Curable compositions of benzoxazine and phthalonitrile resins

Abstract

To provide a thermosetting composition which can provide a low viscosity for RTM applications and can be completely cured at a much lower temperature than phthalonitrile monomers. Also provided is a cured thermoset polymer having excellent thermal and mechanical properties such as high thermal stability, heat resistance, high charge yield and enhanced structural rigidity.SOLUTION: The present disclosure provides a polymerizable thermosetting composition comprising an acetylene-bearing benzoxazine compound and a phthalonitrile monomer.SELECTED DRAWING: None

Description

[Technical Field]

[0001] Cross-reference to related applications This application claims the benefit of backdated U.S. Provisional Patent Application No. 62 / 928,466, filed October 31, 2019, the entire disclosure of which is expressly incorporated herein by reference.

[0002] STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT Not applicable.

[0003] Field The present disclosure relates generally to polymerizable thermosetting compositions comprising phthalonitrile monomers and acetylene-bearing benzoxazine compounds and their use for applications in various industries, such as, but not limited to, building and construction, electronic packaging, energy generation and power generation, aerospace, transportation, and medical device industries. [Background technology]

[0004] background Phthalonitrile monomers are a new class of high-performance monomers developed for high-temperature applications such as in the production of prepregs, laminates, and structural composite parts. For example, U.S. Patent Nos. 5,629,999, 5,729,963, 5,729,973, 5,729,983, 5,729,993, and 5,729,983 disclose various phthalonitrile monomers derived from phenols, aromatic diols reacted with diphenylacetylene, polyphenols and bisphenols from renewable resources. These phthalonitrile monomers have been found to have excellent thermal and thermo-oxidative stability after cure, with initial decomposition temperatures greater than 450°C, as well as numerous other highly attractive performance properties, such as enhanced flame resistance, the absence of a glass transition temperature before thermal decomposition, excellent mechanical properties at high temperatures, low water absorption, excellent corrosion resistance, and advanced UV-shielding behavior.

[0005] However, state-of-the-art phthalonitrile monomers are known to suffer from brittleness due to the rigidity of the monomer precursor and the high degree of cross-linking in the final cured product. Furthermore, these phthalonitrile monomers are generally solid at room temperature and therefore must be melted before use. Furthermore, they may require higher than desired curing temperatures (e.g., greater than 250°C) and longer times for complete cure.

[0006] To overcome these drawbacks, attempts have been made to adjust the chain length between phthalonitrile monomer units to lower their melting points and improve the flexibility of the cured products. Various types of catalysts have also been used to improve the curing behavior of these phthalonitrile monomers. Finally, U.S. Patent Nos. 5,629,999 and 5,729,999 disclose specific phthalonitrile monomers copolymerized with epoxy or benzoxazine resins to improve the processability, curing behavior, and final properties of the cured phthalonitrile products; however, such compositions may still require higher than desired curing temperatures (e.g., well above 250°C) and longer times for complete cure, and have insufficient char yields for carbon-carbon composite applications.

[0007] It would be desirable to further improve the cure cycle in copolymerization of thermosetting compositions that would exhibit even better processability and cure behavior, resulting in products with improved thermal and mechanical properties. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] U.S. Patent No. 6,420,464 [Patent Document 2] U.S. Patent No. 8,039,576 [Patent Document 3] U.S. Patent No. 8,853,343 [Patent Document 4] U.S. Patent No. 9,920,165 [Patent Document 5] US Patent No. 2019 / 0047946 [Patent Document 6] U.S. Patent No. 5,939,508 [Patent Document 7] International Publication No. 2017105890 Brochure Summary of the Invention

[0009] Overview The present disclosure generally provides a polymerizable thermosetting composition that includes (i) an acetylene-bearing benzoxazine compound and (ii) a phthalonitrile monomer.

[0010] The polymerizable thermosetting compositions of the present disclosure can be cured to form thermoset polymers with improved thermal and mechanical properties, and therefore can find use in a variety of applications, including but not limited to, building and construction, electronic packaging, military, energy generation and power generation, aerospace, transportation, and medical device industries.

[0011] Detailed Description The present disclosure generally provides polymerizable thermosetting compositions comprising (i) an acetylene-bearing benzoxazine compound and (ii) a phthalonitrile monomer. Surprisingly, the compositions of the present disclosure have been found to have faster cure than other state-of-the-art benzoxazine / phthalonitrile compositions under comparable conditions. For example, compositions of the present disclosure may require a staged cure at temperatures up to 200°C to 220°C, followed by a post-cure at temperatures ranging from 250°C to 260°C. In comparison, compositions of the present disclosure may require a staged cure at temperatures up to 200°C to 220°C, followed by a post-cure at temperatures ranging from 250°C to 260°C. Nitrile monomers generally require a cure temperature of at least 350°C (see Examples 3-8) for homopolymerization without a catalyst. Phthalonitrile monomers can be crosslinked with the acetylene functionality in the acetylene-bearing benzoxazine, resulting in improved thermal and mechanical properties, such as improved thermal stability, heat resistance, char yield, and enhanced structural rigidity. Without being limited to a particular theory, it is believed that the high enthalpy (e.g., greater than 800 J / g) of the acetylene-bearing benzoxazine compound provides sufficient heat to promote the polymerization of the phthalonitrile monomer. At the same time, the acetylene-bearing benzoxazine compound can also dissolve a certain amount of phthalonitrile monomer at a temperature about 20-40°C below the melting point of the phthalonitrile monomer, resulting in a mixture with a low viscosity that can be more easily processed for injection applications, among other uses.

[0012] The following terms shall have the following meanings:

[0013] The term "comprising" and its derivatives are not intended to exclude the presence of additional components, steps, or methods, whether or not they are disclosed herein. For the avoidance of any doubt, all compositions claimed herein through the use of the term "comprising" may include any additional additives or compounds, unless stated otherwise. In contrast, the term "consisting essentially of," when it appears herein, excludes from the scope of the succeeding recitation any other component, step, or method except those that are not essential to operability, and the term "consisting of," when used, excludes any component, step, or method not specifically stated or listed. The term "or," unless stated otherwise, refers to the listed members individually as well as in any combination.

[0014] The articles "a" and "an" are used herein to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article. For example, "a functionalized phthalonitrile monomer" means one functionalized phthalonitrile monomer or more than one functionalized phthalonitrile monomer.

[0015] Phrases such as "in one aspect," "according to one aspect," and the like generally mean that the particular feature, structure, or characteristic that follows the phrase is included in at least one aspect of the disclosure, and may be included in more than one aspect of the disclosure. Importantly, such phrases do not necessarily refer to the same aspect.

[0016] When the specification states that a component or feature "may," "can," "could," or "might" be included or have a certain property, it does not require that the particular component or feature be included or have that property.

[0017] According to one aspect, the present disclosure provides a polymerizable thermosetting composition comprising an acetylene-bearing benzoxazine compound and a phthalonitrile monomer.

[0018] Such acetylene-bearing benzoxazine compounds are described in WO 1999 / 18092, the disclosure of which is incorporated herein by reference. In particular, acetylene-bearing benzoxazine compounds can be prepared from the reaction of a monophenolic compound, an aldehyde, and a primary amine.

[0019] Monophenolic compounds include phenol, cresol, 2-bromo-4-methylphenol, 2-allylphenol, 1,4-aminophenol, etc. In one embodiment, the phenolic compound is phenol or allylphenol.

[0020] The aldehyde compound is formaldehyde, paraformaldehyde, polyoxymethylene or a compound of formula R a CHO, wherein R a is C1-C 12 It can be a compound that is an aliphatic group In one embodiment, the aldehyde compound is formaldehyde.

[0021] Primary amines can be amines having 2-40 carbons and optionally O, N, S, or halogen heteroatoms with one or more carbon-to-carbon triple bond groups. Between the nitrogen of the primary amine and the carbon-to-carbon triple bond group, there can optionally be a C1-C6 alkyl group optionally substituted with an aromatic group having 6-12 carbons, or an aromatic group having 6-12 carbons optionally substituted with a C1-C6 alkyl group. Carbon-to-carbon triple bond groups have the formula -C≡CR d , -CH2-C≡CR d , [ka] [In the formula, R d is hydrogen, a C1-C5 alkyl group optionally substituted with an aromatic group having 6-12 carbon atoms; In one particular embodiment, the primary amine having one or more carbon-to-carbon triple bonds is 3-aminophenylacetylene and propargylamine.

[0022] In one embodiment, the one or more acetylene-bearing benzoxazine compounds have the following structure: [ka] wherein R1, R2, R3, R4 and R5 each independently represent a hydrogen atom, a substituted or unsubstituted C1-C 20 Alkyl groups, substituted or unsubstituted C2-C 20Alkenyl groups, substituted or unsubstituted C6-C 20 Aryl groups, substituted or unsubstituted C2-C 20 Heteroaryl groups, substituted or unsubstituted C4-C 20 Carbocyclic groups, substituted or unsubstituted C-C 20 heterocyclic group or a C3-C8 cycloalkyl group; b is an integer ranging from 1 to 4, where: when b is 1, Z is a hydrogen atom, a substituted or unsubstituted C1-C8 20 Alkyl groups, substituted or unsubstituted C2-C 20 Alkenyl groups, substituted or unsubstituted C6-C 20 Aryl groups, substituted or unsubstituted C2-C 20 Heteroaryl groups, substituted or unsubstituted C4-C 20 Carbocyclic groups, substituted or unsubstituted C-C 20 Heterocyclic group or C3 -C cycloalkyl group; each R is an alkynyl-substituted C-C 20 Alkyl groups, alkynyl groups C8-C 20 Aryl groups, alkynyl-substituted C2-C 20 Heteroaryl groups, alkynyl-substituted C4-C 20 Carbocyclic groups, alkynyl-substituted C2-C 20 heterocyclic group or alkynyl-substituted C3-C8 cycloalkyl group; when b is 2, Z is a direct bond or a substituted or unsubstituted C1-C 20 Substituted or unsubstituted C2-C with alkyl, aryl or heteroaryl bridges 20 Alkyl groups, substituted or unsubstituted C2-C 20 Alkenyl groups, substituted or unsubstituted C2-C 20 Alkynyl groups, substituted or unsubstituted C6-C 20 Aryl groups, substituted or unsubstituted C2-C 20 heteroaryl groups, O, S, S=O, O=S=O, C=O, or C=CCl2; and b is 3 or 4, Z is a substituted or unsubstituted C-C 20 Alkyl group, aryl or heteroaryl Substituted or unsubstituted C2-C with bridges 20 Alkyl groups, substituted or unsubstituted C2-C 20Alkenyl groups, substituted or unsubstituted C2-C 20 Alkynyl groups, substituted or unsubstituted C6-C 20 Aryl groups, substituted or unsubstituted C2-C 20 and when b is 3 or 4, Z is a substituent. Substituted or unsubstituted C1-C 20 Substituted or unsubstituted alkyl groups, aryl or heteroaryl groups with bridges unsubstituted C2-C 20 Alkyl groups, substituted or unsubstituted C2-C 20 Alkenyl groups, substituted or unsubstituted C2-C 20 Alkynyl groups, substituted or unsubstituted C6-C 20 Aryl groups, substituted or unsubstituted C2-C 20 and each R6 is an alkynyl-substituted C1-C 20 Alkyl, alkynyl substituted C8-C 20 Aryl groups, alkynyl-substituted C2-C 20 Heteroaryl groups, alkynyl-substituted C4-C 20 Carbocyclic groups, alkynyl-substituted C2-C 20 It is a heterocyclic group or an alkynyl-substituted C3-C8 cycloalkyl group.

[0023] In one particular embodiment, the acetylene-bearing benzoxazine compound is phenol 3-aminophenylacetylene benzoxazine or 2-allylphenol 3-aminophenylacetylene benzoxazine.

[0024] Phthalonitrile monomer is obtained from the reaction of (i) a polyfunctional phenolic compound with (ii) 4-nitrophthalonitrile.

[0025] The polyfunctional phenolic compound can be, but is not limited to, resorcinol, bisphenol A, bisphenol C, bisphenol F, bisphenol E, bisphenol S, 2,2',6,6'-tetramethylbisphenol F, 1,2,2,2-tetraphenolethane, thiodiphenol, phenolphthalein, dicyclopentadienyldiphenol, 1,8-hydroxyanthraquinone, 1,6-dihydroxynaphthalene, 2-2'-dihydroxyazobenzene, 1,3,5-trihydroxybenzene, and polyhydric phenolic compounds containing at least one furan or thiophene group.

[0026] In one particular embodiment, the polyfunctional phenolic compound is selected from bisphenol M, bisphenol A, bisphenol C, bisphenol P, 2,2',6,6'-tetramethylbisphenol F, or furanyl-substituted 2,2',6,6'-tetramethylbisphenol F.

[0027] The polyhydric phenol compound containing at least one furan or thiophene group comprises a phenol compound and a compound represented by formula (1) [ka] wherein X is oxygen or sulfur and Q is hydrogen or C1 -C5 alkyl group, and j is an integer from 1 to 3. Examples include, but are not limited to, furfural, 3-furaldehyde, 3-methylfurfural, 5-methylfurfural, 5-ethylfurfural, 2-thiophene-carboxaldehyde, 3-thiophene-carboxaldehyde, 3-methyl-2-thiophene-carboxaldehyde, and the like.

[0028] Phenolic compounds may include, but are not limited to, phenol, cresol, xylenols such as 2,6-xylenol (dimethylphenol), trimethylphenol, 2,5-alkylphenols such as 2-tert-butyl-5-methyl-phenol or 2-tert-butyl-4-methylphenol, allylphenol, alkynylphenol, octylphenol, phenylphenol, diphenylphenol, guaiacol, hydroquinone, resorcinol, catechol, naphthol, dihydroxynaphthalene, methylnaphthol, bisphenol A, bisphenol F, and the like.

[0029] Polyhydric phenol compounds containing at least one furan or thiophene group can generally be prepared by methods known to those skilled in the art. For example, a phenolic compound can be condensed with a compound of formula (1) in the presence of a base and, optionally, an alcohol or monosubstituted benzene at a temperature between about 30°C and about 150°C or between about 60°C and about 90°C. Generally, the amount of phenolic compound and compound of formula (1) present during the condensation can range from about 1.5 moles to about 20 moles of phenolic compound per mole of compound of formula (1). In some embodiments, the amount of phenolic compound relative to compound of formula (1) present during the condensation can range from about 1.8 moles to about 10 moles of phenolic compound per mole of compound of formula (1).

[0030] Examples of bases that can be used include, but are not limited to, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and the like; alkaline earth metal hydroxides such as magnesium hydroxide, calcium hydroxide, and the like; alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, potassium tert-butoxide, and the like; and alkaline earth metal alkoxides such as magnesium methoxide and magnesium ethoxide. These bases can be used alone or in combination of two or more. The base can be used in an amount of between about 0.005 moles and about 2.0 moles per mole of phenolic compound or between about 0.01 and about 1.1 moles per mole of phenolic compound.

[0031] Alcohol or monosubstituted benzene solvents that can be used include, but are not limited to, methanol, ethanol, propanol, isopropanol, toluene, xylene, etc., which can be used alone or in mixtures, and if desired, can be used in an amount of between about 5 parts by weight and about 500 parts by weight per 100 parts by weight of the phenolic compound, or between about 10 parts by weight and about 300 parts by weight per 100 parts by weight of the phenolic compound.

[0032] The reaction can be carried out by adding a base to a mixture of the phenolic compound and the compound of formula (1) (and optionally an alcohol or monosubstituted benzene solvent) and heating the resulting mixture. Alternatively, the compound of formula (1) can be added to a mixture of the phenolic compound and a base (and optionally an alcohol or monosubstituted benzene solvent) under heating. The reaction time can range from about 5 hours to about 100 hours. After the reaction is complete, the reaction mixture can be neutralized. Unreacted materials can then be removed by filtration or by heating under vacuum.

[0033] According to one embodiment, a polyhydric phenol containing at least one furan or thiophene group is The compound is a compound selected from formulas (2) to (10), [ka] wherein n is an integer from about 3 to about 3.2.

[0034] In yet another embodiment, the polyhydric phenol compound containing at least one furan or thiophene group is derived from bisphenol A or bisphenol F and a compound of formula (1) where X is oxygen and Q and j are as defined above.

[0035] According to one embodiment, the phthalonitrile monomer is produced by reacting a polyfunctional phenolic compound with 4-nitrophthalonitrile in the presence of a catalyst and, optionally, a solvent.

[0036] Examples of catalysts include, but are not limited to, the bases mentioned above as well as alkali metal salts such as cesium carbonate, potassium carbonate or sodium carbonate, organolithium reagents such as methyl or n-butyllithium, Grignard reagents or combinations thereof.

[0037] Examples of solvents that may be used include, but are not limited to, any polar or non-polar solvent such as acetone, acetonitrile, alcohol, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, n-methylpyrrolidone, dimethyl sulfoxide, hexamethylphosphoramide, or combinations thereof.

[0038] In another embodiment, the solvent can be a solvent capable of forming an azeotrope with water, such as toluene or xylene. Surprisingly, it has been found that such a solvent can be used to aid in the removal of both the water found in the compounds forming the reaction mixture (i.e., the polyhydric phenol compound containing at least one furan or thiophene group, 4-nitrophthalonitrile, and base) and the water produced during the reaction of the polyhydric phenol compound containing at least one furan or thiophene group with 4-nitrophthalonitrile. A mixture of solvent and water The phthalonitrile monomer can be purified by recrystallization from the phthalonitrile monomer to enrich the resulting product in monomer content.

[0039] According to another embodiment, the polyhydric phenol compound containing at least one furan or thiophene group and the functionalized phthalonitrile monomer can be formed in the same reaction vessel to improve overall processing time and efficiency. In such an embodiment, in a first stage, the polyhydric phenol containing at least one furan or thiophene group is formed in a reaction vessel as described above. In a second stage, 4-nitrophthalonitrile is added to the polyhydric phenol containing at least one furan or thiophene group in the reaction vessel to form the functionalized phthalonitrile monomer. The base, catalyst, and solvent used in the reactions in the first and second stages can be the same or different. In some embodiments, the solvent is toluene or xylene.

[0040] The phthalonitrile monomer has the formula [ka] 2. The thermosetting composition according to claim 1, wherein R1 to R2 are each a compound having the formula: 14 Each of them which are independently a hydrogen atom, a substituted or unsubstituted C1-C 20 Alkyl groups, substituted or unsubstituted C2-C 20 Alkenyl groups, substituted or unsubstituted C2-C 20 Alkynyl groups, substituted or unsubstituted C6-C 20 Aryl groups, substituted or unsubstituted C2-C 20 heteroaryl groups; and Z is a direct bond, Substituted or unsubstituted C1-C 20 Substituted or unsubstituted alkyl groups, aryl or heteroaryl groups with bridges unsubstituted C2-C 20 Alkyl groups, substituted or unsubstituted C2-C 20 Alkenyl groups, substituted or unsubstituted C2-C 20 Alkynyl groups, substituted or unsubstituted C6-C 20Aryl groups, substituted or unsubstituted C2-C 20 Heteroaryl groups include, but are not limited to, O, S, S=O, O=S=O, C=O, C(=O)O or C=CCl2 or polyethers, polyethersulfones or polyetherketones. The polymer chain may be selected from polymer chains containing oxygen in each repeat unit, including but not limited to:

[0041] According to one embodiment, the polymerizable thermosetting composition comprises one or more acetylene-bearing benzoxazine compounds and phthalonitrile monomer in a weight ratio of one or more acetylene-bearing benzoxazine compounds to phthalonitrile monomer of between about 1:1 and about 10:1, or from about 1.5:1 to about 10:1, or from about 2:1 to about 10:1.

[0042] The amount of phthalonitrile monomer present in the polymerizable thermosetting composition can be in an amount of at least about 1 wt%, at least about 5 wt%, or at least about 10 wt%, or at least about 20 wt%, or at least about 30 wt%, or at least about 40 wt%, or at least about 50 wt%, or at least about 60 wt%, or at least about 70 wt%, or at least about 80 wt%, or at least about 90 wt%, or at least about 99 wt%, based on the total weight of the polymerizable thermosetting composition. In other embodiments, the amount of phthalonitrile monomer present in the polymerizable thermosetting composition can be in an amount of between about 1 wt% and about 99 wt%, or between about 5 wt% and about 90 wt%, or between about 10 wt% and about 80 wt%, or between about 20 wt% and about 70 wt%, or between about 30 wt% and about 60 wt%, based on the total weight of the polymerizable thermosetting composition.

[0043] The polymerizable thermosetting composition of the present disclosure can be cured by heating the polymerizable thermosetting composition sufficiently to produce a thermoset polymer. A curing agent can be used to accelerate the thermoset production of the thermoset polymer. Thus, according to another embodiment, the polymerizable thermosetting composition The composition further comprises a curing agent.

[0044] Curing agents that can be used include, but are not limited to, aromatic amines, primary amines, secondary amines, diamines, polyamines, amine-substituted phosphazenes, phenols, strong acids, organic acids, strong organic acids, inorganic acids, metals, metal salts, metal salt hydrates, metal compounds, halogen-containing aromatic amines, clays, and chemically modified clays. The use of clays or chemically modified clays can improve the mechanical properties and flammability of thermoset resins. Typically, chemical modification of clays involves replacing sodium ions with ammonium to form quaternary ammonium salts.

[0045] Specific hardeners include bis(4-(4-aminophenoxy)phenyl sulfone (p-BAPS), bis(4-(3-aminophenoxy)phenyl sulfone (m-BAPS), 1,4-bis(3-aminophenoxy)benzene (p-APB), 1,12-diaminododecane, diphenylamine, epoxy amine hardeners, 1,6-hexanediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, p-toluenesulfonic acid, cuprous iodide, cuprous bromide, 1,3-bis(3-aminophenoxy)benzene (m-APB), 3,3'-dimethyl- 4,4'-Diaminodiphenyl sulfone, 3,3'-diethoxy-4,4'-diaminodiphenyl sulfone, 3,3'-dicarboxy-4,4'-diaminodiphenyl sulfone, 3,3'-dihydroxy-4,4'-diaminodiphenyl sulfone, 3,3'-disulfo-4,4'-diaminodiphenyl sulfone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobenzophenone, 3,3'-dimethoxy-4,4'-diaminobenzophenone, 3,3'-dicarboxy-4,4'- Diaminobenzophenone, 3,3'-dihydroxy-4,4'-diaminobenzophenone, 3,3'-disulfo-4,4'-diaminobenzophenone, 4,4'-diaminodiphenylethylphosphine oxide, 4,4'-diaminodiphenylphenylphosphine oxide, bis(3-aminophenoxy-4'-phenyl)phenylphosphine oxide, methylenedianiline, hexakis(4-aminophenoxy)cyclotriphosphazene, 3,3'-dichloro-4,4'-diaminodiphenylsulfone, 2,2'-bis(trifluoromethyl)- 4,4'-Diaminobiphenyl, 2,2'-bis(4-aminophenyl)hexafluoropropane, bis[4-(4-aminophenoxy)phenyl]2,2'-hexafluoropropane, 1,1-bis(4-aminophenyl)-1-phenyl-2,2,2-trifluoroethane, 3,3'-dichloro-4,4'-diaminobenzophenone, 3,3'-dibromo-4,4'-diaminobenzophenone, aniline-2-sulfonic acid, 8-aniline-1-naphthalenesulfonic acid, benzenesulfonic acid, butylsulfonic acid, 10-camphorsulfonic acid, 2,5-Diaminobenzenesulfonic acid, 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-naphthalenedisulfonic acid, picrylsulfonic acid hydrate, 2-pyridineethanesulfonic acid, 4-pyridineethanesulfonic acid, 3-pyridinesulfonic acid, 2-pyridinylhydroxymethanesulfonic acid, sulfanilic acid, 2-sulfobenzoic acid water hydrate, 5-sulfosalicylic acid hydrate, 2,4-xylene sulfonic acid, sulfonic acid-containing dyes, organic phosphorus-containing acids, phenylphosphinic acid, diphenylphosphinic acid, propylphosphonic acid, 1-aminoethylphosphonic acid, 4-aminophenylphosphonic acid, butylphosphonic acid, t-butylphosphonic acid, 2-carboxyethylphosphonic acid, 2-chloroethylphosphonic acid, dimethylphosphonic acid, ethylphosphonic acid, methylenediphosphonic acid, methylphosphonic acid, phosphonoacetic acid, bis(hydroxymethyl)phosphonic acid, chloromethylphosphonic acid, di-n-butylphosphonic acid, dichloromethylphosphonic acid, diphenyldithiophosphonic acid, 1,2-ethylenediphosphonic acid, n-histadelylphosphonic acid (n, -hystaderylphosphonic acid), hydroxymethylphosphonic acid, n-octadecylphosphonic acid, n-octylphosphonic acid, phenylphosphonic acid, propylene diphosphonic acid, n-tetradecylphosphonic acid, concentrated sulfuric acid, phenylphosphonic acid, copper, iron, zinc, nickel, chromium, molybdenum, vanadium, beryllium, silver, mercury, tin, lead, antimony, calcium, barium, manganese, magnesium, cobalt, palladium, platinum, cuprous bromide, cuprous cyanide, cuprous ferricyanide, zinc chloride, zinc bromide, zinc iodide, zinc cyanide, zinc ferricyanide, zinc acetate, zinc sulfide, silver chloride, ferrous chloride, ferric chloride, ferrous ferricyanide, ferrous chloroplatinate, ferrous fluoride, ferrous sulfate, cobaltous chloride (cobaltous chloride), cobaltous sulfate, cobaltous cyanide, nickel chloride, nickel cyanide, nickel sulfate, nickel carbonate, stannic chloride, stannous chloride hydrate, stannous chloride dihydrate, aluminum nitrate hydrate, aluminum nitrate nonahydrate, triphenylphosphine oxide complex, montmorillonite, chemically modified montmorillonite, 4,4'-(1,3-phenylenedioxy)dianiline, 4,4'-(1,4-phenylenedioxy)dianiline, bis(4-(4-aminophenoxy)phenyl)sulfone, 4,4'-(4,4'-isopropylidenediphenyl-1,1'-diyldioxy)dianiline, 4,4'-(1,3-phenylenedioxy)dianiline 4,4'-(1,4-phenylenediisopropylidene)dianiline, 4,4'-(1,1'-biphenyl-4,4'-diyldioxy)dianiline, 4,4'-methylenedianiline, 4,4'-sulfonyldianiline, 4,4'-methylene-bis(2-methylaniline), 3,3'-methylenedianiline, 3,4'-methylenedianiline, 4,4'-oxydianiline, 4,4'-(isopropylidene)dianiline, 4,4'-(hexafluoroisopropylidene)dianiline, 4,4'-(hexafluoroisopropylidene)bis(p-phenyleneoxy)dianiline, 4,4'-diaminobenzophenone, compounds [ka] and mixtures thereof.

[0046] The curing agent can be present in the polymerizable thermosetting composition in an amount of at least about 0.5 wt%, or at least about 1 wt%, or at least about 2 wt%, or at least about 5 wt%, or at least about 10 wt%, or at least about 15 wt%, or even at least about 20 wt%, based on the total weight of the polymerizable thermosetting composition.

[0047] In other embodiments, the curing agent is present in an amount less than about 40 wt.%, or less than about 35 wt.%, or less than about 30 wt.%, or less than about 25 wt.%, based on the total weight of the polymerizable thermosetting composition. In yet another embodiment, the curing agent can be present in an amount between about 0.25 wt % and about 45 wt % or between about 1 wt % and about 40 wt % based on the total weight of the polymerizable thermosetting composition.

[0048] The polymerizable thermosetting composition can be prepared by mixing the acetylene-bearing benzoxazine compound with the phthalonitrile monomer at a temperature below the melting point (for example, but not limited to, 35 to 40°C or lower than the melting point of the components) by using conventional equipment such as a stirred vessel, a stirring rod, a ball mill, a sample mixer, a static mixer, or a ribbon blender to form the thermosetting composition.

[0049] The polymerizable thermosetting composition can then be cured to form a thermoset polymer. As used herein, the term "curing" refers to the conversion of the thermosetting composition to an insoluble, infusible crosslinked product that can be simultaneously molded to provide a shaped article, such as a molding, pressing, or laminate, or to provide a two-dimensional structure, such as a coating, enamel, or adhesive bond. Typical curing methods include room temperature curing to elevated temperature curing using heat, radiation, or any combination of energy sources. Typical curing temperatures can range from about 50°C to about 500°C, such as from about 75°C to about 375°C, or from about 80°C to about 300°C, for a time sufficient to at least partially, substantially, or completely cure the composition, such as from 3 to 20 hours, or from about 5 to 15 hours, or from about 6 to about 15 hours, or from about 7 to about 12 hours, or from about 8 to about 10 hours.

[0050] Further curing can be carried out in one or more cure stages. For example, the polymerizable thermosetting composition can be subjected to an initial cure at a temperature ranging from about 50°C to about 500°C, such as between about 75°C and about 375°C or between about 80°C and about 300°C, for a time sufficient to at least partially cure the composition, such as for a time ranging from 3 to 10 hours, and then post-cured at a temperature below 300°C, or up to 280°C, and even up to 260°C, for a time sufficient to substantially or completely cure the composition, such as for a time ranging from 2 to 4 hours. The polymerizable thermosetting composition can have a viscosity at 75°C prior to curing of less than 3000 centipoise, or less than 1000 centipoise, or less than 500 centipoise, or less than 175 centipoise.

[0051] According to one embodiment, the polymerizable thermosetting composition of the present disclosure can further comprise an additional monofunctional benzoxazine or polyfunctional benzoxazine, or a combination thereof, and one or more curing agents or optional additives, or a second phthalonitrile monomer, to form another thermosetting composition. The additives may include, but are not limited to, fillers such as carbon nanotubes, clay, carbon nanofibers, metal oxides, zinc oxide, diatomaceous earth, barium sulfate, talc, silica, calcium carbonate, calcium fluoride, and combinations thereof, colorants, antioxidant stabilizers, thermal degradation stabilizers, light stabilizers, flow agents, thickeners, matting agents, binders, foaming agents, fungicides, bactericides, surfactants, plasticizers, rubber toughening agents, and other additives known to those skilled in the art. When present, these additives are added in amounts effective for their intended purpose.

[0052] As described above, polymerizable benzoxazine compounds can be prepared by mixing at least one acetylene-bearing benzoxazine compound and one phthalonitrile monomer, other monofunctional or polyfunctional benzoxazine or second phthalonitrile monomers, and optional curing agents and additives in any order using conventional equipment such as a stirred vessel, a stirring rod, a ball mill, a sample mixer, a static mixer, or a ribbon blender to form a thermosetting composition. A thermosetting composition can be prepared, which can then be cured as described above to form a thermoset polymer.

[0053] According to one embodiment, the additional benzoxazine can be a monofunctional benzoxazine. Monofunctional benzoxazine compounds are compounds obtained from the reaction of a monophenolic compound, an aldehyde, such as formaldehyde, and a primary amine.

[0054] The monophenolic compound can be, but is not limited to, phenol, cresol, 2-bromo-4-methylphenol, 2-allylphenol, 1,4-aminophenol, etc. In one particular embodiment, the phenol type is phenol.

[0055] The aldehyde compound is formaldehyde, paraformaldehyde, polyoxymethylene or a compound of formula R a CHO, wherein R a is C1-C 12 It can be a compound that is an aliphatic group In one particular embodiment, the aldehyde compound is paraformaldehyde.

[0056] The primary amine can be, but is not limited to, the primary amines having at least one carbon-to-carbon triple bond group described above, as well as aniline, o-, m-, and p-phenylenediamine, benzidine, 4,4'-diaminodiphenylmethane, cyclohexylamine, 1,4-diaminocyclohexyl, butylamine, methylamine, hexylamine, allylamine, furfurylamine, ethylenediamine, propylenediamine, and diaminodiphenylsulfone. In one particular embodiment, the primary amine is furfurylamine.

[0057] According to another embodiment, the additional benzoxazine can be a polyfunctional benzoxazine. The polyfunctional benzoxazine has the formula [ka] wherein b is an integer ranging from 2 to 4; and each R is independently hydrogen, substituted or unsubstituted C-C 20 Alkyl groups, substituted or unsubstituted C2-C 20 Alkenyl groups, substituted or unsubstituted C6-C 20 Aryl groups, substituted or unsubstituted C2-C 20 Heteroaryl groups, substituted or unsubstituted C4-C 20 Carbocyclic groups, substituted or unsubstituted C-C 20a heterocyclic group or a C3-C8 cycloalkyl group; each R1 is independently hydrogen, C1-C 20 Alkyl groups, C2-C 20 Arkeny C6-C 20 and when b is 2, Z is a direct bond, a substituted or is unsubstituted C1-C 20 Alkyl groups, substituted or unsubstituted C6-C 20 Aryl groups, substituted or unsubstituted C2-C 20 a heteroaryl group, O, S, S=O, O=S=O or C=O, and b is When Z is 3 or 4, Z is a substituted or unsubstituted C-C 20 Alkyl groups, substituted or unsubstituted C6-C 20 Aryl groups, substituted or unsubstituted C2-C 20 It is a heteroaryl group.

[0058] Substituents include hydroxy, C1-C 20 Alkyl, C2-C 10 Alkoxy, mercapto, C3 -C8 cycloalkyl, C6-C 14 Heterocyclic, C6-C 14 Aryl, C6-C 14 Heteroaryl, halogen, cyano, nitro, nitrone, amino, amido, acyl, oxyacyl, kaolin These include, but are not limited to, carboxyl, carbamate, sulfonyl, sulfonamide and sulfuryl.

[0059] According to one embodiment, the polyfunctional benzoxazine compound is a compound obtained from the reaction of a polyfunctional phenolic compound, an aldehyde such as formaldehyde, and a primary amine.

[0060] The polyfunctional phenolic compound can be, but is not limited to, resorcinol, bisphenol A, bisphenol F, bisphenol E, bisphenol S, 1,2,2,2-tetraphenolethane, thiodiphenol, phenolphthalein, dicyclopentadienyldiphenol, 1,8-hydroxyanthraquinone, 1,6-dihydroxynaphthalene, 2-2'-dihydroxyazobenzene, and 1,3,5-trihydroxybenzene. In one particular embodiment, the polyfunctional phenolic compound is 4'4-diphenol or 4,4-thiodiphenol.

[0061] The primary amine can be, but is not limited to, the primary amines having at least one carbon-to-carbon triple bond group described above, as well as aniline, o-, m-, and p-phenylenediamine, benzidine, 4,4'-diaminodiphenylmethane, cyclohexylamine, 1,4-diaminocyclohexyl, butylamine, methylamine, hexylamine, allylamine, furfurylamine, ethylenediamine, propylenediamine, and diaminodiphenylsulfone. In one particular embodiment, the primary amine is aniline or furfurylamine.

[0062] In yet another aspect, a thermoset polymer is provided by contacting any suitable substrate with any one of the polymerizable thermoset compositions described above and subjecting the substrate / polymerizable thermoset composition to a heat, radiation, or a combination of energy sources to cure the substrate / polymerizable thermoset composition. In one aspect, the polymerizable thermoset composition of the present disclosure can be used to bond one or more substrates, similar or dissimilar, by contacting one or more surfaces of the substrates to be bonded with the polymerizable thermoset composition under conditions sufficient to cure the polymerizable thermoset composition.

[0063] In another embodiment, the polymerizable thermosetting compositions of the present disclosure can be cured to provide composite articles by methods well known in the industry, such as pultrusion, injection, molding, encapsulation, or coating. Thus, the polymerizable thermosetting compositions of the present disclosure can be used in the production of composite articles such as castings, prepregs, adhesive sheets, laminates, and metal foil-coated laminates.

[0064] The addition of reinforcing fibers can tailor the properties of composite products to specific applications. Examples of reinforcing fibers include glass, quartz, carbon, alumina, ceramic, metal, aramid, natural fibers (e.g., flax, jute, sisal, hemp), paper, acrylic, and polyethylene fibers, as well as mixtures thereof. The reinforcing fibers can be in any of a variety of forms, such as strands or rovings formed by aligning continuous or discontinuous fibers (short fibers) in one direction, woven or mat-like fabrics, braids, unidirectional, bidirectional, random, quasi-isotropically, or three-dimensionally distributed mat-like materials, non-uniform lattice or mesh materials, and three-dimensional materials such as triaxial woven fabrics.

[0065] Thus, in another aspect, there is provided a method for producing a composite article, comprising the steps of contacting a layer of reinforcing fibers with a polymerizable thermosetting composition to coat and / or impregnate the reinforcing fibers; and curing the coated and / or impregnated reinforcing fibers to produce the composite article.

[0066] The coating and / or impregnation can be carried out by either a wet method or a hot melt method, in which the thermosetting composition is first dissolved in a solvent to reduce the viscosity, after which the reinforcing fibers are coated and / or impregnated, and the solvent is evaporated, for example, using an oven.

[0067] In the hot melt method, the coating and / or impregnation can be carried out by directly coating and / or impregnating the reinforcing fibers with the polymerizable thermosetting composition, which can be heated to reduce its viscosity, or alternatively, a film coated with the polymerizable thermosetting composition can be first made on a release paper or the like, and the film can be placed on one or both sides of the reinforcing fibers, and the coating and / or impregnation can be carried out by applying heat or pressure.

[0068] According to another aspect, there is provided a method for producing a composite product in an RTM system, the method comprising the steps of: a) introducing a fiber preform containing reinforcing fibers into a mold; b) injecting a polymerizable thermosetting composition into the mold; c) impregnating the fiber preform with the polymerizable thermosetting composition; and d) heating the resin-impregnated preform for a time to provide an at least partially cured solid product; and optionally e) subjecting the partially cured solid product to additional heating.

[0069] In yet another embodiment, a method for producing a composite product in a VaRTM system is provided, the method comprising the steps of: a) introducing a fiber preform including reinforcing fibers into a mold; b) injecting a polymerizable thermosetting composition into the mold; c) reducing the pressure within the mold; d) maintaining the mold at approximately the reduced pressure; e) impregnating the fiber preform with the polymerizable thermosetting composition; f) heating the resin-impregnated preform to provide an at least partially cured solid product; and optionally g) subjecting the at least partially cured solid product to additional heating.

[0070] In addition to RTM and VaRTM systems, the polymerizable thermosetting compositions can be used in other methods and systems for the manufacture of composite products, including prepreg hot pressing, sheet molding compounds, molding, casting, pultrusion, and filament winding.

[0071] In another aspect, the polymerizable thermoset composition upon curing provides a thermoset polymer having a balance of excellent physical, mechanical, and thermal properties. The balance of polymerizable thermoset polymer properties according to the present disclosure includes a glass transition temperature (T) above about 250°C, or above about 270°C, or above about 290°C. g );Higher than 3500MPa or 3750MPa storage modulus higher than or higher than 4000 MPa; and a char yield at 800° C. under nitrogen of at least 60%, or at least 65%, or at least 70%.

[0072] The polymerizable thermosetting compositions and composite products of the present disclosure can be used in a variety of applications, for example, in aerospace applications where they can be used as aircraft primary structural materials (wings, tails, floor beams, etc.), secondary structural materials (flaps, ailerons, cowls, fairings, interior trim, etc.), rocket motor cases, structural materials for satellites, or other vehicles such as automobiles, boats and rail cars, drive shafts, fuel cells, leaf springs, wind turbine blades, pressure vessels, flywheels, papermaking rollers, and civil engineering and building materials (roofing, cables, rebar, reinforcement). DETAILED DESCRIPTION OF THE INVENTION

[0073] Working Example: Chemical analysis methods such as NMR, FTIR, LC-MS, GPC and HPLC are available from Hunts The analytical analysis was performed by the Analytical Services Group within Mann Corporation; DSC, DMA and TGA were performed on TA instruments such as DSCQ2000, DSC 2500, DMA 800, TGA 5000, SDT650, and viscosity was performed on a Brookfield CAP+ 2000.

[0074] Example 1: Synthesis and homopolymerization of phenol 3-aminophenylacetylenebenzoxazine (Phenol-APA) [ka] A 3000 mL four-neck round-bottom flask equipped with a thermometer, condenser, and nitrogen inlet was charged with phenol (376 g, 4.0 mol), paraformaldehyde (263.8 g, 8.8 mol), and toluene (1200 mL). The mixture was heated to 60°C, and then 3-aminophenylacetylene (468.1 g, 4.0 mol) was added to the stirred mixture. The resulting mixture was then heated to 80°C for 1 hour and then further heated to 100°C to azeotropically remove most of the water. The reaction mixture was further heated to 110°C until the reaction was complete, yielding the product. After filtration, the product was washed with 3N sodium hydroxide and then with water and dried. The remaining toluene was then removed under vacuum, and the product was further dried in vacuo at 110°C for 3 hours and cooled to give 835 g (89%) of the product as a brown solid. The material was measured by DSC scanning at 10° C. / min and had a melting range between 53-55° C. GPC analysis showed that the main monomer was about 73%, dimer was about 20% and trimer was about 7%, with the monomer having the following spectrum: 1 H NMR (400MHz; ppm, in CDCl3): 7.20 (dd, 1H), 7.15 (d, 1H), 7.00-7.10 (m, 3H), 6. 95(d,1H),6.86(dd,1H),6.81(d,1H),5.29(s,2H),4.56(s,2H),3.02(s,1H); 13 C NMR (400MHz; ppm, in CDCl3) :154.2,148.2,129.2,127.9,126.7,125.0,122.9,121.4,120.9,120.56,118.6,117.0,83.8,78.8,77.1,50.2. LCMS:236.1074(M+H + ,Calculated value 236 .1075)

[0075] An aluminum dish was charged with 14 grams of phenol 3-aminophenylacetylene benzoxazine (Phenol-APA). The aluminum dish was then placed in a vacuum oven at 80°C for 1 hour to melt and degas. After degassing, the material was step-cured at 120°C for 2 hours, 150°C for 2 hours, 180°C for 2 hours, and 200°C for 2 hours. The DSC of the as-prepared sample and the DMA and TGA of one half of the cured product were determined. The other half of the cured product was further post-cured at 250°C for 3 hours, and the DMA and TGA of this cured product were also determined. The results are shown below in Tables 1 and 2.

[0076] Example 2: Synthesis and homopolymerization of 2-allylphenol 3-aminophenylacetylenebenzoxazine (AllylPh-APA) [ka] A 1000 mL four-neck round-bottom flask equipped with a thermometer, condenser, and nitrogen inlet was charged with 2-allylphenol (134 g, 1.0 mol), paraformaldehyde (62.9 g, 2.1 mol), toluene (2050 mL), and butanol (34 mL). The mixture was heated to 70°C, and then 3-aminophenylacetylene (117 g, 1.0 mol) was added to the stirred mixture. The resulting mixture was then heated to 100°C to remove most of the water by azeotropy. The reaction mixture was further heated to 110°C to achieve completion. After filtration, the product was washed with 3N sodium hydroxide and then water and dried. After removal of the solvent in vacuo, the product was further dried in vacuo at 100°C for 3 hours to give 250 g (90%) of product as a brownish liquid. GPC analysis indicated approximately 76% main monomer, approximately 12% dimer, and approximately 5% trimer. The major components were: 1 H NMR(p pm, CDCl3):7.10-7.30(m,4H),6.90-7.00(m,2H ),6.81(dd,1H),5.88-5.96(m,1H),5.43(s,2H),4.95-5.05(m,2H),4.62(s,2H),4.08(s,1H),3.24(d,2H);13 C NMR (ppm, CDCl3): 151.7, 147.9 136.5,129.6,128.1,127.9,127.1,125.3,123.8,122.4,120.7,120.1, 120.0,118.1,115.6,83.8,80.1,78.2,49.4,31.3;LC-MS:276.1388(M+H + ;Calculated value 276.1388).

[0077] An aluminum dish was charged with 14 grams of 2-allylphenol 3-aminophenylacetylene benzoxazine (AllPh-APA). The aluminum dish was then placed in a vacuum oven at 80°C for 1 hour to melt and degas. After degassing, the material was step-cured at 120°C for 2 hours, 150°C for 2 hours, 180°C for 2 hours, and 200°C for 2 hours. The DSC of the as-prepared sample and the DMA and TGA of one half of the cured product were determined. The other half of the cured product was further post-cured at 250°C for 3 hours, and the DMA and TGA of this cured product were also determined. The results are shown below in Tables 1 and 2.

[0078] Example 3: Synthesis and homopolymerization of 2,2',6,6'-tetramethylbisphenol F phthalonitrile (TMBF-PN) [ka] A 1000 mL four-neck round-bottom flask equipped with a thermometer, condenser, and nitrogen inlet was charged with 2,2',6,6'-tetramethylbisphenol F (100 g, 0.39 mol), 4-nitrophthalonitrile (135.1 g, 0.78 mol), and DMF (350 mL). K2CO3 (148.6 g, 1.05 mol) was then added. The resulting mixture was heated to 80-90 °C for 2-3 hours. The mixture was cooled to room temperature and poured into dilute HCl to precipitate. The precipitate was collected by filtration and washed with water until neutral, then with methanol. The solid was dried under vacuum to give 194 g (98%) of crude product as a light brown solid with a purity greater than 95% by HPLC analysis at 254 nm. Further recrystallization from acetonitrile gave the product as an off-white powder with a purity greater than 97%. Melting point 191-193°C by DSC scan at 10°C / min up to 400°C. 1 H NMR(ppm,CDCl3):7.73(d, 2H),7.14-7.17(m,4 H),7.01(s,4H),3.91 (s,2H),2.21 (s,2H),1.99(s,12H); 13 C NMR (ppm, CDCl): 161.164 (2C), 147.872(2C),139.112(2C),135.652(2C),130. 582(4C),130.010(4C),119.823(2C),119.660(2C),117.744(2C),115.498(2C),115.130(2C),108.246(2C),40.690(1C),16.192(4C);FTIR (cm-1)3105.88,3077.27,3042.23,2949.33,2916.23,2860.75,2231.82,1592.23,1567.61,1479.62,1 444.10,1420.06,1411.25,1382.71,1372.87,1329.94,1307.01,1277.14,1244.61,1191.46,1162.48, 1134.01,1085.95,1020.57,980.57,972.99,961.75,949.15,904.55,895.84,885.14,868.92,848.79, 840.06,808.47,765.01,757.67,727.54,720.58,688.45,662.06;LC-MS:C33H24N4O2(MW:508,98.16%).

[0079] An aluminum dish was charged with 14 grams of phthalonitrile monomer. The aluminum dish was then placed in an oven at 200°C to melt the material. The material was then step-cured at 260°C for 6 hours, 300°C for 3 hours, and 350°C for 4 hours. The DMA and TGA of the cured product were also determined. The results are shown below in Tables 1 and 2.

[0080] Example 4: Synthesis and homopolymerization of furanyl-2,2'-6,6'-tetramethylbisphenol F phthalonitrile (FTMBF-PN) [ka] Step 1: A 500 ml four-neck round-bottom flask equipped with a mechanical stirrer and reflux condenser was charged with 61.08 grams of 2,6-xylenol and 32.4 grams of methanol. Then, 2 grams of sodium hydroxide was added and stirred to dissolve. The resulting mixture was heated to reflux, and 24.0 grams of furfural was added dropwise under reflux over a period of 2 hours. The mixture was then refluxed for an additional 15 hours and monitored by HPLC for complete conversion, after which the mixture was neutralized with 35 grams of 20% aqueous sodium dihydrogen phosphate. The precipitated crystals were collected by filtration, washed with a 1:1 methanol / water solution, and dried in a vacuum drying oven to produce 72.6 grams of tetramethylbisphenolfuran (90.8%). The product was found to be highly pure by HPLC (99.7%). [ka]

[0081] Step 2: To a 1000 mL four-neck round-bottom flask equipped with a thermometer, a Dean-Stark trap with a condenser, and a nitrogen inlet, add furanyl-tetramethylbisphenol from Step 1 (32.2 grams, 0.1 mole), powdered KCO (33.2 grams, 0.24 mole), toluene (100 mL), and N,N-dimethylformamide (DMF) ( Toluene (146.1 grams) was added. The resulting mixture was degassed with nitrogen, and the mixture was heated to reflux at 140°C for 10-12 hours. The toluene was then removed by distillation, and the reaction mixture was cooled to 30°C. 4-Nitrophthalonitrile (35.3 grams, 0.204 moles) was then added in one portion, and the reaction mixture was heated to 80°C and monitored by HPLC for complete conversion. The mixture was then cooled to room temperature and poured into cold deionized water to produce a solid. The precipitated crystals were collected by filtration and washed with cold deionized water until neutral, then with a 1:1 methanol / water solution. The resulting dark yellow solid was dried under vacuum to give 54.5 grams (95%) of the title product. The melting point of the product was found to be 219.6°C by DSC scanning at 10°C / min. 1H NMR(ppm,CDCl3):7.733(d,2H),7.437(dd,1H),7.13-7.17(m,4H),7.00-7.03(s,4H),6.374(dd,1H),6.036(d,1H),5.39(s,1H),2.09(s,12H); 13 C NMR (ppm, CDCl3): 160.981 (2C) ,155.809(1C),148.253(2C),142.181(1C),139.815(2C),135.694(2C),130.663(4C),129.794(4C),119.817(2C) ,119.714(2C),117.689(2C),115.499(2C),115.123(2C),110.266(1C),108.500(1C),108.280(2C),49.745(1C),1 6.296(4C);FTIR(cm-1)3111.2,3075.5,3043.7,2963.5,2921.2,2862.4,2231.2,1673.8,1582.7,1564.0,1478.0 ,1421.8,1310.4,1276.7,1244.7,1182.0,1163.2,1133.4,1087.2.80,1011.5,950.0,880.4,835.6,781.3,734.8.

[0082] An aluminum dish was charged with 14 grams of phthalonitrile monomer. The aluminum dish was then placed in an oven at 220°C to melt the material. The material was then step-cured at 260°C for 6 hours, 300°C for 3 hours, and 350°C for 4 hours. The DMA and TGA of the cured product were also determined. The results are shown below in Tables 1 and 2.

[0083] Example 5: Synthesis and homopolymerization of bisphenol A phthalonitrile (BisA-PN) [ka] A 1000 mL four-neck round-bottom flask equipped with a thermometer, condenser, and nitrogen inlet was charged with bisphenol A (80 g, 0.35 mol), 4-nitrophthalonitrile (121.3 g, 0.7 mol), and DMF (300 mL). Ground K2CO3 (133.5 g, 1.05 mol) was then added. The resulting mixture was heated to 80-90 °C for 2-3 hours. The mixture was cooled to room temperature and poured into dilute HCl to form a solid. The precipitate was collected by filtration and washed with water until neutral, then with methanol. The solid was dried under vacuum to give 166 g (99%) of crude product as a green powder with a purity of approximately 93% by HPLC analysis at 280 nm. Further recrystallization from acetonitrile gave the product as green crystals (82.5% yield) with a purity greater than 97%. Melting point 198 °C by DSC scan at 10 °C / min. 1 H NMR(ppm,CDCl3):7.733(d,2H),7.33-7.36(m,4H),7.27-7.29(m,4H),7.00-7.03(m,4H),3.91(s,2H),2.21(s,2H),1.759 (s,6H); 13 C NMR(ppm,CDCl3):161.818(2C),151. 584(2C),148.304(2C),135.419(2C),128.979( 4C),121.619(2C),121.364(2C),120.223(4C),117.597(2C),115.401(2C),115.043(2C),108.796(2C),42.707(1C),30.93 8(2C);FTIR(cm-1)3074.13,3050.53,2973.19,2935.48,1876.84,2233.15,1915.12,1669.92,1589.05,1560.79,1502.11, 1485.78, 1422.65, 1407.54, 1388.51, 1366.70, 1305.39, 1288.35, 1251.36, 1209.84, 1176.79, 1163.28, 1112.99, 1103.00, 1081.80, 1016.02, 952.72, 922.78, 903.99, 887.50, 854.97, 854.07, 825.63, 777.60, 745.25, 717.42, 697.67, 671.03; LC-MS C31H20N4O2 (exact mass 480, 97.79%).

[0084] An aluminum dish was charged with 14 grams of phthalonitrile monomer. The aluminum dish was then placed in an oven at 220°C to melt the material. The material was then step-cured at 260°C for 6 hours, 300°C for 3 hours, and 350°C for 4 hours. The DMA and TGA of the cured product were also determined. The results are shown below in Tables 1 and 2.

[0085] Example 6: Synthesis and homopolymerization of bisphenol C phthalonitrile (BisC-PN) [ka] A 1000 mL four-neck round-bottom flask equipped with a thermometer, condenser, and nitrogen inlet was charged with bisphenol C (76.9 g, 0.27 mol), 4-nitrophthalonitrile (94.7 g, 0.55 mol), and DMF (250 mL). Ground K2CO3 (104.2 g, 0.82 mol) was then added. The resulting mixture was heated to 80-90°C for 2-3 hours. The mixture was cooled to room temperature and poured into dilute HCl to form a solid. The precipitate was collected by filtration and washed with water until neutral, then with methanol. The solid was dried under vacuum to give 142 g (99%) of crude product as a yellow solid with a purity greater than about 97% by HPLC analysis at 280 nm. Further recrystallization from acetonitrile gave the product as a light tan powder (87.5% yield) with a purity greater than 99%. Melting point: 198°C by DSC scan at 10°C / min. 1 H NMR (ppm in DMSO) )8.126(d,2H),7.860(d,2H),7.43-7.50(m,6H),7.21-7.25(m,4H); 13 C NMR (ppm in DMSO) 160.191 (2C), 153.850 (2C), 139.172 (1C), 136 299(2C),135.697(2C),131.119(4C),123.343(2C),122.636(2C),119.849(4C),119.039(1C),116.734(2C),115.740(2C),115.25 4(2C),108.726(2C),41.246(2C),29.284(4C);FTIR(cm-1)3066.78,3041.52,2228.20,1606.69,1590.35,1560.94,1499.85,1483. 70,1416.10,1306.05,1295.19,1279.97,1246.74,1210.05,1169.39,1161.41,1154.56,1102.68,1089.03,1016.18,978.14,967.0 0,952.81,941.27,916.08,878.81,869.26,857.37,844.35,829.40,819.90,781.88,744.44,721.67,703.65,692.30,681.79;LC-M S: C32H14Cl2N4O2, (exact mass 532, 99.31%);

[0086] An aluminum dish was charged with 14 grams of phthalonitrile monomer. The aluminum dish was then placed in an oven at 220°C to melt the material. The material was then step-cured at 260°C for 6 hours, 300°C for 3 hours, and 350°C for 4 hours. The DMA and TGA of the cured product were also determined. The results are shown below in Tables 1 and 2.

[0087] Example 7: Synthesis and homopolymerization of bisphenol M phthalonitrile (BisM-PN) [ka] A 1000 mL four-neck round-bottom flask equipped with a thermometer, condenser, and nitrogen inlet was charged with bisphenol M (120 g, 0.35 mol), 4-nitrophthalonitrile (119.9 g, 0.69 mol), and DMF (420 mL). Ground K2CO3 (105.6 g, 0.83 mol) was then added. The resulting mixture was heated to 80-90°C for 2-3 hours. The mixture was cooled to room temperature and poured into dilute HCl to form a solid. The precipitate was collected by filtration and washed with water until neutral, then with methanol. The solid was dried under vacuum to give 205 g (98%) of crude product as a dark tan solid with a purity greater than about 96% by HPLC analysis at 280 nm. Further recrystallization from acetonitrile gave the product as a light tan powder (78% yield) with a purity greater than 98%. Melting point by DSC scan at 10°C / min: 135.12°C. 1 H NMR (in DMSO) ppm)8.066(d,2H),7.67(d,2H),7.20-7.35(m,7H),7.05-7.11(m,7H),1.638(s,12H); 13C NMR (ppm in DMSO) 159.988 (2C), 150.192 (2C), 148.376 (2C), 146.734 (2C), 135.092 (2C), 127.485 (4C), 126.664 (1C), 122.913 (1C), 122.631 (2C), 121.147 (2C), 120.525 (2C),118.561(4C),115.516(2C),114.665(2C),114.170(2C),106.860(2C),41.246( 2C),29.284(4C);FTIR(cm-1)3108.42,3074.20,3040.59,2967.77,2932.21,2870.46, 2234.51,1799.58,1591.81,1563.28,1503.29,1488.99,1460.22,1449.76,1417.43,1404.26,1386.74,1364.16,1310.41,1285.60,1257.00,1248.90,1212.76,1174.34,1 164.33,1122.44,1102.23,1085.13,1075.58,967.63,954.21,931.93,900.74,889.0 1,853.17,833.42,799.02,767.81,755.62,709.86,669.62;LC-MS:C40H30N4O2 (exact mass 598,98.69%).

[0088] An aluminum dish was charged with 14 grams of phthalonitrile monomer. The aluminum dish was then placed in an oven at 160°C to melt the material. The material was then step-cured at 260°C for 6 hours, 300°C for 3 hours, and 350°C for 4 hours. The DMA and TGA of the cured product were also determined. The results are shown below in Tables 1 and 2.

[0089] Example 8: Synthesis and homopolymerization of bisphenol-P-phthalonitrile (BisP-PN) [ka] A 1000 mL four-neck round-bottom flask equipped with a thermometer, condenser, and nitrogen inlet was charged with bisphenol P (120 g, 0.35 mol), 4-nitrophthalonitrile (119.9 g, 0.69 mol), and DMF (420 mL). Ground K2CO3 (105.6 g, 0.83 mol) was then added. The resulting mixture was heated to 80-90°C for 2-3 hours. The mixture was cooled to room temperature and poured into dilute HCl to form a solid. The precipitate was collected by filtration and washed with water until neutral, then with methanol. The solid was dried under vacuum to give 203 g (97%) of crude product as a green solid with a purity greater than approximately 90% by HPLC analysis at 280 nm. Further recrystallization from acetonitrile gave the product as a light brown powder (77% yield) with a purity of approximately 96%. Melting point 202°C by DSC scan at 10°C / min. 1 H NMR (ppm in CDCl3) 7.72(dd,2H),7.25-7.35(m,8H),7.18(s,4H),6.97(d,4H),1.711(s,12H); 13 C NMR (ppm in CDCl3) 161.887(2C),151.282(2C),148.938(2C),147.390(2C),135.388(2C),129 .002(4C),126.422(4C),121.528(1C),121.355(1C),119.960(4C),117.495 (2C),115,437(2C),115.054(2C),108.607(2C),42.424(2C),30.837(4C); FTIR(cm-1)3084.57,3066.92,3042.90,2963.99,2373.24,2233.54,1915.8 2, 1670.85, 1590.88, 1565.28, 1502.28, 1483.15, 1425.21, 1405.91, 1393.05, 1362.04, 1303.82, 1290.16, 1280.14, 1247.91, 1211.87, 1175.44, 1156. 94,1122.50,1087.47,1082.14,1014.40,954.30,890.11,879.46,855.92, 831.87,767.27,719.31,699.82;LC-MS:C40H30N4O2 (exact mass: 598,96.34%);.

[0090] An aluminum dish was charged with 14 grams of phthalonitrile monomer. The aluminum dish was then placed in an oven at 200°C to melt the material. The material was then step-cured at 260°C for 6 hours, 300°C for 3 hours, and 350°C for 4 hours. The DMA and TGA of the cured product were also determined. The results are shown below in Tables 1 and 2.

[0091] Example 9: Synthesis and homopolymerization of phenol furfurylamine benzoxazine (Phenol-FA) [ka] Phenol (300 g, 3.19 mol), paraformaldehyde (200.9 g, 6.69 mol), and toluene (880 mL) were added to a 2000 mL four-neck round-bottom flask equipped with a thermometer, condenser, and nitrogen inlet. The mixture was heated to 60° C., and then furfurylamine (309.4.1 g, 3.19 mol) was added to the stirred mixture. The mixture was then heated to 80°C for 1 hour, then to 100°C to remove most of the water by azeotropy. The reaction mixture was further heated to 110°C to achieve completion. After filtration, it was washed with 3N sodium hydroxide and then with water, and dried. After removal of the toluene under vacuum, the product was further dried in vacuo at 100°C for 3 hours and cooled to give 646g (94.5%) of product as a brown solid. The material had a melting range between 54-56°C by DSC scanning at 10°C / min and was used directly in the composition without further purification. GPC analysis indicated that the main monomer was about 73% and the dimer was about 11%, with the monomer having the following spectrum: 1 H NMR(ppm,CDCl3):7.40(d,1H),7.11(dd,1H),6.93(d,1H),6.87(dd,1H),6. 80(d,1H),6.32(d,1H),6.23(d,1H),4.87(s,2H),4.00(s,2H),3.91(s,2H); 13 C NMR (ppm, CDCl3 ):154.0,151.7,142.6,127.8,127.6,120.8,119.7,116.5,110.2,108.9,81.8,49.6,48.2.LC-MS:236.1074(M+H + ,calculated value 236.1075).

[0092] An aluminum dish was charged with 14 grams of phenol furfurylamine benzoxazine. The aluminum dish was then placed in a vacuum oven at 80°C for 1 hour to melt and degas. After degassing, the material was step-cured at 120°C for 2 hours, 150°C for 2 hours, 180°C for 2 hours, and 200°C for 2 hours. The DSC of the as-prepared sample and the DMA and TGA of one half of the cured product were determined. The other half of the cured product was further post-cured at 250°C for 3 hours, and the DMA and TGA of this cured product were also determined. The results are shown below in Tables 1 and 2.

[0093] Example 10: Synthesis and homopolymerization of 4,4'-thiodiphenolanilinebenzoxazine (TDP-AN) [ka] A 2000 mL four-neck round-bottom flask equipped with a thermometer, condenser, and nitrogen inlet was charged with 4,4'-thiodiphenol (66 g, 0.3 mol), paraformaldehyde (38.1 g, 1.27 mol), and toluene (300 mL). Aniline (56.3 g, 0.6 mol) was then added dropwise. The reaction mixture was then heated to 80°C for 1 hour and further heated to 100°C to collect water by azeotropic distillation. After 14 hours, the reaction mixture was cooled, the toluene was removed by rotary evaporation, and the residue was further dried overnight in a vacuum oven at 80°C to give 420 g (94.5%) of product as a sticky solid. The material had a melting point of 0°C by DSC scanning at 10°C / min and was used directly in the composition without further purification. GPC analysis indicated approximately 52% monomer, approximately 18% dimer, approximately 11% trimer, and approximately 6% tetramer, with the monomer having the following spectrum: 1 H NMR (ppm, CDCl3):7.0-7.3(m,12H),6.856(dd,2H),6.72( d,2H),5.432(s,4H),4.610(s,4H); 13 C NMR(ppm,CDCl3):153.552(2C),147.518(2C),130.746( 1C),129.996(1C),129.046(6C),128.823(1C),128.116(1C),126.097(1C),122.4 08(1C),120.562(2C),117.304(6C),78.818(2C),43.629(2C).LCMS:453.1694(M+H + ,calculated value 453.1637).

[0094] An aluminum dish was charged with 14 grams of benzoxazine. The material was placed in a vacuum oven at 80°C and melted and degassed for 1 hour. After degassing, the material was step-cured at 120°C for 2 hours, 150°C for 2 hours, 180°C for 2 hours, and 200°C for 2 hours. The DSC of the as-prepared sample and the DMA and TGA of one half of the cured product were determined. The other half of the cured product was further post-cured at 250°C for 3 hours, and the DMA and TGA of this cured product were also determined. The results are shown below in Tables 1 and 2.

[0095] Example 11: Synthesis and homopolymerization of 4,4'-biphenolfurfurylaminebenzoxazine (BP-FA) [ka] A 2000 mL four-neck round-bottom flask equipped with a thermometer, condenser, and nitrogen inlet was charged with diphenol (200 g, 1.07 mol), paraformaldehyde (135.4 g, 4.51 mol), furfurylamine (208.5 g, 2.15 mol), and (720 ml). The mixture was heated to 100°C until complete. After cooling, the white precipitate was collected by filtration and washed with additional dioxane and ethanol. The product was further dried overnight in a vacuum oven at 80°C to give 420 g (94.5%) of the product as an off-white solid. The material had a melting point of approximately 8°C by DSC scanning at 10°C / min and was used directly in the composition without further purification. GPC analysis indicated that the major component was approximately 88%, with the following spectra: 1H NMR(ppm,CDCl3):7.21(d,2H),7.30(dd,2H),7.09(dd,2H),6,83(d,2H),6.34(m,2H),6.23(m,2H),4.90(s,2H),4.04(s,2H),3.96(s, 2H); 13 C NMR(ppm,CDCl3):153.2(2C),151. 6(2C),142.6(2C),133.9(2C),126.0(2C),125.7(2C),119.8(2C),116.6(2C),110.3(2C),108.9(2C),82.0(2C),49.7(2C),48.3(2C).LCMS:

[0096] An aluminum pan was charged with 14 grams of the material. The pan was then placed in a vacuum oven at 150°C for 1 hour to melt and degas. After degassing, the material was step-cured at 150°C for 2 hours, 160°C for 2 hours, 180°C for 2 hours, and 200°C for 2 hours. The DSC of the as-prepared sample and the DMA and TGA of one half of the cured product were determined. The other half of the cured product was further post-cured at 250°C for 3 hours, and the DMA and TGA of this cured product were also determined. The results are shown below in Tables 1 and 2.

[0097] Examples 12-17: Copolymerization of phthalonitrile monomer / benzoxazine (Phenol-APA / TMBF-PN; Phenol-APA / FTMBF-PN; Phenol-APA / BisA-PN; Phenol-APA / BisC-PN; Phenol-APA / BisM-PN; Phenol-APA / BisP-PN) Six 4-ounce glass bottles were each charged with 20 grams of phenol 3-aminophenylacetylene benzoxazine (Phenol-APA; Example 1). The bottles were then placed in an oven at 80°C until the material melted, and then 6 grams of the compounds described in Examples 3 and 7 were added to each bottle with stirring. The resulting mixtures were heated to 95°C (Example 16, Phenol-APA / BisM-PN, using BisM-PN; Example 7), 120°C (Phenol-APA / TMBF-PN, Example 12, using TMBF-PN Example 3), and 140°C (Phenol-APA / FTMBF-PN; Example 13, using FTMBF-PN, Example 4) for short periods of time until the added material dissolved in the molten benzoxazine. The mixture was heated with occasional stirring at 160°C (using Phenol-APA / BisP-PN, Example 17, and BisP-PN, Example 8) and 160°C (using Phenol-APA / BisA-PN and Phenol-APA / BisC-PN, Examples 14 and 15, and BisA-PN and BisC-PN, Examples 5 and 6). Approximately 13 grams of the mixture was then transferred into an aluminum dish. After degassing at 85°C, the mixture was cured stepwise at 120°C for 2 hours, 150°C for 2 hours, 180°C for 2 hours, and 200°C for 2 hours, or at 160°C for 2 hours, 170°C for 2 hours, 180°C for 2 hours, and 200°C for 2 hours. DSC of the freshly prepared sample and DMA and TGA of one half of the cured product were determined. The other half of the cured product was further post-cured at 250°C or 260°C for 3-4 hours, and the DMA and TGA of the cured product were determined. The results are shown below in Tables 1 and 2.

[0098] Example 18: Copolymerization of phthalonitrile monomer / benzoxazine (Phenol-APA / FTMBF-PN) A 4-ounce glass bottle was charged with 12 grams of phenol 3-aminophenylacetylene benzoxazine (Phenol-APA; Example 1). The bottle was then placed in an 80°C oven until the material melted, and then 2.4 grams of phthalonitrile prepared from furanyl-2,2',6,6'-tetramethylbisphenol F (FTBMF-PN; Example 5) was added to the bottle with stirring. The resulting mixture was gradually heated to 150°C with occasional stirring until the added material dissolved in the molten benzoxazine. Approximately 12.5 grams of the mixture was transferred to an aluminum pan. After degassing at 65°C, the mixture was cured in stages at 120°C for 2 hours, 150°C for 2 hours, 180°C for 2 hours, and 200°C for 2 hours. DSC of the freshly prepared sample and DMA and TGA of one half of the cured product were determined. The other half of the cured product was further post-cured at 250° C. for 3 more hours, and the DMA and TGA of this cured product were also determined. The results are shown below in Tables 1 and 2.

[0099] Example 19: Copolymerization of phthalonitrile monomer / benzoxazine (Phenol-APA / FTMBF-PN) A 4-ounce glass bottle was charged with 10.8 grams of phenol 3-aminophenylacetylene benzoxazine (Phenol-APA; Example 1). The bottle was then placed in an 80°C oven until the materials melted, and then 5.38 grams of phthalonitrile (FTMBF-PN; Example 5) was added to the bottle with stirring. The resulting mixture was gradually heated to 150°C with occasional stirring until the added materials were dissolved in the molten benzoxazine. Approximately 12.5 grams of the mixture was transferred to an aluminum pan. After degassing at 65°C, the mixture was step-cured at 120°C for 2 hours, 150°C for 2 hours, 180°C for 2 hours, and 200°C for 2 hours. DSC of the freshly prepared sample and DMA and TGA of one half of the cured product were determined. The other half of the cured product was further post-cured at 250°C for 3 hours, and the DMA and TGA of this cured product were also determined. The results are shown below in Tables 1 and 2.

[0100] Example 20: Copolymerization of phthalonitrile monomer / benzoxazine (Phenol-APA / BisM-PN) A 4-ounce glass bottle was charged with 20 grams of phenol 3-aminophenylacetylene benzoxazine (Phenol-APA; Example 1). The bottle was then placed in an 80°C oven until the material melted, and then 10 grams of bisphenol M-phthalonitrile (BisM-PN; Example 7) was added to the bottle with stirring until completely dissolved (maximum 130°C). Approximately 12.5 grams of the mixture was transferred to an aluminum pan. The mixture was cured in stages at 140°C for 2 hours, 180°C for 2 hours, and 220°C for 3 hours. The DSC of the freshly prepared sample and the DMA and TGA of one half of the cured product were determined. The other half of the cured product was further post-cured at 260°C for 4 hours, and the DMA and TGA of this cured product were also determined. The results are shown below in Tables 1 and 2.

[0101] Example 21: Copolymerization of phthalonitrile monomer / benzoxazine (Phenol-APA / TMBF-PN) A 4-ounce glass bottle was charged with 21 grams of phenol 3-aminophenylacetylene benzoxazine (Phenol-APA; Example 1). The bottle was then placed in an 80°C oven until the material melted, and then 9 grams of 2,2',6,6'-tetramethylbisphenol F-derived phthalonitrile (TMBF-PN; Example 3) was added to the bottle with stirring. The resulting mixture was gradually heated to 150°C with occasional stirring until the added material was dissolved in the molten benzoxazine. Approximately 12.5 grams of the mixture was transferred to an aluminum pan. The mixture was step-cured at 140°C for 1 hour, 160°C for 2 hours, 180°C for 2 hours, and 200°C for 2 hours. DSC of a freshly prepared sample and DMA and TGA of one half of the cured product were determined. The other half of the cured product was further post-cured at 260°C for 4 hours, and the DMA and TGA of this cured product were also determined. The results are shown below in Tables 1 and 2.

[0102] Example 22: Copolymerization of phthalonitrile monomer / benzoxazine (AllylPh-APA / BisM-PN) A 4-ounce glass bottle was charged with 20 grams of 2-allylphenol 3-aminophenylacetylene benzoxazine (AllylPh-APA; Example 2) and 6 grams of bisphenol M-phthalonitrile (BisM-PN; Example 7). The bottle was then placed in an oven at 80°C. The oven was gradually heated to 130°C, and the resulting mixture was stirred occasionally until the added materials were dissolved in the molten benzoxazine. Approximately 12.5 grams of the mixture was transferred to an aluminum pan. After degassing at 85°C, the mixture was step-cured at 140°C for 1 hour, 160°C for 2 hours, 180°C for 2 hours, and 220°C for 3 hours. The DSC of a freshly prepared sample and the DMA and TGA of one half of the cured product were determined. The other half of the cured product was further post-cured at 260°C for 3 hours, and the DMA and TGA of this cured product were also determined. The results are shown below in Tables 1 and 2.

[0103] Example 23: Copolymerization of phthalonitrile monomer / benzoxazine (AllylPh-APA / TMBF-PN) A 4-ounce glass bottle was charged with 20 grams of 2-allylphenol 3-aminophenylacetylene benzoxazine (AllylPh-APA; Example 2), and then 6 grams of TMBF-phthalonitrile (TMBF-PN; Example 3) was added to the bottle while stirring. The bottle was then placed in an oven at 80°C. The oven was gradually heated to 130°C, and the resulting mixture was stirred occasionally until the added materials were dissolved in the molten benzoxazine. Approximately 12.5 grams of the mixture was transferred to an aluminum pan. After degassing at 85°C, the mixture was step-cured at 140°C for 1 hour, 160°C for 2 hours, 180°C for 2 hours, and 220°C for 3 hours. The DSC of a freshly prepared sample and the DMA and TGA of one half of the cured product were determined. The other half of the cured product was further post-cured at 260°C for 3 hours, and the DMA and TGA of this cured product were also determined. The results are shown below in Tables 1 and 2.

[0104] Example 24: Copolymerization of phthalonitrile monomer / benzoxazine (Phenol-APA / Phenol-FA / BisM-PN) A 4-ounce glass bottle was charged with 10 grams of phenol 3-aminophenylacetylene benzoxazine (Phenol-APA; Example 1) and 10 grams of phenol furfurylamine benzoxazine (Phenol-FA, Example 9). The bottle was then placed in a 90°C oven until the materials were melted, and then 6.0 grams of phthalonitrile derived from bisphenol M (BisM-PN, Example 7) was added to the bottle with stirring. The temperature was then raised to 130°C. The resulting mixture was heated to 130°C until the added materials were melted. The mixture was stirred occasionally until dissolved in benzoxazine. After degassing at 100°C, the mixture was step-cured at 120°C for 2 hours, 150°C for 2 hours, 180°C for 2 hours, and 200°C for 2 hours. The DSC of the freshly prepared sample and the DMA and TGA of one half of the cured product were determined. The other half of the cured product was further post-cured at 250°C for 3 hours, and the DMA and TGA of this cured product were also determined. The results are shown below in Tables 1 and 2.

[0105] Example 25: Copolymerization of phthalonitrile monomer / benzoxazine (Phenol-APA / TDP-AN / BisM-PN) A 4-ounce glass bottle was charged with 20 grams of phenol 3-aminophenylacetylene benzoxazine (Phenol-APA; Example 1) and 10 grams of 4,4'-thiodiphenolaniline benzoxazine (TDP-AN; Example 10). The bottle was then placed in a 90°C oven until the materials melted, and then 10 grams of bisphenol M phthalonitrile (BisM-PN; Example 7) was added to the bottle with stirring. The resulting mixture was stirred occasionally until the added materials were dissolved in the molten benzoxazine. Approximately 12.5 grams of the mixture was transferred to an aluminum pan. After degassing at 100°C, the mixture was step-cured at 120°C for 2 hours, 150°C for 2 hours, 180°C for 2 hours, and 200°C for 2 hours. DSC of the freshly prepared sample and DMA and TGA of one half of the cured product were determined. The other half of the cured product was further post-cured at 250° C. for 3 more hours, and the DMA and TGA of this cured product were also determined. The results are shown below in Tables 1 and 2.

[0106] Example 26: Copolymerization of phthalonitrile monomer / benzoxazine (Phenol-APA / MT35700 / TMBF-PN) A 4-ounce glass bottle was charged with 16 grams of phenol 3-aminophenylacetylene benzoxazine (Phenol-APA, Example 1). The bottle was then placed in a 110°C oven to melt, and 4.0 grams of phthalonitrile derived from 2,2',6,6'-tetramethylbisphenol F (TMBF-PN, Example 3) was added to the bottle with stirring. The resulting mixture was stirred occasionally until the added materials were dissolved in the molten benzoxazine. Seven grams of commercially available Araldite MT35700 (MT35700, bisphenol F / phenol aniline benzoxazine resin; available in-house) were then added until everything was melted together, and approximately 12.5 grams of the mixture was transferred to an aluminum pan. The mixture was step-cured at 140°C for 2 hours, 160°C for 2 hours, 180°C for 2 hours, and 200°C for 2 hours. DSC of the freshly prepared sample and DMA and TGA of one half of the cured product were determined. The other half of the cured product was further post-cured at 250° C. for 4 days, and the DMA and TGA of this cured product were also determined. The results are shown below in Tables 1 and 2.

[0107] Example 27: Copolymerization of phthalonitrile monomer / benzoxazine (Phenol-APA / Phenol-FA / BP-FA / BisM-PN) A 4-ounce glass bottle was charged with 5 grams of phenol 3-aminophenylacetylene benzoxazine (Phenol-APA, Example 1) and 5 grams of phenol furfurylamine benzoxazine (Phenol-FA, Example 9). The bottle was then placed in a 90°C oven until the materials melted, and then 3.0 grams of phthalonitrile derived from bisphenol M (BisM-PN, Example 7) was added to the bottle with stirring. 13 grams of 4,4'-diphenol furfurylamine benzoxazine (BP-FA, Example 11) was then added to the bottle with stirring. The resulting mixture was stirred occasionally until the added materials were dissolved in the molten benzoxazine. Approximately 12.5 grams of the mixture was transferred to an aluminum dish. After degassing at 100°C, the mixture was cured in stages at 120°C for 2 hours, 150°C for 2 hours, 180°C for 2 hours, and 200°C for 2 hours. DSC of the freshly prepared sample and DMA and TGA of half of the cured product were determined. The other half of the cured product was further post-cured at 250°C for 3 more hours, and the DMA and TGA of this cured product were also determined. The results are shown below in Tables 1 and 2.

[0108] Example 28: Copolymerization of phthalonitrile monomer / benzoxazine (Phenol-APA / TDP-AN / FTMBF-PN) A 4-ounce glass bottle was charged with 20 grams of a mixture of benzoxazine and phthalonitrile (Phenol-APA / FTMBF-PN; Example 13). The bottle was then placed in a 110°C oven until the material melted, and then 7 grams of 4,4'-thiodiphenolanilineamine benzoxazine (TDP-AN; Example 10) was added to the bottle with stirring. The resulting mixture was stirred occasionally until the added material melted. Approximately 12.5 grams of the mixture was transferred to an aluminum pan. The mixture was step-cured at 140°C for 2 hours, 160°C for 2 hours, 180°C for 2 hours, and 200°C for 2 hours. The DSC of the freshly prepared sample and the DMA and TGA of one half of the cured product were determined. The other half of the cured product was further post-cured at 250°C for 4 hours, and the DMA and TGA of this cured product were also determined. The results are shown below in Tables 1 and 2.

[0109] Example 29: Copolymerization of phthalonitrile monomer / benzoxazine (Phenol-APA / / FTMBF-PN / TMBF-PN) A 4-ounce glass bottle was charged with 20 grams of the previously prepared example mixture (Phenol-APA / FTMBF-PN, Example 13). The bottle was then placed in a 90°C oven to melt, and 4.0 grams of phthalonitrile derived from 2,2',6,6'-tetramethylbisphenol F (TMBF-PN, Example 3) was then added to the bottle with stirring. The oven temperature was gradually increased to 150°C, and the resulting mixture was stirred occasionally until the added material was dissolved in the molten benzoxazine. Approximately 12.5 grams of the mixture was transferred to an aluminum pan. The mixture was cured in stages at 150°C for 1 hour, 160°C for 2 hours, 180°C for 2 hours, and 200°C for 2 hours. DSC of the freshly prepared sample and DMA and TGA of one half of the cured product were determined. The other half of the cured product was further post-cured at 260°C for 4 hours, and the DMA and TGA of this cured product were also determined. The results are shown below in Tables 1 and 2.

[0110] Example 30: Copolymerization of phthalonitrile monomer / benzoxazine (Phenol-APA / BisM-PN / BisA-PN) A 4-ounce glass bottle was charged with 12 grams of phenol 3-aminophenylacetylene benzoxazine (Phenol-APA; Example 1). The bottle was then placed in a 130°C oven to melt, and 8.0 grams of phthalonitrile derived from bisphenol M (BisM-PN; Example 7) was added to the bottle with stirring. The resulting mixture was stirred occasionally until the added material was dissolved in the molten benzoxazine. 2 grams of phthalonitrile derived from bisphenol A (BisA-PN; Example 5) was then added with stirring until dissolved. Approximately 12.5 grams of the mixture was transferred to an aluminum pan. The mixture was step-cured at 140°C for 2 hours, 160°C for 2 hours, 180°C for 2 hours, and 200°C for 2 hours. DSC of the fresh sample and DMA and TGA of one half of the cured product were determined. The other half of the cured product was further post-cured at 250°C for 4 hours, and the DMA and TGA of this cured product were also determined. The results are shown below in Tables 1 and 2. [Table 1-1] [Table 1-2] [Table 1-3] [Table 2-1] [Table 2-2] [Table 2-3]

[0111] While the making and using of various embodiments of the present invention have been described in detail above, it should be recognized that the present invention provides many applicable inventive concepts that can be embodied in a wide variety of specific contexts. The specific embodiments discussed herein are merely examples of specific ways to make and use the invention and do not limit the scope of the invention.

Claims

1. A polymerizable thermosetting composition comprising (i) one or more acetylene-bearing benzoxazine compounds and (ii) a phthalonitrile monomer.

2. The one or more acetylene-bearing benzoxazine compounds have the following structure: 【Chemistry 1】 [In the formula, R 1 , R 2 , R 3 , R 4 and R 5 Each of the groups independently represents a hydrogen atom, a substituted or unsubstituted C 1 -C 20 alkyl group, substituted or unsubstituted C 2 -C 20 Alkenyl group, substituted or unsubstituted C 6 -C 20 an aryl group, substituted or unsubstituted C 2 -C 20 Heteroaryl group, substituted or unsubstituted C 4 -C 20 Carbocyclic group, substituted or unsubstituted C 2 -C 20 Heterocyclic group or C 3 -C 8 cycloalkyl groups; b is an integer ranging from 1 to 4, where: When b is 1, Z is a hydrogen atom, a substituted or unsubstituted C 1 -C 20 Alkyl groups, substituted or unsubstituted Substitution C 2 -C 20 Alkenyl group, substituted or unsubstituted C 6 -C 20 an aryl group, substituted or unsubstituted C 2 -C 20 Heteroaryl group, substituted or unsubstituted C 4 -C 20 Carbocyclic group, substituted or unsubstituted C 2 -C 20 Heterocyclic group or C 3 -C 8 is a cycloalkyl group; each R 1 is an alkynyl-substituted C 1 -C 20 Alkyl group, alkynyl-substituted C 8 -C 20 Aryl group, alkynyl-substituted C 2 -C 20 Heteroaryl group, alkynyl-substituted C 4 -C 20 Carbocyclic Group, Alkynyl-Substituted C 2 -C 20 Heterocyclic or alkynyl-substituted C 3 -C 8 is a cycloalkyl group; When b is 2, Z is a direct bond or a substituted or unsubstituted C 1 -C 20 Alkyl groups, aryl groups Substituted or unsubstituted C with an aryl or heteroaryl bridge 2 -C 20 Alkyl groups, substituted or unsubstituted Substitution C 2 -C 20 Alkenyl group, substituted or unsubstituted C 2 -C 20 Alkynyl group, substituted or unsubstituted C 6 -C 20 an aryl group, substituted or unsubstituted C 2 -C 20 Heteroaryl groups, O, S, S=O, O=S=O, C=O or C=CCl 2 and When b is 3 or 4, Z is a substituted or unsubstituted C 1 -C 20 Alkyl, aryl or hexyl Substituted or unsubstituted C having a heteroaryl bridge 2 -C 20 alkyl group, substituted or unsubstituted C 2 -C 20 Alkenyl group, substituted or unsubstituted C 2 -C 20 Alkynyl group, substituted or unsubstituted C 6 -C 20 an aryl group, substituted or unsubstituted C 2 -C 20 is a heteroaryl group; and Each R 6 is an alkynyl-substituted C 1 -C 20 Alkyl group, alkynyl-substituted C 8 -C 20 Aryl group, alkynyl-substituted C 2 -C 20 Heteroaryl group, alkynyl-substituted C 4 -C 20 Carbocyclic Group, Alkynyl-Substituted C 2 -C 20 Heterocyclic or alkynyl-substituted C 3 -C 8 is a cycloalkyl group ］ 2. The polymerizable thermosetting composition of claim 1, wherein:

3. The phthalonitrile monomer has the following formula: 【Chemistry 2】 [In the formula, R 1 Or R 14 Each of the groups independently represents a hydrogen atom, a substituted or unsubstituted C 1 -C 20 Archi C 2 -C 20 Alkenyl group, substituted or unsubstituted C 2 -C 20 Alkynyl group, substituted or unsubstituted C 6 -C 20 an aryl group, substituted or unsubstituted C 2 -C 20 heteroaryl groups; and Z is a direct bond, substituted or unsubstituted C 1 -C 20 Alkyl group, aryl group or hetero group Substituted or unsubstituted C with an aryl bridge 2 -C 20 alkyl group, substituted or unsubstituted C 2 -C 20 Alkenyl group, substituted or unsubstituted C 2 -C 20 Alkynyl group, substituted or unsubstituted C 6 -C 20 an aryl group, substituted or unsubstituted C 2 -C 20 Heteroaryl groups, O, S, S=O, O=S=O, C=O , C(=O)O or C=CCl 2 Or, a polymer containing oxygen in each repeating unit of the polymer chain Selected from polymer chains 10. The polymerizable thermosetting composition of claim 1, wherein the compound is one or more compounds having the formula:

4. 10. The polymerizable thermosetting composition of claim 1, further comprising at least one monofunctional benzoxazine, polyfunctional benzoxazine, or mixtures thereof.

5. A thermosetting polymer obtained by curing the thermosetting composition according to any one of claims 1 to 4.

6. 10. A method for producing a composite product, comprising contacting a layer of reinforcing fibers with the polymerizable thermosetting composition of any one of claims 1 to 4 to coat and / or impregnate the reinforcing fibers; and curing the coated and / or impregnated reinforcing fibers to produce the composite product.

7. 10. A method for producing a composite product in an RTM system, comprising the steps of: a) introducing a fiber preform containing reinforcing fibers into a mold; b) injecting a polymerizable thermosetting composition according to any one of claims 1 to 4 into the mold; c) impregnating the fiber preform with the thermosetting composition; d) heating the resin-impregnated preform for a time to provide an at least partially cured solid product; and optionally e) subjecting the partially cured solid product to additional heating.

8. 10. A method for producing a composite product in a VaRTM system, comprising the steps of: a) introducing a fiber preform containing reinforcing fibers into a mold; b) injecting a thermosetting composition according to any one of claims 1 to 4 into the mold; c) reducing the pressure within the mold; d) holding the mold at approximately the reduced pressure; e) allowing the thermosetting composition to impregnate the fiber preform; f) heating the resin-impregnated preform to provide an at least partially cured solid product; and optionally g) subjecting the at least partially cured solid product to additional heating.

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