosetting composition comprising the 4,4′-(((3-oxo-isoindoline-1,1-diyl)bis(4,1-arylene))bis(oxy))diphthalonitrile compound (1). The method includes contacting an inorganic base and a 3,3-bis(4-hydroxyaryl)-2-arylisoindolin-1-one of formula (2)
to provide a metal salt precursor, and reacting the metal salt precursor with 4-nitrophthalonitrile under conditions effective to provide the 4,4′-(((3-oxo-isoindoline-1,1-diyl)bis(4,1-arylene))bis(oxy))diphthalonitrile compound of formula (1).
In formula 2, each occurrence of R1 is independently a hydrogen, a phenyl, or a C1-6 alkyl, more preferably a hydrogen or a C1-3 alkyl. Each occurrence of R2 and R3 is independently a hydrogen, a halogen, or a C1-25 hydrocarbyl, preferably a hydrogen or a C1-6 alkyl, more preferably a hydrogen or a C1-3 alkyl. In formula (2), r, p, and q are each independently 0 to 4, preferably 0 or 1, more preferably 0. For example, each occurrence of R1 is independently a hydrogen or a C1-3 alkyl, each occurrence of R2 and R3 is independently a hydrogen or a C1-6 alkyl, and r, p, and q are each 0 or 1. In another example, each occurrence of R1 is independently a hydrogen or a C1-3 alkyl, each occurrence of R2 and R3 is independently a hydrogen or a C1-3 alkyl, and r, p, and q are each 0.
In a preferred example, the 3,3-bis(4-hydroxyaryl)-2-arylisoindolin-1-one (2) is a 3,3-bis(4-hydroxyaryl)-2-arylisoindolin-1-one of formula (2a)
wherein each occurrence of R1 is independently a hydrogen or a C1-3 alkyl and r and p are each independently 0 or 1, preferably 0. For example, each occurrence of R1 is independently a hydrogen or a C1-3 alkyl, and r and p are each 0. In a specific example, the 3,3-bis(4-hydroxyaryl)-2-arylisoindolin-1-one (2) is 3,3-bis(4-hydroxyphenyl)-2-arylisoindolin-1-one of formula (2b)
Exemplary inorganic bases include alkali metal and alkaline earth metal salts of carbonate, sulfate, and phosphate. In some aspects, the inorganic base is lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate, or a combination thereof. In a particular example, the base is potassium carbonate.
The 4,4′-(((3-oxo-isoindoline-1,1-diyl)bis(4,1-arylene))bis(oxy))diphthalonitrile compound can be prepared in a solvent. For example, the solvent can comprise an alkyl pyrrolidone solvent, an aromatic solvent, a halogenated aromatic solvent, or a combination thereof. Exemplary solvents include N-methyl-2-pyrrolidone, toluene, xylene, ortho-dichlorobenzene, 1,3-dimethyl-2-imidazolinone, 2-pyrrolidone, or a combination thereof.
The reacting can further include the presence of a phase transfer catalyst. Examples of suitable phase transfer catalysts include quaternary ammonium salts, quaternary phosphonium salts, sulphoxides, sulpholanes, guanidinium salts, and imidazolium salts. Exemplary catalysts include tetramethyl ammonium chloride, tetramethyl ammonium bromide, trimethylbenzylammonium chloride, triethylbenzylammonium chloride, cetyltrimethylammonium bromide, methyltrioctylammonium chloride, trioctylbenzylammonium chloride, tributylbenzylammonium chloride, tetrabutylammonium bromide, tetraphenylphosphonium halides, methyltriphenylphosphonium iodide, and ethyltriphenylphoshonium chloride, dimethylsulfoxide, diphenylsulfoxide, dibutylsulfoxide, sulfolane, 2,4-dimethylsulfolane, dimethylsulfone, diphenylsulfone, hexaethylguanidinium chloride, and 1-butyl-3-methylimidazolium chloride. The phase transfer catalyst can be present in an amount of 0.1-80 mol %, based on the moles of the compound of formulas (2), (2a), or (2b).
Also provided is a thermosetting composition including the 4,4′-(((3-oxo-isoindoline-1,1-diyl)bis(4,1-arylene))bis(oxy))diphthalonitrile compound of formula (1), (1a), or (1b), and a curing agent. The thermosetting composition optionally can further include a comonomer, preferably wherein the comonomer is a diphthalonitrile different from formulas (1), (1a), and (1b). Exemplary diphthalonitriles include, but are not limited to, 3,3′-(1,3-phenyl-enedioxy)diphthalonitrile, 4,4′-[4,4′-biphenyldiylbis(oxy)]diphthalonitrile, (N-phenyl-2,2′-iminodiethanoxy)diphthalonitrile, [2,2′-(piperidine-1,4-diyldiethylene)di(tosylimino)] diphthalonitrile, or the like.
The curing agent can be a diamine, a triamine, a higher amine, an acid salt of an amine, or an organic acid having an acid dissociation constant (pKa) of less than 4. Preferably, the curing agent is an amine-containing phosphazene, an aromatic diamine, an aromatic diamine/metal salt complex, an aromatic ether amine, an amine salt of p-toluene sulfonic acid, or an organic acid exhibiting a pKa in water of less than 3. More preferably the curing agent can be an aromatic diamine or an organic acid exhibiting a pKa in water of less than 2. A combination of curing agents can also be used.
The curing agent can be included in the thermosetting composition in an effective amount. For example, the amount by weight of the curing agent can be 1 to 40 weight percent (wt %), preferably 1 to 20 wt %, more preferably 5 to 10 wt %, based on the total weight of the diphthalonitrile compounds. In a particular example, the curing agent is an amine and the amount of curing agent is 1 to 20 wt %, preferably 1 to 15 wt %, more preferably 5 to 10 wt %, based on the total weight of the diphthalonitrile compounds.
The curing agent can be an organic acid or combination of organic acids exhibiting a pKa in water of less than 1.0. More preferably, a strong organic acid exhibits a pKa in water of less than 0.80. Strong organic acids include, for example, aromatic acids containing inorganic acidic substituents, such as the sulfonic acid group (—SO3H). Exemplary organic aromatic acids include p-toluenesulfonic acid, aniline-2-sulfonic acid, 8-aniline-1-naphthalenesulfonic acid, benzenesulfonic acid, butylsulfonic acid, 10-camphorsulfonic acid,2,5-diaminobenzenesulfonicacid,6-dimethylamino-4-hydroxy-2-naphthalenesulfonic acid, 5-dimethylamino-1-naphthalenesulfonic acid, 4-hydroxy-3-nitroso-1-naphthalenesulfonic acid tetrahydrate, 8-hydroxyquinoline-5-sulfonic acid, methylsulfonic acid, phenylboric acid, 1-naphthalenesulfonic acid, 2-naphthalenesulfonic acid, 1,5-naphthalenedisulfonic acid, 2,6-naphthalenedisulfonic acid, 2,7-napththalenedisulfonic acid, picrylsulfonic acid hydrate, 2-pyridineethanesulfonic acid, 4-pyridineethanesulfonic acid, 3-pyridinesulfonic acid, 2-pyridinylhydroxymethanesulfonic acid, sulfanilic acid, 2-sulfobenzoic acid hydrate, 5-sulfosalicylic acid hydrate, 2,4-xylenesulfonic acid, sulfonic acid containing dyes, or a combination thereof.
The curing agent can be an aromatic diamine. The aromatic diamine can be a substituted or unsubstituted aromatic diamine of the formula (3)
Z(NH2)2 (3)
wherein Z is a C6-22 arylene or a substituted derivative thereof. Exemplary aromatic diamines include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl ether, 1,5-diaminonaphthalene, 3,3′-dimethylbenzidine, 3,3′-dimethoxybenzidine, 2,4-bis(β-amino-t-butyl)toluene, bis(p-β-amino-t-butyl)ether, bis(p-β-methyl-o-aminopentyl)benzene, 1,3-diamino-4-isopropylbenzene, 1,2-bis(3-aminopropoxy)ethane, benzidine, m-xylylenediamine, p-xylylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(4-aminophenoxy)phenyl]sulfone, 4,4′-bis(3-aminophenoxy)biphenyl, 4,4′-bis(4-aminophenoxy)biphenyl, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, or a combination thereof.
The curing agent can be a salt of any one or more of the amines disclosed herein. Exemplary curing salts include bis(3-aminophenoxy)-1,3-benzene p-toluene sulfonate, p-phenylenediamine p-toluenesulfonate, bis(4-aminophenyl)methane hydrochloride, N-phenylbenzamidine p-toluene sulfonate, or a combination thereof.
The curing agent can be metal salt complex of the diamines disclosed herein. Examples of suitable metal salts include cuprous chloride, cuprous bromide, cuprous cyanide, cuprous ferricyanide, zinc chloride, zinc bromide, zinc iodide, zinc cyanide, zinc ferrocyanide, zinc acetate, zinc sulfide, silver chloride, ferrous chloride, ferric chloride, ferrous ferricyanide, ferrous chloroplatinate, ferrous fluoride, ferrous sulfate, cobaltous chloride, cobaltic sulfate, cobaltous cyanide, nickel chloride, nickel cyanide, nickel sulfate, nickel carbonate, stannic chloride, stannous chloride hydrate, a complex of triphenylphosphine oxide and stannous chloride, or a combination thereof.
The curing agent can be an aromatic ether amine. Aromatic ether amines include those described in U.S. Pat. No. 5,003,078, the entire content of which is incorporated herein by reference. Exemplary aromatic ether amines include 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4′-bis(3-aminophenoxy)biphenyl, 4,4′-bis(4-aminophenoxy)biphenyl, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, or a combination thereof.
The curing agent can be an amine-containing phosphazene. Amine-containing phosphazenes include those described in U.S. Pat. No. 5,208,318, the entire content of which is incorporated herein by reference.
Provided also is a thermoset polymer composition comprising the crosslinked product of the thermosetting composition. The thermoset polymer composition can be prepared by any suitable method, including by polymerizing a 4,4′-(((3-oxo-isoindoline-1,1-diyl)bis(4,1-arylene))bis(oxy))diphthalonitrile compound of formulas (1), (1a), and/or (1b) under conditions effective to form the crosslinked product.
The method of polymerizing includes heating the thermosetting compound. The heating can be at a temperature of 200 to 500° C., preferably 200 to 400° C., more preferably 200 to 300° C., even more preferably 220 to 300° C., optionally in the presence of a curing agent. The heating can further be at a pressure of 1 to 100 atmospheres (atm) (101.3 to 10132.5 kilopascals (kPa)), preferably 1 to 10 atm (101.3 to 1013.3 kPa), more preferably 1 to 5 atm (101.3 to 506.7 kPa). For example, the heating can be at a temperature of 200 to 500° C., preferably 200 to 400° C., more preferably 200 to 300° C., even more preferably 220 to 300° C. and at a pressure of 1 to 100 atm (101.3 to 10132.5 kPa), preferably 1 to 10 atm (101.3 to 1013.3 kPa), more preferably 1 to 5 atm (101.3 to 506.7 kPa).
The heating can comprise a cure cycle. For example, the cure cycle can include a two-part cure of 225 to 260° C. for 5 to 20 hours and 300 to 315° C. for 5 to 20 hours; a three-part cure of 180 to 240° C. for 2 to 16 hours, 240 to 300° C. for 2 to 8 hours, and 300 to 315° C. for 4 to 20 hours; or a four-part cure of 200 to 240° C. for 1 to 3 hours, 240 to 270° C. for 2 to 4 hours, 270 to 300° C. for 4 to 6 hours, and 300 to 315° C. for 4 to 20 hours.
The diphthalonitrile monomers are generally solids at room or ambient temperatures, and can have melting points between 200 to 300° C. The polymerization of the diphthalonitrile monomers can be sluggish and can require heating at elevated temperature for extended time before a vitrified product is obtained. Therefore, a curing agent can be used to promote the thermal polymerization reaction of the diphthalonitrile monomers. Suitable curing agents include, but are not limited to, organic amines, phenols, strong organic acids (e.g., organic acids having a pH of less than 4), and amine salts thereof, metals and salts thereof, or a combination thereof.
The thermosetting composition or the thermoset polymer composition can further include an additive. The additive can be a particulate filler, a fibrous filler, an antioxidant, a heat stabilizer, a light stabilizer, a ultraviolet light stabilizer, a ultraviolet light-absorbing compound, a near infrared light-absorbing compound, an infrared light-absorbing compound, a plasticizer, a lubricant, a release agent, a antistatic agent, an anti-fog agent, a antimicrobial agent, a colorant, a surface effect additive, a radiation stabilizer, a flame retardant, an anti-drip agent, a fragrance, a polymer different from the thermoset polymer, or a combination thereof.
Examples of polymers different than the thermoset polymer include polyacetals (e.g., polyoxyethylene and polyoxymethylene), poly(C1-6 alkyl)acrylates, polyacrylamides, polyamides, (e.g., aliphatic polyamides, polyphthalamides, and polyaramides), polyamideimides, polyanhydrides, polyarylates, polyarylene ethers (e.g., polyphenylene ethers), polyarylene sulfides (e.g., polyphenylene sulfides), polyarylene sulfones (e.g., polyphenylene sulfones), polybenzothiazoles, polybenzoxazoles, polycarbonates (including polycarbonate copolymers such as polycarbonate-siloxanes, polycarbonate-esters, and polycarbonate-ester-siloxanes), polyesters (e.g., polyethylene terephthalates, polybutylene terephthalates, polyarylates, and polyester copolymers such as polyester-ethers), polyetheretherketones, polyetherimides (including copolymers such as polyetherimide-siloxane copolymers), polyetherketoneketones, polyetherketones, polyethersulfones, polyimides (including copolymers such as polyimide-siloxane copolymers), poly(C1-6 alkyl)methacrylates, polymethacrylamides, polynorbornenes (including copolymers containing norbornenyl units), polyolefins (e.g., polyethylenes, polypropylenes, polytetrafluoroethylenes, and their copolymers, for example ethylene-alpha-olefin copolymers), polyoxadiazoles, polyoxymethylenes, polyphthalides, polysilazanes, polysiloxanes, polystyrenes (including copolymers such as acrylonitrile-butadiene-styrene (ABS) and methyl methacrylate-butadiene-styrene (MBS)), polysulfides, polysulfonamides, polysulfonates, polysulfones, polythioesters, polytriazines, polyureas, polyurethanes, polyvinyl alcohols, polyvinyl esters, polyvinyl ethers, polyvinyl halides, polyvinyl ketones, polyvinyl thioethers, polyvinylidene fluorides, or the like, or a combination thereof.
Also provided is an article including the thermosetting composition or the thermoset polymer composition. The article can be in the form of a composite, a foam, a fiber, a layer, a coating, an encapsulant, an adhesive, a sealant, a component (e.g., a molded component), a prepreg, a casing, or a combination thereof. Specific examples of the articles include an electronic substrate, an electronic housing, a microelectronic device, a printed electronic component, a tooling, a geothermal tool, an oil rig component, a flame retardant component, a sizing resin, a resin infusion molded component, a resin transfer molded component, or a combination thereof. In still other examples, the article is a carbon fiber composite, a fiberglass composite, a fiber coating, a weather resistant coating, a scratch resistant coating, a food packaging coating, an electrical insulative coating, a carbon fiber composite, a fiberglass composite, an industrial component, an oil rig component, a missile component, a rocket component, a building component, a bridge component, a transportation component, an electrical component, a computer component, an appliance component, a furniture component, a pump component, a electrolytic cell component, a tooling, a flame retardant component, a body protective component, a sporting equipment component, a container, a filament winding, a resin infusion molding component, a resin transfer molding component, or a combination thereof.
For example, the article can be an exhaust stack, a scrubber, a stair case, a walkway, a tile, a vehicle, an aircraft or watercraft exterior component, submersible watercraft component, a floor pan, an air scoop, a pipe, a duct, a fan component, a fan housing, a blower, an industrial mixer component, a tile, a business machine component, or a pultruded part for structural applications. In other examples, the article can be a water craft hull, a watercraft deck, a marine terminal fender, a bridge deck, a bridge support, a railing, a building panel, a business machine housing or tray, a concrete modifier, a dishwasher or refrigerator part, an electrical encapsulant, an electrical panel, a electrorefining tank, a water softener tank, a fuel tank, a pressure tank, a filament-wound tank, a tank lining, a garage door, a grating, a protective body gear, a luggage component, a printed circuit board, an optical waveguide, a radome, a tank car, a hopper car cover, a car door, a truck bed liner, a satellite dish, a sign, a solar energy panel, a telephone switchgear housing, a tractor part, a transformer cover, a ground insulation, a turn insulation, a phase separation insulation for rotating machines, a commutator, a core insulation, a cord, a lacing tape, a drive shaft coupling, a propeller blade, a rocket motor case, a wing section, a sucker rod, a fuselage section, a wing skin wing fairing, an engine narcelle, a cargo door, a tennis racquet, a golf club shaft, a fishing rod, a ski, a ski pole, a bicycle part, a transverse leaf spring, an automotive smog pump component, a such as electrical cable joint, a wire winding, a sealant for an electromechanical device, a battery case, a resistor, a fuse, a thermal cut-off device, a capacitor, a transformer, a crankcase heater, a coil, a resistor, a semiconductor, a steel replacement component in chemical processing, a pulp and paper, a power generation, a and wastewater treatment, a scrubbing tower, a gratings, a safety rail, a component for a swimming pool, a swimming pool slide, a hot-tub, a or sauna, a drive shaft, a dry toner polymer for copying machine, a heat shield, a submarine hull, a laminated trim, a drilling fixture, a bonding jig, an inspection fixture, an industrial metal forming die, an aircraft stretch block and hammer form, a vacuum molding tool, a flooring, a antistatic articles, a decorative flooring, expansion joints for a bridge, an injectable mortar for patch and repair of cracks in structural concrete, a grouting for tile, a machinery rail, a bolt and post, a storage tank repair, or a light emitting diode (LED) encapsulant.
Processes useful for preparing the articles and materials include those generally known to the art for the processing of thermosetting polymers. Such processes have been described in the literature as in, for example, Engineered Materials Handbook, Volume 1, Composites, ASM International Metals Park, Ohio, copyright 1987 Cyril A. Dostal Senior Ed, pp. 105-168 and 497-533, and “Polyesters and Their Applications” by Bjorksten Research Laboratories, Johan Bjorksten (pres.) Henry Tovey (Ch. Lit. Ass.), Betty Harker (Ad. Ass.), James Henning (Ad. Ass.), Reinhold Publishing Corporation, New York, 1956. Processing techniques include polymer transfer molding; sheet molding; bulk molding; pultrusion; injection molding, including reaction injection molding (RIM); atmospheric pressure molding (APM); casting, including centrifugal and static casting open mold casting; lamination including wet or dry lay up and spray lay up; also included are contact molding, including cylindrical contact molding; compression molding; including vacuum assisted polymer transfer molding and chemically assisted polymer transfer molding; matched tool molding; autoclave curing; thermal curing in air; vacuum bagging; pultrusion; Seeman's Composite Resin Infusion Manufacturing Processing (SCRIMP); open molding, continuous combination of polymer and glass; and filament winding, including cylindrical filament winding. For example, an article can be prepared from the disclosed thermoset polymer product via a polymer transfer molding process.
The compositions and methods described herein are further illustrated by the following non-limiting examples.
The materials listed in Table 1 were used in the following examples.
3,3-Bis(4-hydroxyphenyl)-2-phenylisoindolin-1-one (2b) (10.0 grams (g), 0.0254 moles (mol)) and potassium carbonate (8.77 g, 0.0635 mol) were combined in N-methyl 2-pyrrolidine (NMP) (100 milliliters (mL)) and stirred at 20° C. to 25° C. for 30 minutes. After that, 4-nitrophthalonitrile (8.79 g, 0.0508 mol) was added gradually to the reaction mixture over about 10 minutes. The reaction mixture was then maintained for 24 hours at 20° C. to 25° C. Progress of the reaction was monitored by thin-layer chromatography (TLC) [eluents: ethyl acetate (4 mL): hexane (6 mL)]. Once starting material (1b) was no longer observed by TLC, the resulting reaction mixture was filtered. The resulting residue was added to a 50 wt % sodium chloride aqueous solution to obtain a slightly yellowish colored solid. The solid was washed with methanol to obtain 15.6 g (83%) of an off-white colored crystalline solid. The product (1b) was subsequently dried under vacuum at 70° C. for 16 hours.
The dried product was then analyzed using a Shimadzu high performance liquid chromatography (HPLC) system equipped with a quaternary solvent delivery system, an auto sampler, DAD detector, and a column compartment instrumentation that was controlled by ChemStation software. The column was a Poroshell 120, EC-C18, having column dimensions of 4.6 millimeters (mm)×100 mm×2.7 micrometers (μm). The mobile phase (A) was water and mobile phase (B) was acetonitrile. The gradient program used was 0-min B:20%, 10 min B:20%, 15 min B:90%, 22 min B:90%, 23 min B:20%, and 30 min B:20%. The wavelength monitored was at 230 nanometers (nm) and the flow rate was 1.0 milliliter per minute (mL/min). The HPLC purity was 99.0%.
Liquid chromatography (LC-MS) analyses were conducted on a Waters triple quadruple Quattro micro mass spectrometer system, with the instrumentation controlled and synchronized by Mass Lync software. The instrument was operated with an electrospray ionization (EI) source in positive ion mode. The following are the LC-MS parameters used: Capillary voltage—3.5 kilovolts (kV); Cone voltage 30 volts (V); Extractor voltage 5 V; RF lens 0.1 V; Source temperature 1,300° C.; Desolvation temperature: 3,500° C.; dissolution gas flow rate 650 liters per hours (L/hr); Cone gas flow rate 30 L/hr. The structure was confirmed by LC-MS as M/Z: 645.3; M+1 peak: 646.3; Molecular weight: 645.68 Daltons.
Characterization by proton nuclear magnetic resonance (1H NMR): (400 MHz, CDCl3): chemical shift (δ) (parts per million, ppm)=6.90 ppm (d, 2H), 7.1 ppm (d, 4H), 7.2 ppm (dd, 3H), 7.3 ppm (d, 4H), 7.4 ppm (d, 2H), 7.6 ppm (triplet, 1H), 7.65 ppm (triplet, 1H), 7.7 ppm (d, 1H), 7.75 ppm (d, 2H), 7.9 ppm (d, 1H), 8.1 ppm (d, 2H).
The melting point was 243.1° C., as determined by differential scanning calorimetry (DSC).
Attempts were made to prepare the 4,4′-(((3-oxo-2-phenylisoindoline-1,1-diyl)bis(4,1-phenylene))bis(oxy)) diphthalonitrile (1b) using other reaction conditions and without first reacting 3,3-Bis(4-hydroxyphenyl)-2-phenylisoindolin-1-one (2b) with potassium carbonate prior to the addition of nitrophthalonitrile.
The following procedure was used to prepare Comparative Examples 1 to 4. A mixture of 3,3-Bis(4-hydroxyphenyl)-2-phenylisoindolin-1-one (2b) (10 g), 0.0254 mol) and nitrophthalonitrile in 20 mL of a solvent was stirred at room temperature (20 to 25° C.) under nitrogen. Potassium carbonate (8.77 g, 0.0635 mol) was added to the mixture over a period of 2 hours with stirring. After stirring the reaction mixture for a further period of time, the undissolved salt was removed by filtration. The product was isolated and characterized using the same methods as provided in Example 1.
The results are provided in Table 2.
Table 2 shows that the method of Example 1 provides the diphthalonitrile compound (1b) at a purity of 99%. In contrast, Comparative Examples 1 to 4 only afforded 2 to 12% of the diphthalonitrile compound (1b), with a major impurity being the monofunctional phthalonitrile compound. Accordingly, pre-forming the potassium salt of 2b prior to reaction with nitrophthalonitrile provided superior results as compared to forming a potassium salt in-situ.
An exemplary thermosetting composition can include the 4,4′-(((3-oxo-2-phenylisoindoline-1,1-diyl)bis(4,1-phenylene))bis(oxy)) diphthalonitrile (1b), o-phenylenediamine as a curing agent, and a second diphthalonitrile having a structure different from formula (1). The thermosetting composition can be heated at a temperature of 200-500° C. to provide a crosslinked thermoset polymer product having excellent high heat properties.
The disclosure is further illustrated by the following non-limiting aspects.
Aspect 1. A 4,4′-(((3-oxo-isoindoline-1,1-diyl)bis(4,1-arylene))bis(oxy))diphthalonitrile compound of formula (1) wherein each occurrence of R1 is independently a hydrogen, a phenyl, or a C1-6 alkyl, more preferably a hydrogen or a C1-3 alkyl; each occurrence of R2 and R3 is independently a hydrogen, a halogen, or a C1-25 hydrocarbyl, preferably a hydrogen or a C1-6 alkyl, more preferably a hydrogen or a C1-3 alkyl; and r, p, and q are each independently 0-4, more preferably 0 or 1, preferably 0.
Aspect 2. The compound of aspect 1, wherein the compound of formula (1) is a 4,4′-(((3-oxo-2-arylisoindoline-1,1-diyl)bis(4,1-phenylene))bis(oxy))diphthalonitrile of formula (1a) wherein each occurrence of R1 is independently a hydrogen or a C1-3 alkyl; and r and p are each independently 0 or 1, preferably 0.
Aspect 3. The compound of aspect 1, wherein the compound is 4′-(((3-oxo-2-phenylisoindoline-1,1-diyl)bis(4,1-phenylene))bis(oxy))diphthalonitrile of formula (1b).
Aspect 4. A method for the manufacture of the 4,4′-(((3-oxo-isoindoline-1,1-diyl)bis(4,1-arylene))bis(oxy))diphthalonitrile compound (1) of aspect 1, the method comprising contacting an inorganic base and a 3,3-bis(4-hydroxyaryl)-2-arylisoindolin-1-one of formula (2) to provide a metal salt precursor; and reacting the metal salt precursor with 4-nitrophthalonitrile under conditions effective to provide the 4,4′-(((3-oxo-isoindoline-1,1-diyl)bis(4,1-arylene))bis(oxy))diphthalonitrile compound of formula (1), wherein each occurrence of R1 is independently a hydrogen, a phenyl, or a C1-6 alkyl, more preferably a hydrogen or a C1-3 alkyl; each occurrence of R2 and R3 is independently a hydrogen, a halogen, or a C1-25 hydrocarbyl, preferably a hydrogen or a C1-6 alkyl, more preferably a hydrogen or a C1-3 alkyl; and r, p, and q are each independently 0-4, more preferably 0 or 1, preferably 0.
Aspect 5. The method of aspect 4, wherein the 3,3-bis(4-hydroxyaryl)-2-arylisoindolin-1-one (2) is a 3,3-bis(4-hydroxyphenyl)-2-arylisoindolin-1-one of formula (2a) wherein each occurrence of R1 is independently a hydrogen or a C1-3 alkyl and r and p are each independently 0 or 1, preferably 0; preferably wherein the 3,3-bis(4-hydroxyaryl)-2-arylisoindolin-1-one (2) is 3,3-bis(4-hydroxyphenyl)-2-arylisoindolin-1-one of formula (2b).
Aspect 6. The method of aspect 4 or aspect 5, wherein the inorganic base is lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate, or a combination thereof, more preferably wherein the inorganic base comprises potassium carbonate.
Aspect 7. The method of any one or more of aspects 4 to 6, wherein the reacting is in a solvent, preferably wherein the solvent is an alkyl pyrrolidone solvent, an aromatic solvent, a halogenated aromatic solvent, or a combination thereof, more preferably wherein the solvent is N-methyl-2-pyrrolidone, toluene, xylene, ortho-dichlorobenzene, 1,3-dimethyl-2-imidazolinone, 2-pyrrolidone, or a combination thereof.
Aspect 8. A thermosetting composition, comprising the 4,4′-(((3-oxo-isoindoline-1,1-diyl)bis(4,1-arylene))bis(oxy))diphthalonitrile compound of any at least one of aspects 1-3; and a curing agent.
Aspect 9. The thermosetting composition of aspect 7, wherein the curing agent comprises a diamine, a triamine, a higher amine, an acid salt of an amine, or an organic acid having a pKa of less than 4; preferably an amine-containing phosphazene, an aromatic diamine, an aromatic diamine/metal salt complex, an aromatic ether amine, an amine salt of p-toluene sulfonic acid, or an organic acid exhibiting a pKa in water less than 3; more preferably an aromatic diamine or an organic acid exhibiting a pKa in water of less than 2.
Aspect 10. The thermosetting composition of aspect 8, wherein the aromatic diamine is o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl ether, 1,5-diaminonaphthalene, 3,3′-dimethylbenzidine, 3,3′-dimethoxybenzidine, 2,4-bis(β-amino-t-butyl)toluene, bis(p-β-amino-t-butyl)ether, bis(p-β-methyl-o-aminopentyl)benzene, 1,3-diamino-4-isopropylbenzene, 1,2-bis(3-aminopropoxy)ethane, benzidine, m-xylylenediamine, p-xylylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(4-aminophenoxy)phenyl]sulfone, 4,4′-bis(3-aminophenoxy)biphenyl, 4,4′-bis(4-aminophenoxy)biphenyl, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, or a combination comprising at least one of the foregoing.
Aspect 11. The thermosetting composition of any at least one of aspects 7-9, further comprising a comonomer, preferably wherein the comonomer is a diphthalonitrile different from formulas (1), (1a), and (1b).
Aspect 12. The thermosetting composition of any at least one of aspects 7-10, further comprising an additive, preferably wherein the additive is a particulate filler, fibrous filler, antioxidant, heat stabilizer, light stabilizer, ultraviolet light stabilizer, ultraviolet light-absorbing compound, near infrared light-absorbing compound, infrared light-absorbing compound, plasticizer, lubricant, release agent, antistatic agent, anti-fog agent, antimicrobial agent, colorant, surface effect additive, radiation stabilizer, flame retardant, anti-drip agent, fragrance, a polymer different from the thermoset polymer, or a combination thereof.
Aspect 13. A thermoset polymer composition comprising a crosslinked product of the thermosetting composition of any one or more of the preceding aspects.
Aspect 14. An article comprising the thermoset polymer composition of aspect 12, wherein the article is a composite, a foam, a fiber, a layer, a coating, an encapsulant, an adhesive, a sealant, a component, a prepreg, a casing, or a combination thereof.
Aspect 15. The article of aspect 14, wherein the article is an electronic substrate, an electronic housing, a microelectronic device, a printed electronic component, a tooling, a geothermal tool, an oil rig component, a flame retardant component, a sizing resin, a resin infusion molded component, a resin transfer molded component, or a combination thereof.
The compositions, methods, and articles can alternatively comprise, consist of, or consist essentially of, any appropriate materials, steps, or components herein disclosed. The compositions, methods, and articles can additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any materials (or species), steps, or components, that are otherwise not necessary to the achievement of the function or objectives of the compositions, methods, and articles.
All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other (e.g., ranges of “up to 25 wt %, or, more specifically, 5 wt % to 20 wt %”, is inclusive of the endpoints and all intermediate values of the ranges of “5 wt % to 25 wt %,” etc.). “Combinations” is inclusive of blends, mixtures, alloys, reaction products, and the like. The terms “a” and “an” and “the” 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. “Or” means “and/or” unless clearly stated otherwise. Reference throughout the specification to “some embodiments”, “an embodiment”, and so forth, means that a particular element 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 can be combined in any suitable manner in the various embodiments. “Combination thereof” is an open term that includes one or more of the named elements, optionally together with a like element not named.
Unless specified to the contrary herein, all test standards are the most recent standard in effect as of the filing date of this application, or, if priority is claimed, the filing date of the earliest priority application in which the test standard appears.
Unless defined otherwise, technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art to which this application belongs. All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if a term in the present application contradicts or conflicts with a term in the incorporated reference, the term from the present application takes precedence over the conflicting term from the incorporated reference.
The term “hydrocarbyl” and “hydrocarbon” refers broadly to a group comprising carbon and hydrogen, optionally with 1 to 3 heteroatoms, for example, oxygen, nitrogen, halogen, silicon, sulfur, or a combination thereof. The term “aliphatic” means a branched or unbranched, saturated or unsaturated group containing carbon and hydrogen, optionally with 1 to 3 heteroatoms, for example, oxygen, nitrogen, halogen, silicon, sulfur, or a combination thereof. The term “cycloaliphatic” means a saturated or unsaturated group comprising carbon and hydrogen optionally with 1 to 3 heteroatoms, for example, oxygen, nitrogen, halogen, silicon, sulfur, or a combination thereof. The term “alkyl” means a branched or straight chain, saturated monovalent hydrocarbon group, e.g., methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, s-pentyl, and n- and s-hexyl. “Alkenyl” means a straight or branched chain, monovalent hydrocarbon group having at least one carbon-carbon double bond (e.g., ethenyl (—HC═CH2)). “Alkoxy” means an alkyl group that is linked via an oxygen (i.e., alkyl-O—), for example methoxy, ethoxy, and sec-butyloxy groups. “Alkylene” means a straight or branched chain, saturated, divalent hydrocarbon group (e.g., methylene (—CH2—) or, propylene (—(CH2)3—)). “Cycloalkylene” means a divalent cyclic alkylene group, —CnH2n-x, wherein x is the number of hydrogens replaced by cyclization(s). “Cycloalkenyl” means a monovalent group having one or more rings and one or more carbon-carbon double bonds in the ring, wherein all ring members are carbon (e.g., cyclopentyl and cyclohexyl). “Aryl” means a monovalent aromatic hydrocarbon group containing the specified number of carbon atoms, such as phenyl, tropone, indanyl, or naphthyl. “Arylene” means a divalent aryl group. “Alkylarylene” means an arylene group substituted with an alkyl group. “Arylalkylene” means an alkylene group substituted with an aryl group (e.g., benzyl). The terms “heteroaryl” and “heteroarylene” mean a monovalent aromatic group and divalent aromatic group respectively wherein at least one carbon in a ring is replaced by a heteroatom (S, O, P, or N). The prefix “halo” means a group or compound including one more of a fluoro, chloro, bromo, or iodo substituent. A combination of different halo groups (e.g., bromo and fluoro), or only chloro groups can be present.
Unless otherwise indicated, each of the foregoing groups can be unsubstituted or substituted, provided that the substitution does not significantly adversely affect synthesis, stability, or use of the compound. “Substituted” means that the compound, group, or atom 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), C1-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, C1-6 haloalkyl, C1-9 alkoxy, C1-6 haloalkoxy, C3-12 cycloalkyl, C5-18 cycloalkenyl, C6-12 aryl, C7-13 arylalkylene (e.g., benzyl), C7-12 alkylarylene (e.g., toluyl), C4-12 heterocycloalkyl, C3-12 heteroaryl, C1-6 alkyl sulfonyl (—S(═O)2-alkyl), C6-12 arylsulfonyl (—S(═O)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 compound or group, excluding those of any substituents. Thus, a compound of the formula —CH2CH2CN is a C2 alkyl group (—CH2CH3) substituted with a cyano group (—CN).
While particular aspects have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are or may be presently unforeseen may arise to applicants or others skilled in the art. Accordingly, the appended claims as filed and as they may be amended are intended to embrace all such alternatives, modifications variations, improvements, and substantial equivalents.
| Number | Date | Country | Kind |
|---|---|---|---|
| 18161688.9 | Mar 2018 | EP | regional |
