WO2015183518A1 - Synthèse d'additifs de durcissement de phthalonitriles - Google Patents

Synthèse d'additifs de durcissement de phthalonitriles Download PDF

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WO2015183518A1
WO2015183518A1 PCT/US2015/029812 US2015029812W WO2015183518A1 WO 2015183518 A1 WO2015183518 A1 WO 2015183518A1 US 2015029812 W US2015029812 W US 2015029812W WO 2015183518 A1 WO2015183518 A1 WO 2015183518A1
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compound
mixture
phthalonitrile
curing
composition
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PCT/US2015/029812
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English (en)
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Teddy M. Keller
Matthew Laskoski
Andrew SAAB
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The Government Of The United States Of America, As Represented By The Secretary Of The Navy
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Priority claimed from EP13826354.6A external-priority patent/EP2880079B1/fr
Priority claimed from US14/287,316 external-priority patent/US8859712B2/en
Priority claimed from US14/483,264 external-priority patent/US8981036B2/en
Application filed by The Government Of The United States Of America, As Represented By The Secretary Of The Navy filed Critical The Government Of The United States Of America, As Represented By The Secretary Of The Navy
Publication of WO2015183518A1 publication Critical patent/WO2015183518A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • C08G65/33365—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing cyano group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment

Definitions

  • the present disclosure is generally related to synthesis of oligomeric phthalonitriles and low temperature curing additives for phthalonitriles.
  • Phthalonitrile-based polymers exhibit superior flammability and high temperature properties relative to other high temperature polymers.
  • the phthalonitrile technology may be used to replace polyimides for aircraft applications and vinyl esters/epoxy resins for ship applications due to their improved processability and superior physical characteristics.
  • Phthalonitrile resins may show potential as matrix materials for advanced composites for numerous applications. Until the synthesis of the oligomeric aromatic phthalonitrile, the polymerization reactions had to be performed at temperatures at or greater than 250°C, which is slightly greater than the melting point of the first generation aromatic phthalonitriles, synthesized from the salts of the bisphenols and 4-nitrophthalonitrile. The phthalonitrile monomers polymerize through the cyano groups with the aid of an appropriate curing agent to yield a crosslinked polymeric network with high thermal and oxidative stabilities.
  • thermoset polymer/composite that does not exhibit a glass transition temperature.
  • high aromatic content of the thermoset affords a high char yield (80-90%) when pyrolyzed to 1000°C under inert conditions.
  • the high thermal stability and the ability to form a high char yield (very little gas formation) upon pyrolysis contribute to the outstanding fire performance of the phthalonitrile polymer.
  • the fire performance of phthalonitrile-carbon and phthalonitrile-glass composites are superior to that of other thermoset-based composites currently in use for aerospace, ship and submarine applications.
  • the phthalonitriles are still the only polymeric material that meets MIL-STD-2031 for usage inside of a submarine.
  • a low viscosity resin enables composite processing by resin transfer molding (RTM), filament winding, and resin infusion molding (RIM) methods and potentially by automated composite
  • a low melt viscosity and a larger processing window are useful for fabrication of thick composite sections where the melt has to impregnate into thick fiber performs.
  • a method comprising: providing a solution comprising a
  • dichloroaromatic compound comprising an electron- withdrawing group bound to each aromatic ring containing one of the chloride groups; a dihydroxyaromatic compound or anion thereof; wherein the molar ratio of the dihydroxyaromatic compound to the dichloroaromatic compound is greater than 2: 1; base; and a solvent; and heating the solution to a temperature at which the dichloroaromatic compound and the dihydroxyaromatic compound react to form a dimetallic salt of an aromatic ether oligomer. Water formed during the heating is concurrently distilled from the solution.
  • composition comprising a mixture of: a first compound having the formula:
  • Ar 1 and Ar 2 are independently selected aromatic groups, and the mole ratio of the first compound to the second compound is at least 1:20.
  • composition comprising phthalonitrile compounds that comprise at least 5 mol of the first compound.
  • the improved method involves the reaction of a bisphenol with chlorobenzophenone in the optional presence of a base, such as an alkaline hydroxide base, and a soluble organic copper complex or a copper, platinum, or palladium salt.
  • a base such as an alkaline hydroxide base
  • a soluble organic copper complex or a copper, platinum, or palladium salt A high boiling solvent such as NMP may be used.
  • the reaction may be performed at temperatures in excess of 150°C to initially form the oligomeric aromatic ether- aromatic ketone terminated as a phenolate salt.
  • the reaction may readily occur in high yield for the lower molecular weight oligomeric phthalonitriles.
  • Further reaction of the phenolate salt with 4-nitrophthalonitrile affords the oligomeric aromatic ether- aromatic ketone phthalonitrile in high yields.
  • the oligomeric phthalonitrile was synthesized with the more reactive and more costly fluorobenzophenone, which readily occurred at 150°C in dipolar aprotic solvents.
  • the present reaction may be performed at a higher temperature due to the lower reactivity of the chlorobenzophenone relative to
  • the oligomeric phthalonitriles typically have melting points or glass transition temperatures and exist as liquids between about 40° and 100°C.
  • the curing mixture composed of a combination of metal salts and strong inorganic and/or strong organic acids affords the ability to partial cure (B-stage) phthalonitrile resins/monomers and perform gelation to a shaped solid at temperatures below 200°C, for which there are no known prior reports achieving this for the phthalonitrile resins/monomers. Being able to form the shaped solid below 200°C may be important to users having curing autoclaves with temperature limitations below 200 °C.
  • the methods disclosed herein are targeted towards developing high temperature and flame resistant polymers/composites and addressing processability of the phthalonitrile resins to a shaped solid at temperature below 250°C.
  • more reactive curing agent(s) that more strongly interact with the cyano units of the phthalonitrile moieties and readily propagate the curing reaction are used.
  • the time to gelation is controlled as a function or reactivity of the curing additive, amount of curing additive, and the temperature.
  • the phthalonitrile is not fully cured but has been partially polymerized from the liquid phase to a shaped solid in the presence of the curing additives.
  • the partially cured (B- stage) may be stable under ambient conditions without the need to store in a freezer. This is in contrast to epoxies and certain polyimides that have to be stored under freezer conditions to reduce the curing, which continues to slowly occur.
  • the B-staged phthalonitrile may be stable indefinitely under ambient conditions and only continues to cure when heated above 150°C.
  • the gelled shaped solid can be further cured at higher temperatures to complete the cure or polymerization reaction and improve on the physical properties.
  • the gelled shaped solids can be isolated and stored indefinitely under ambient conditions until ready to complete the cure at elevated temperatures.
  • Highly aromatic phthalonitriles have not been previously converted to the gelled solid below 250°C.
  • the phthalonitrile polymers, formed from the novel oligomeric phthalonitrile monomers, may exhibit outstanding flammability properties for ship, submarine, aerospace, and other domestic applications and may be able to withstand high temperatures (300-375°C) in oxidative environments such as air.
  • Liquid precursor resins such as the low melting, liquid oligomeric phthalonitriles may be useful in composite fabrication by a variety of cost effective methods such as resin infusion molding (RIM), resin transfer molding (RTM), filament winding, and prepreg consolidation. Furthermore, resins with a large window between the melting point or liquid phase and the cure temperature are desirable to control the viscosity and the rate of curing for fabrication of shaped fiber reinforced composite composites by the cost effective methods.
  • RIM resin infusion molding
  • RTM resin transfer molding
  • filament winding filament winding
  • prepreg consolidation resin infusion molding
  • resins with a large window between the melting point or liquid phase and the cure temperature are desirable to control the viscosity and the rate of curing for fabrication of shaped fiber reinforced composite composites by the cost effective methods.
  • processability to shaped composite components may be achieved in autoclave and non-autoclave conditions below 200°C and by the cost effective methods.
  • Oligomeric aromatic ether-aromatic ketone-containing phthalonitriles have been synthesized by a more cost effective method from a bisphenol and chlorobenzophenone in the presence of a base, such as sodium hydroxide or potassium hydroxide, and an optional organic copper complex.
  • a base such as sodium hydroxide or potassium hydroxide
  • Various amounts of, for example, bisphenol and chlorobenzenophenone are used with bisphenol always in excess to ensure termination of the oligomeric composition as the diphenolate (Eqs. (l)-(2)) (also referred to as a dimetallic salt of the dihydroxyaromatic compound).
  • the phenolate terminated composition can be end-capped by reaction with the 4-nitrophthalonitrile to afford the oligomeric phthalonitrile (Eqs. (3)-(4)).
  • Ratios between the adjacent integer ratios above, such as for example 2.5: 1 or excesses of 5, 10, 20, 30, or 40 mol , will produce a significant amount of the diphenolate salt of the dihydroxyaromatic compound.
  • These salts also react with 4-nitrophthalonitrile to form phthalonitrile monomers that can cure to a thermoset with or without longer phthalonitrile monomers. They may help to reduce the viscosity of the monomer blend before it cures, while still producing suitable properties in the thermoset. The reduced viscosity may allow for formation of fibers, including textile fibers, from the monomer blend.
  • the use of excess dihydroxyaromatic may also decrease the time required for high yields to, for example, 5-6 hr at 160-170°C.
  • the first compound and the second compound together make up at least 50, 60, 70, 80, 90, or 95 mol of all the phthalonitrile compounds in the composition.
  • the first compound may make up at least 5, 10, 20, 30, 40, or 50 mol of all the phthalonitrile compounds in the composition.
  • the synthesis of the oligomeric phthalonitrile using the chlorobenzophenone rather than fluorobenzophenone is an advanced synthetic method that is more cost effective and a superior commercialization method.
  • the reaction of the chlorobenzophenone with a bisphenol (or any dihydroxyaromatic) in the presence of a base may not occur with the typical dipolar aprotic solvents (DMF or DMAC) but may be carried out at higher temperatures using a higher boiling solvent such as DMSO or NMP to convert to high yields (>95 ) of the phenolate salt.
  • End capping of the salt with 4-nitrophthalonitrile may be performed from ambient to 100°C to afford quantitative yields of the oligomeric phthalonitrile.
  • Low melting oligomeric phthalonitriles may be cured to gelation or a shaped solid in the presence of various highly reactive curing additives below 250°C (Eq. (5)).
  • various highly reactive curing additives below 250°C (Eq. (5)).
  • Various amounts of the curing additive mixture (including but not limited to 1-10 wt or 2-5 wt%) relative to the phthalonitrile have been evaluated.
  • the precursor composition phthalonitrile monomer and curing additive
  • the precursor composition may be mixed under ambient conditions or may be added at any temperature in the melt state up to the decomposition temperature.
  • the precursor composition can be heated to a B-staged mixture (liquid) in which some reaction has occurred but before gelation occurs. Further heating below 250°C will result in the composition becoming rubbery before gelation to the shaped solid.
  • the solid can retain its shape, be stored indefinitely under ambient condition, or be placed in a high temperature furnace/oven at temperatures up to 500°C to fully cure to a polymer that does not exhibit a glass transition temperature (T g ) (Eq. (5)).
  • T g glass transition temperature
  • any phthalonitrile monomer that exists in the liquid state below 250°C can be cured to a shaped solid by the curing additives of this invention.
  • the curing additive composed of a combination of metal salt and strong inorganic and/or organic acid
  • such phthalonitriles include the simple bisphenol-based phthalonitriles of bisphenol A (bisphenol A phthalonitrile, m. p. 195- 198°C) and resorcinol (resorcinol phthalonitrile, m.p. 173-175°C), the multiple aromatic ether oligomeric phthalonitriles, and the aromatic ether PEEK-like phthalonitriles.
  • Strong acids that have been used to form the curing additive include sulfuric acid, sulfurous acid, phosphoric acid, p-toluene sulfonic acid, and naphthalenesulfonic acid.
  • Transition metal salts are typically used as the metal source in the curing additive mixtures including the metal salts of Cu, Co, Fe, Sn, Zn, Ni, and Pd.
  • the new curing compositions/mixtures for the curing of the liquid or low melting phthalonitriles may afford the ability to convert to a shaped, partially cured solid at temperatures below 250°C. There are no known prior reports of gelation being achieved at these temperatures. When used alone, most of the reactive aromatic diamines [e.g.
  • l,3-bis(3-aminophenoxy)benzene; m-APB or l,4-bis(4-aminophenoxy)benzene; p-APB] used as a curing additive must be added to the melt or liquid of the phthalonitrile at 250°C for quick reaction due to the volatility of the amine curing additive (Sastri et al, "Phthalonitrile Cure Reaction with Aromatic Diamines" J. Polym. Sci. A: Polym. Chem. 36, 1885-1890 (1998)).
  • the less reactive thermally stable diamine, bis[4-(4-aminophenoxy)phenyl]sulfone; p-BAPS] has been typically used to cure the
  • the first step was the addition of the diamine curing agent to the monomer melt at 250-255°C in air followed by quenching the reaction after 10-15 min to form a phthalonitrile prepolymer or B-staged resin.
  • the second stage involved phthalonitrile polymer by heating the prepolymer under inert conditions or in air over an extended period of time above 250°C.
  • Precursor compositions involving the phthalonitrile and the metal salts can be formulated under ambient conditions and heated to the required polymerization temperature without fear of volatility or the curing additive can be added directly to the liquid at the initial polymerization temperature.
  • the oligomeric phthalonitriles and bisphenol-based phthalonitriles with melting points below 200°C can be partially cured to a shaped solid from a precursor composition heated from ambient to the initial curing temperature below 200°C or can be added directly to the phthalonitrile at the initial curing temperature.
  • the partially cured phthalonitrile-based solids may exhibit a glass transition temperature usually below the initial curing temperature.
  • the oligomeric and bisphenol-based phthalonitriles were cured in the presence of aromatic amines at or greater than 250°C to achieve gelation in a timely manner.
  • the shaped solid can be stored indefinitely at room temperature without further reaction.
  • the phthalonitrile-curing composition/mixture can be formulated at room temperature and stored indefinitely under ambient conditions.
  • a prepolymer mixture (B-stage) can be produced at temperatures up to 250°C and quenched before gelation and stored indefinitely under ambient conditions for usage such as coatings needing a high molecular weight prepolymer to achieve a continuous film and for other applications needing a fast cure to gelation.
  • the B- staged mixture is soluble in common solvents.
  • Phthalonitrile prepregs containing the curing composition can be stored indefinitely under ambient condition without the new for storage under freezer conditions, which is the case with other resin systems such as epoxy curing compositions. Heating can be longer at about 200°C or with larger concentration of aromatic amines and cure at 200°C. In textile applications, the B-staged or prepolymer composition may slowly cure at as low as 150°C. By controlling the initial cure to the shaped solid below 200°C, existing autoclaves designed for epoxy technology can be used to fabricate composite
  • shaped solids and composite components can be fabricated by cost effective method such as resin transfer molding (RTM), resin infusion molding (RIM), filament winding, and prepreg consolidation and potentially by automated composite manufacturing techniques such as automated tape laying and automated fiber placement.
  • RTM resin transfer molding
  • RIM resin infusion molding
  • filament winding filament winding
  • prepreg consolidation and potentially by automated composite manufacturing techniques such as automated tape laying and automated fiber placement.
  • automated composite manufacturing techniques such as automated tape laying and automated fiber placement.
  • the ability to cure to a shaped solid below 250°C and the superior physical properties relative to other high temperature polymers such as polyimides enhances the importance of the phthalonitrile system.
  • the phthalonitrile-based polymers Due to the low water absorptivity, processability at a temperature comparable to epoxy resins, and the superior thermo-oxidative stability of fully cured phthalonitriles to temperatures in excess of 375°C, the phthalonitrile-based polymers have potential for a variety of applications not envisioned before including its use in the fabrication of advanced composites by conventional prepreg consolidation, RTM, injection molding, RIM, and filament winding.
  • the oligomeric phthalonitrile-based polymers would be expected to exhibit improvements in specific physical properties, e.g., toughness and processability, relative to systems with a short spacer (bisphenol A phthalonitrile and resorcinol phthalonitrile) between the terminal phthalonitrile moieties.
  • a solution that includes the dichloroaromatic compound, the dihydroxyaromatic compound, the organic transition metal complex or the transition metal salt, if used, the base, and the solvent is provided.
  • All references to the dihydroxyaromatic compound and the dichloroaromatic compound include mixtures of more than one of such compounds for producing phthalonitriles that can incorporate more than one of the compounds. Statements of relative amounts of these compounds can refer to the entire amount of each type of compound.
  • the dichloroaromatic compound is activated by one or more electron withdrawing groups. The electron withdrawing group(s) are bound to each of the aromatic rings that has one of the chloride groups.
  • the compound may have a single electron withdrawing group that activates both chlorides, either in a single ring or bridging two rings.
  • Benzophenone has an electron withdrawing carbonyl unit to activate the chloro units being displaced by the nucleophilic reaction of the dipotassium or disodium salt of the dihydroxy- terminated aromatic reactant.
  • Dichlorobenzophenenones including 4,4'-dichlorobenzophenenone, are suitable.
  • Another suitable compound is bis(4-chlorophenyl)sulfoxide. Any dihydroxyaromatic compound may be used, including but not limited to, a bisphenol,2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4- hydroxyphenyl)-l, l,l,3,3,3-hexafluoropropane, or resorcinol may be used.
  • Other suitable reactants are disclosed in US Patent Nos.
  • the dichloro- and dihydroxy- compounds also include trifunctional and higher such compounds.
  • the reaction proceeds essentially the same way regardless of the dichloroaromatic and dihydroxyaromatic selected.
  • the organic transition metal complex may be in solution with the reactants, but this is not required. Transition metal salts may be only partially soluble at a given temperature, but may still be used in the reaction. Multiple such catalysts may be used to enhance the reaction conditions. Suitable transition metals include Cu, Zn, Fe, Co, Ni, Pd, and Pt.
  • One suitable copper complex is bromotris(triphenylphosphine)copper(I) ((PPh 3 ) 3 CuBr).
  • Other suitable compounds may be found in the above cited patents as well as in US Patent Nos. 8,288,454; 7,897,715; 7,723,420; 7,511,113; 7,348,395; 7,342,085; 7,087,707; and 5,980,853.
  • One suitable base is potassium carbonate. Other suitable bases may be found in the above cited patents.
  • Any solvent that dissolves the aromatic compounds and can be heated to a temperature that causes the reaction may be used.
  • Higher boiling point solvents may be suitable as the chloro compounds are less reactive than the similar fluoro compounds.
  • Suitable solvents include, but are not limited to, dimethylsulfoxide (DMSO), ⁇ , ⁇ -dimethylacetamide (DMAC), N- methylpyrrolidinone (NMP), and others disclosed in the above cited patents.
  • DMSO may allow for higher reaction temperatures such as 170°, resulting faster reaction times, and in the absence of the copper catalyst.
  • Lower boiling solvents such as DMAC and DMF may be suitable at lower temperatures when a copper catalyst is used.
  • the solution may be heated to, for example 130-150°C, 165°C, 170°C, 180°C, or higher, causing formation of the aromatic ether oligomer.
  • the oligomer may be formed as a salt of the metal from the base, such as a potassium or sodium salt. Formation of the hydroxyl form may also occur in the presence of water.
  • the initial addition of water dissolves the base and enhances with the bisphenol.
  • the added water and water formed from the reaction of the aromatic compounds is distilled as the reaction progresses in order to move the reaction to completion.
  • the use of high temperatures, along with the copper compound can increases the reaction yield, which may be, for example, at least 90% or at least 95%. The yield may be higher than typically seen using the fluoro analogs of the chloro compounds.
  • Bisphenols may generally have a higher yield than resorcinol.
  • the aromatic ether oligomer or the mixture containing the aromatic ether oligomer and excess dimetallic bisphenol (short spacer) salt is reacted with 4- nitrophthalonitrile to form a phthalonitrile monomer.
  • the presence of the short spacer phthalonitrile within the product mixture may act to reduce the viscosity and flow properties for processability into shaped polymers and composite components.
  • the reaction generally occurs upon addition of the 4-nitrophthalonitrile and heating. Methods of performing this reaction are described below and in the above cited patents.
  • the phthalonitrile monomer is cured to form a phthalonitrile thermoset.
  • the curing may occur in two steps. An initial cure to gelation at 250°C or less or 200°C or less, followed by a postcure at higher temperatures, such as up to 450°C, to form a fully cured thermoset.
  • the initial cure may be performed in a mold so that the monomer may be converted to a melt and form an article having a desired shape. That shape can remain the same during the postcure.
  • Suitable acids for the curing additive include, but are not limited to, sulfuric acid, sulfurous acid, phosphoric acid, /?-toluene sulfonic acid, naphthalenesulfonic acid, and
  • Metal salts may be used as the curing agent including but not limited to, copper (II) acetylacetonate, palladium (II) acetylacetonate, zinc (II) naphthenate, cobalt (II) acetylacetonate, nickel (II) acetylacetonate, iron (III) acetylacetonate, and tin (II) oxalate.
  • copper (II) acetylacetonate palladium (II) acetylacetonate, zinc (II) naphthenate, cobalt (II) acetylacetonate, nickel (II) acetylacetonate, iron (III) acetylacetonate, and tin (II) oxalate.
  • suitable salts as well as organic or diamine curing agents are disclosed herein and in the above cited patents.
  • the curing may be performed using phthalonitrile compound, whether or not formed by the above synthesis procedure.
  • the aromatic ether oligomer or diphenolate salt thereof may be synthesized without subsequently synthesizing the phthalonitrile monomer or thermoset.
  • the curing may be performed on a mixture of phthalonitriles, including the presence of a significant amount of the phthalonitrile made from the dihydroxyaromatic
  • Toluene was used to control the refluxing azeotropic removal of water and to control the temperature of the reaction content.
  • the resulting mixture was degassed with nitrogen at ambient temperature and the Dean-Stark trap was filled with toluene.
  • the mixture was refluxed at 135-145°C under a nitrogen atmosphere for 6 hr or until no more water was observed being collected in the Dean-Stark trap.
  • the toluene was then slowly distilled off causing the temperature to rise in the reaction vessel to enhance the yield of the intermediate hydroxyl salt and high conversion to this intermediate.
  • the reaction mixture was heated above 180°C for an additional 12 hr with a very small amount of toluene present to control the temperature and to totally remove the water formed as a by-product, so that the reaction could be pushed to completion and high conversion to the hydroxyl salt intermediate.
  • the mixture was cooled to 50°C.
  • 4-nitrophthalonitrile (11.7 g, 67.5 mmol) was added in one portion and the reaction mixture was heated at 80°C for 6-8 hr.
  • the mixture was allowed to cool to ambient temperature and poured into a 5% aqueous HC1 solution resulting in the formation of a solid.
  • the material was broken up and collected using a Buchner funnel.
  • the resulting mixture was degassed with nitrogen at ambient temperature and the Dean-Stark trap was filled with toluene.
  • the mixture was refluxed at 135-145°C under a nitrogen atmosphere for 6 hr or until no more water was observed being collected in the Dean-Stark trap.
  • the toluene was then slowly distilled off causing the temperature to rise in the reaction vessel to enhance the yield of the intermediate hydroxyl salt and high conversion to this intermediate.
  • the reaction mixture was heated above 180°C for an additional 12 hr with a very small amount of toluene present to control the temperature and to remove the total water formed as a by-product, so that the reaction could be pushed to completion and high conversion to the hydroxyl salt intermediate.
  • the mixture was cooled and the dipotassium salt of the 2: 1 oligomeric hydroxyl compound was left in solution to use in further reactions.
  • Toluene was used to control the refluxing azeotropic removal of water and to control the temperature of the reaction content.
  • the resulting mixture was degassed with nitrogen at ambient temperature and the Dean-Stark trap was filled with toluene.
  • the mixture was refluxed at 135-145°C under a nitrogen atmosphere for 6-16 hr or until no more water was observed being collected in the Dean-Stark trap.
  • the toluene was then slowly distilled and the mixture was cooled to 50°C. At this time, 4-nitrophthalonitrile (7.90 g, 45.6 mmol) was added in one portion and the reaction mixture was heated at 80°C for 6-8 hr.
  • the mixture was allowed to cool to ambient temperature and poured into a 5% aqueous HC1 solution resulting in the formation of a solid.
  • the material was broken up and collected using a Buchner funnel.
  • the white solid was washed with 200 mL of a 5% aqueous KOH solution, with 200 mL portions of distilled water until neutral, with 200 mL of a 5% aqueous HC1 solution, and finally with 200 mL portions of water until neutral.
  • the isolated solid was vacuum dried to yield the 2: 1 oligomeric phthalonitrile (23.8 g, 97% yield).
  • Toluene was used to control the refluxing azeotropic removal of water and to control the temperature of the reaction content.
  • the resulting mixture was degassed with nitrogen at ambient temperature and the Dean-Stark trap was filled with toluene.
  • the mixture was refluxed at 135-145°C under a nitrogen atmosphere for 8-16 hr or until no more water was observed being collected in the
  • Toluene was used to control the refluxing azeotropic removal of water and to control the temperature of the reaction content.
  • the resulting mixture was degassed with nitrogen at ambient temperature and the Dean-Stark trap was filled with toluene.
  • the mixture was refluxed at 135-145°C under a nitrogen atmosphere for 8-16 hr or until no more water was observed being collected in the Dean-Stark trap.
  • the toluene was then slowly distilled off causing the temperature to rise in the reaction vessel to enhance the yield of the intermediate hydroxyl salt and high conversion to this intermediate.
  • the mixture was cooled to 50°C.
  • Toluene was used to control the refluxing azeotropic removal of water and to control the temperature of the reaction content.
  • the resulting mixture was degassed with nitrogen at ambient temperature and the Dean-Stark trap was filled with toluene.
  • the mixture was refluxed at 135-145°C under a nitrogen atmosphere for 6 hr or until no more water was observed being collected in the Dean-Stark trap.
  • the toluene was then slowly distilled off causing the temperature to rise in the reaction vessel to enhance the yield of the intermediate hydroxyl salt and high conversion to this intermediate.
  • the reaction mixture was heated above 180°C for an additional 12 hr with a very small amount of toluene present to control the temperature and to totally remove the water formed as a by-product, so that the reaction could be pushed to completion and high conversion to the hydroxyl salt intermediate.
  • the mixture was cooled to 50°C.
  • 4-nitrophthalonitrile 99.1 g, 573 mmol was added in one portion and the reaction mixture was heated at 80°C for 6-8 hr.
  • the mixture was allowed to cool to ambient temperature and poured into a 5% aqueous HCl solution resulting in the formation of a solid.
  • the material was broken up and collected using a Buchner funnel.
  • Toluene was used to control the refluxing azeotropic removal of water and to control the temperature of the reaction content.
  • the resulting mixture was degassed with nitrogen at ambient temperature and the Dean-Stark trap was filled with toluene.
  • the mixture was refluxed at 135-145°C under a nitrogen atmosphere for 6 hr or until no more water was observed being collected in the Dean-Stark trap.
  • the toluene was then slowly distilled off causing the temperature to rise in the reaction vessel to enhance the yield of the intermediate hydroxyl salt and high conversion to this intermediate.
  • the reaction mixture was heated above 180°C for an additional 12 hr with a very small amount of toluene present to control the temperature and to totally remove the water formed as a by-product, so that the reaction could be pushed to completion and high conversion to the hydroxyl salt intermediate.
  • the mixture was cooled to 50°C.
  • 4-nitrophthalonitrile (52.7 g, 304 mmol) was added in one portion and the reaction mixture was heated at 80°C for 6-8 hr.
  • the mixture was allowed to cool to ambient temperature and poured into a 5% aqueous HCl solution resulting in the formation of a solid.
  • the material was broken up and collected using a Buchner funnel.
  • the white solid was washed with 200 mL of a 5% aqueous KOH solution, with 200 mL portions of distilled water until neutral, with 200 mL of a 5% aqueous HCl solution, and finally with 200 mL portions of water until neutral.
  • the isolated solid was vacuum dried to yield the product mixture of 2: 1 oligomeric phthalonitrile and resorcinol phthalonitrile (70.6 g, 90% yield).
  • the mixture was placed in a furnace and cured under air by heating at 190°C for 16 hr (overnight) to afford a polymer; gelation to a shaped solid occurred after 1 hr. At this point the polymer exhibited a glass transition (T g ) at around 165°C.
  • the polymer Upon post-curing to above 375°C, the polymer no longer exhibited a T g .
  • the polymer exhibited excellent thermal and oxidative stability up to 450°C before any weight loss was detected as determined by a thermo gravimetric analysis (TGA). Catastrophic decomposition occurred after 500°C in air.
  • acetylacetonate (5 wt%) cured at 200°C -
  • the mixture was placed in a furnace and cured under air by heating at 200°C for 16 hr (overnight) to afford a polymer; gelation to a shaped solid occurred after 0.5 hr. At this point, the polymer exhibited a T g at around 170°C.
  • acetylacetonate (2.5 wt%) cured at 200°C -
  • the 2: 1 oligomeric phthalonitrile from Example 2 (1000 mg), p-toluenesulfonic acid (10 mg), and copper (II) acetylacetonate (25 mg) were stirred at 190°C for 2 minutes, whereby the mixture darkened and began to turn green.
  • the mixture was placed in a furnace and cured under air by heating at 200°C for 16 hr (overnight) to afford a polymer; gelation to a shaped solid occurred after 4 hr. At this point, the polymer exhibited a T g at around 160°C.
  • the polymer Upon post-curing to above 375°C, the polymer no longer exhibited a T g .
  • the polymer exhibited excellent thermal and oxidative stability up to 450°C before any weight loss was detected as determined by TGA. Catastrophic decomposition occurred after 500°C in air.
  • acetylacetonate (5 wt%) cured at 175°C -
  • the mixture was placed in a furnace and cured under air by heating at 175°C for 16 hr (overnight) to afford a polymer; gelation to a shaped solid occurred after 6 hr. At this point, the polymer exhibited a T g at around 126°C.
  • the mixture was placed in a furnace and cured under air by heating at 250°C for 16 hr (overnight) to afford a polymer; gelation to a shaped solid occurred after 15 min. At this point, the polymer exhibited a T g at around 220°C. Upon post-curing to above 375°C, the polymer no longer exhibited a T g . The polymer exhibited excellent thermal and oxidative stability up to 450°C before any weight loss was detected as determined by TGA. Catastrophic decomposition occurred after 500°C in air.
  • acetylacetonate (5 wt%) cured at 200°C -
  • the mixture was placed in a furnace and cured under air by heating at 200°C for 16 hr (overnight) to afford a polymer; gelation to a shaped solid occurred after 0.5 hr. At this point, the polymer exhibited a T g at around 155°C.
  • the polymer Upon post-curing to above 375°C, the polymer no longer exhibited a T g .
  • the polymer exhibited excellent thermal and oxidative stability up to 450°C before any weight loss was detected as determined by TGA. Catastrophic decomposition occurred after 500°C in air.
  • acetylacetonate (5 wt%) cured at 200°C -
  • the mixture was placed in a furnace and cured under air by heating at 200°C for 16 hr (overnight) to afford a polymer; gelation to a shaped solid occurred after 1 hr. At this point, the polymer exhibited a T g at around 165°C.
  • the polymer Upon post-curing to above 375°C, the polymer no longer exhibited a T g .
  • the polymer exhibited excellent thermal and oxidative stability up to 450°C before any weight loss was detected as determined by TGA. Catastrophic decomposition occurred after 500°C in air.
  • acetylacetonate (5 wt%) cured at 225 °C -
  • the mixture was placed in a furnace and cured under air by heating at 225 °C for 16 hr (overnight) to afford a polymer; gelation to a shaped solid occurred after 0.5 hr. At this point, the polymer exhibited a T g at around 200°C.
  • the mixture was placed in a furnace and cured under air by heating at 200°C for 16 hr (overnight) to afford a polymer; gelation to a shaped solid occurred after 3 hr. At this point, the polymer exhibited a T g at around 160°C. Upon post-curing to above 375°C, the polymer no longer exhibited a T g .
  • the polymers exhibited excellent thermal and oxidative stability up to 450°C before any weight loss was detected as determined by TGA. Catastrophic decomposition occurred after 500°C in air.
  • the polymer exhibited a T g at around 175°C. Upon post-curing to above 375°C, the polymer no longer exhibited a T g .
  • the polymer exhibited excellent thermal and oxidative stability up to 450°C before any weight loss was detected as determined by TGA. Catastrophic decomposition occurred after 500°C in air.
  • acetylacetonate (5 wt%) cured at 150°C -
  • the 2: 1 oligomeric phthalonitrile from Example 4 (230 mg), sulfuric acid (5 mg), and copper (II) acetylacetonate (12 mg) were stirred at 150°C for 2 minutes, whereby the mixture darkened and turned red.
  • the mixture was placed in a furnace and cured under air by heating at 150°C for 16 hr (overnight) to afford a polymer; gelation to a shaped solid occurred after 5 hr.
  • the polymer exhibited a T g at around 95 °C.
  • the polymer Upon post-curing to above 375°C, the polymer no longer exhibited a T g .
  • the polymers exhibited excellent thermal and oxidative stability up to 450°C before any weight loss was detected as determined by TGA. Catastrophic decomposition occurred after 500°C in air.
  • the mixture was placed in a furnace and cured under air by heating at 200°C for 16 hr (overnight) to afford a polymer; gelation to a shaped solid occurred after 3 hr. At this point, the polymer exhibited a T g at around 158°C. Upon post-curing to above 375°C, the polymer no longer exhibited a T g . The polymer exhibited excellent thermal and oxidative stability up to 450°C before any weight loss was detected as determined by TGA. Catastrophic decomposition occurred after 500°C in air.
  • acetylacetonate (5 wt%) cured at 200°C -
  • the mixture was placed in a furnace and cured under air by heating at 200°C for 16 hr (overnight) to afford a polymer;
  • the mixture was placed in a furnace and cured under air by heating at 200°C for 16 hr (overnight) to afford a polymer; gelation to a shaped solid occurred after 1 hr. At this point, the polymer exhibited a T g at around 152°C. Upon post-curing to above 375°C, the polymer no longer exhibited a T g . The polymer exhibited excellent thermal and oxidative stability up to 450°C before any weight loss was detected as determined by TGA. Catastrophic decomposition occurred after 500°C in air.
  • the mixture was placed in a furnace and cured under air by heating at 200°C for 16 hr (overnight) to afford a polymer; gelation to a shaped solid occurred after 15 min. At this point, the polymer exhibited a T g at around 137°C. Upon post-curing to above 375°C, the polymer no longer exhibited a T g . The polymer exhibited excellent thermal and oxidative stability up to 450°C before any weight loss was detected as determined by TGA. Catastrophic decomposition occurred after 500°C in air.
  • An oligomeric phthalonitrile (1615 mg), prepared from the reaction of 2 moles of resorcinol and 1 mole of 1,3-dibromobenzene under modified Ullmann conditions followed by end capping of the intermediate salt with 4-nitrophthalonitrile, trifluoromethanesulfonic acid (13 mg), and cobalt (II) acetylacetonate (33 mg) were stirred at 150°C for 2 minutes, whereby the mixture darkened and began to turn green.
  • the mixture was placed in a furnace and cured under air by heating at 200°C for 16 hr (overnight) to afford a polymer; gelation to a shaped solid occurred after 1 hr. At this point, the polymer exhibited a T g at around 155°C. Upon post-curing to above 375°C, the polymer no longer exhibited a T g . The polymer exhibited excellent thermal and oxidative stability up to 450°C before any weight loss was detected as determined by TGA. Catastrophic decomposition occurred after 500°C in air.
  • the mixture was placed in a furnace and cured under air by heating at 200°C for 16 hr (overnight) to afford a polymer; gelation to a shaped solid occurred after 2 hr. At this point, the polymer exhibited a T g at around 165°C. Upon post-curing to above 375°C, the polymer no longer exhibited a T g . The polymer exhibited excellent thermal and oxidative stability up to 450°C before any weight loss was detected as determined by TGA. Catastrophic decomposition occurred after 500°C in air.
  • the mixture was placed in a furnace and cured under air by heating at 200°C for 16 hr (overnight) to afford a polymer; gelation to a shaped solid occurred after 2 hr. At this point, the polymer exhibited a T g at around 145°C. Upon post-curing to above 375°C, the polymer no longer exhibited a T g . The polymer exhibited excellent thermal and oxidative stability up to 450°C before any weight loss was detected as determined by TGA. Catastrophic decomposition occurred after 500°C in air.
  • the mixture was placed in a furnace and cured under air by heating at 200°C for 16 hr (overnight) to afford a polymer; gelation to a shaped solid occurred after 3 hr. At this point, the polymer exhibited a T g at around 155°C. Upon post-curing to above 375°C, the polymer no longer exhibited a T g . The polymer exhibited excellent thermal and oxidative stability up to 450°C before any weight loss was detected as determined by TGA. Catastrophic decomposition occurred after 500°C in air.
  • the mixture was placed in a furnace and cured under air by heating at 200°C for 16 hr (overnight) to afford a polymer; gelation to a shaped solid occurred after 3 hr. At this point, the polymer exhibited a T g at around 165°C. Upon post-curing to above 375°C, the polymer no longer exhibited a T g . The polymer exhibited excellent thermal and oxidative stability up to 450°C before any weight loss was detected by TGA. Catastrophic decomposition occurred after 500°C in air.
  • the mixture was placed in a furnace and cured under air by heating at 200°C for 16 hr (overnight) to afford a polymer; gelation to a shaped solid occurred after 1 hr. At this point the polymer exhibited a glass transition (T g ) at around 165°C. Upon post-curing to above 375°C, the polymer no longer exhibited a T g . The polymer exhibited excellent thermal and oxidative stability up to 450°C before any weight loss was detected as determined by TGA. Catastrophic decomposition occurred after 500°C in air.
  • Toluene was used to control the refluxing azeotropic removal of water and to control the temperature of the reaction content.
  • the resulting mixture was degassed with nitrogen at ambient temperature and the Dean-Stark trap was filled with toluene.
  • the mixture was refluxed at 170-175°C under a nitrogen atmosphere for 8-16 h or until no more water was observed being collected in the Dean-Stark trap.
  • the toluene was then slowly distilled off causing the temperature to rise in the reaction vessel to enhance the yield of the intermediate hydroxyl salt and high conversion to this intermediate.
  • the mixture was cooled and the potassium salt of the 2: 1 oligomeric hydroxyl compound with a 30% excess of bisphenol- A6F was left in solution to use in further reactions.
  • Toluene was used to control the refluxing azeotropic removal of water and to control the temperature of the reaction content.
  • the resulting mixture was degassed with nitrogen at ambient temperature and the Dean-Stark trap was filled with toluene.
  • the mixture was refluxed at 170-175°C under a nitrogen atmosphere for 8-16 h or until no more water was observed being collected in the Dean-Stark trap.
  • the toluene was then slowly distilled off causing the temperature to rise in the reaction vessel to enhance the yield of the intermediate hydroxyl salt and high conversion to this intermediate.
  • the mixture was cooled to 50°C.
  • Toluene was used to control the refluxing azeotropic removal of water and to control the temperature of the reaction content.
  • the resulting mixture was degassed with nitrogen at ambient temperature and the Dean-Stark trap was filled with toluene.
  • the mixture was refluxed at 170-180°C under a nitrogen atmosphere for 6 h or until no more water was observed being collected in the Dean- Stark trap.
  • the toluene was then slowly distilled off causing the temperature to rise in the reaction vessel to enhance the yield of the intermediate hydroxyl salt and high conversion to this intermediate.
  • the reaction mixture was heated above 180°C for an additional 12 h with a very small amount of toluene present to control the temperature, to totally remove the water, formed as a by-product, so that the reaction could be pushed to completion and high conversion to the hydroxyl salt intermediate.
  • the mixture was cooled to 50°C.
  • 4-nitrophthalonitrile 99.1 g, 573 mmol
  • the mixture was allowed to cool to ambient temperature and poured into a 5% aqueous HCl solution resulting in the formation of a solid.
  • the material was broken up and collected using a Buchner funnel.
  • Toluene was used to control the refluxing azeotropic removal of water and to control the temperature of the reaction content.
  • the resulting mixture was degassed with nitrogen at ambient temperature and the Dean-Stark trap was filled with toluene.
  • the mixture was refluxed at 170-180°C under a nitrogen atmosphere for 6 h or until no more water was observed being collected in the Dean-Stark trap.
  • the toluene was then slowly distilled off causing the
  • reaction mixture was heated above 180°C for an additional 12 h with a very small amount of toluene present to control the temperature, to totally remove the water, formed as a by-product, so that the reaction could be pushed to completion and high conversion to the hydroxyl salt intermediate.
  • the mixture was cooled to 50°C.
  • 4-nitrophthalonitrile (52.7 g, 304 mmol) was added in one portion and the reaction mixture was heated at 80°C for 6-8 h.
  • the mixture was allowed to cool to ambient temperature and poured into a 5% aqueous HCl solution resulting in the formation of a solid.
  • the mixture was refluxed at 135-145 °C under a nitrogen atmosphere for 8-16 h or until no more water was observed being collected in the Dean-Stark trap.
  • the toluene was then slowly distilled off causing the temperature to rise in the reaction vessel to enhance the yield of the intermediate hydroxyl salt and high conversion to this intermediate.
  • the mixture was cooled and the potassium salts of the 2: 1 oligomeric hydroxyl compound and the excess of bisphenol A6F were left in solution to use in further reactions.
  • Toluene was used to control the refluxing azeotropic removal of water and to control the temperature of the reaction content.
  • the resulting mixture was degassed with nitrogen at ambient temperature and the Dean-Stark trap was filled with toluene.
  • the mixture was refluxed at 135-145 °C under a nitrogen atmosphere for 8-16 h or until no more water was observed being collected in the Dean-Stark trap.
  • the toluene was then slowly distilled off causing the temperature to rise in the reaction vessel to enhance the yield of the intermediate hydroxyl salt and high conversion to this intermediate.
  • the mixture was cooled to 50 °C.
  • Toluene was used to control the refluxing azeotropic removal of water and to control the temperature of the reaction content.
  • the resulting mixture was degassed with nitrogen at ambient temperature and the Dean-Stark trap was filled with toluene.
  • the mixture was refluxed at 135-145 °C under a nitrogen atmosphere for 6 h or until no more water was observed being collected in the Dean-Stark trap.
  • the toluene was then slowly distilled off causing the temperature to rise in the reaction vessel to enhance the yield of the intermediate hydroxyl salt and high conversion to this intermediate.
  • the mixture was cooled to 50 °C.
  • Toluene was used to control the refluxing azeotropic removal of water and to control the temperature of the reaction content.
  • the resulting mixture was degassed with nitrogen at ambient temperature and the Dean-Stark trap was filled with toluene.
  • the mixture was refluxed at 135-145 °C under a nitrogen atmosphere for 6 h or until no more water was observed being collected in the Dean-Stark trap.
  • the toluene was then slowly distilled off causing the temperature to rise in the reaction vessel to enhance the yield of the intermediate hydroxyl salt and high conversion to this intermediate.
  • the mixture was cooled to 50 °C.
  • the resulting mixture was degassed with nitrogen at ambient temperature and the Dean-Stark trap was filled with toluene.
  • the mixture was refluxed at 135-145 °C under a nitrogen atmosphere for 6 to 18 h or until no more water was observed being collected in the Dean-Stark trap.
  • the reaction mixture was cooled to 20 °C and 4,4'-dichlorobenzophenone (38.5 g, 0.153 mol) was added and the mixture refluxed until NMR or FTIR indicated that all of the 4,4'- dichlorobenzophenone was consumed.
  • the toluene was then slowly distilled off causing the temperature to rise to 180 °C in the reaction vessel to enhance the yield of the intermediate hydroxyl salt and high conversion to this intermediate.
  • phthalonitrile composition (192 g, 97% yield).
  • Toluene was used to control the refluxing azeotropic removal of water and to control the temperature of the reaction content.
  • the resulting mixture was degassed with nitrogen at ambient temperature and the Dean-Stark trap was filled with toluene.
  • the mixture was refluxed at 145-155 °C under a nitrogen atmosphere for 8-16 h or until no more water was observed being collected in the Dean-Stark trap.
  • the toluene was then slowly distilled off causing the temperature to rise in the reaction vessel to enhance the yield of the intermediate hydroxyl salt and high conversion to this intermediate.
  • the mixture was cooled and the sodium salt of the 2: 1 oligomeric hydroxyl compound with a 43% excess of bisphenol A was left in solution to use in further reactions.
  • Toluene was used to control the refluxing azeotropic removal of water and to control the temperature of the reaction content.
  • the resulting mixture was degassed with nitrogen at ambient temperature and the Dean-Stark trap was filled with toluene.
  • the mixture was refluxed at 145-155 °C under a nitrogen atmosphere for 8-16 h or until no more water was observed being collected in the Dean-Stark trap.
  • the toluene was then slowly distilled off causing the temperature to rise in the reaction vessel to enhance the yield of the intermediate hydroxyl salt and high conversion to this intermediate.
  • the mixture was cooled to 50 °C.

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Abstract

La présente invention concerne un procédé consistant à : fournir une solution d'un composé dichloroaromatique ayant un groupe attracteur d'électrons lié à chaque noyau aromatique contenant l'un des groupes chlorure ; un composé dihydroxyaromatique ou un de ses anions ; un complexe organique de métal de transition ou un sel de métal de transition ; une base ; et un solvant ; et chauffer la solution à une température à laquelle le composé dichloroaromatique et le composé dihydroxyaromatique réagissent pour former un sel dimetallique d'un oligomère d'éther aromatique. Le rapport molaire entre le composé dihydroxyaromatique et le composé dichloroaromatique est supérieur à 2 : 1. L'eau formée au cours du chauffage est simultanément distillée de la solution. La présente invention concerne également une composition comportant un mélange des composés mentionnés ci-dessous ayant un rapport molaire d'au moins 1 : 20. Ar1 et Ar2 sont des groupes aromatiques choisis indépendamment. La présente invention concerne également une composition comprenant des composés phtalonitrile qui comprennent au moins 5 % en moles du premier composé mentionné ci-dessous.
PCT/US2015/029812 2013-03-15 2015-05-08 Synthèse d'additifs de durcissement de phthalonitriles WO2015183518A1 (fr)

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EP13826354.6A EP2880079B1 (fr) 2012-08-02 2013-03-15 Synthèse de phtalonitriles et additifs durcissants pour phtalonitriles
US14/287,316 2014-05-27
US14/287,316 US8859712B2 (en) 2012-08-02 2014-05-27 Synthesis of and curing additives for phthalonitriles
US14/483,264 2014-09-11
US14/483,264 US8981036B2 (en) 2012-08-02 2014-09-11 Synthesis of and curing additives for phthalonitriles
EP13826354.6 2015-02-27
IN1680DE2015 2015-02-27
IN1680/DELNP/2015 2015-02-27

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CN114133341A (zh) * 2021-11-17 2022-03-04 中钢集团鞍山热能研究院有限公司 一种邻苯二甲腈封端聚芳醚腈低聚物的连续化合成方法及装置
CN116903546A (zh) * 2023-09-13 2023-10-20 浙江华宇钠电新能源科技有限公司 一种带灭火功能的钠离子电池包及车辆

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US8288454B2 (en) * 2009-08-11 2012-10-16 The United States Of America, As Represented By The Secretary Of The Navy Polymeric compositions containing microspheres
WO2014021946A1 (fr) * 2012-08-02 2014-02-06 The Gov. Of The U.S. Of America As Represented By The Secretary Of The Navy Synthèse de phtalonitriles et additifs durcissants pour phtalonitriles

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US8288454B2 (en) * 2009-08-11 2012-10-16 The United States Of America, As Represented By The Secretary Of The Navy Polymeric compositions containing microspheres
WO2014021946A1 (fr) * 2012-08-02 2014-02-06 The Gov. Of The U.S. Of America As Represented By The Secretary Of The Navy Synthèse de phtalonitriles et additifs durcissants pour phtalonitriles

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114133341A (zh) * 2021-11-17 2022-03-04 中钢集团鞍山热能研究院有限公司 一种邻苯二甲腈封端聚芳醚腈低聚物的连续化合成方法及装置
CN114133341B (zh) * 2021-11-17 2024-02-06 中钢集团鞍山热能研究院有限公司 一种邻苯二甲腈封端聚芳醚腈低聚物的连续化合成方法及装置
CN116903546A (zh) * 2023-09-13 2023-10-20 浙江华宇钠电新能源科技有限公司 一种带灭火功能的钠离子电池包及车辆
CN116903546B (zh) * 2023-09-13 2023-12-15 浙江华宇钠电新能源科技有限公司 一种带灭火功能的钠离子电池包及车辆

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