Crosslinkable networks derived from functionalized polyetherimides and thermoset polymers obtained therefrom

Abstract

An epoxy resin composition comprising one or more epoxy resins each independently having at least two epoxy groups per molecule, an epoxy resin curing agent, optionally a curing catalyst, and a substituted or unsubstituted C 4-40 Bis-anhydrides and substituted or unsubstituted C 1-40 A curable epoxy composition comprising a functionalized polyetherimide prepared from an organic diamine and, optionally, an organic compound, wherein the functionalized polyetherimide has the formula (C 1-40 hydrocarbylene)-NH2, (C 1-40 hydrocarbylene)-OH, (C 1-40 hydrocarbylene)-SH, (C 4-40 1. A curable epoxy composition comprising a functionalized polyetherimide having a total reactive end group concentration of 50 to 1,500 μeq / g and a residual organic diamine concentration of 0.05 to 1,000 ppm by weight, the functionalized polyetherimide being obtained by precipitation or devolatilization from solution using an organic anti-solvent, the organic compound comprising at least two functional groups / molecule.

Description

[Technical Field]

[0001] The present disclosure relates to crosslinkable networks derived from functionalized polyetherimides and thermoset polymers obtained therefrom. [Background technology]

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of European Patent Application Publication No. 19159168.4, filed February 25, 2019, the contents of which are incorporated herein by reference in their entirety.

[0003] Polyimides, especially polyetherimides (PEI), have glass transition temperatures (T) above 180°C. g Polyetherimides are amorphous, transparent, high-performance thermoplastic polymers having a molecular weight of 1000 to 12000. Polyetherimides further possess high strength, toughness, heat resistance and modulus, as well as broad chemical resistance, and are therefore widely used in diverse industries such as automotive, telecommunications, aerospace, electrical / electronics, transportation, and healthcare. Polyetherimides have demonstrated versatility, demonstrating their applicability to techniques including injection molding, extrusion, and thermoforming in a variety of manufacturing processes to prepare a variety of articles. Summary of the Invention [Problem to be solved by the invention]

[0004] In addition to curable epoxy compositions, polyetherimides can be incorporated into cured thermosets, for example to function as toughening agents. However, polyetherimides are typically high viscosity materials with high T g The high viscosity combined with the high viscosity can prevent its use in certain manufacturing operations. Cured thermosets may also lack chemical resistance to commonly used solvents. Thus, there remains a need for polyetherimides suitable for use in the manufacture of thermoset materials with improved properties. [Means for solving the problem]

[0005] According to one embodiment, the curable epoxy composition comprises an epoxy resin composition comprising one or more epoxy resins each independently having at least two epoxy groups per molecule, an epoxy resin curing agent, optionally a curing catalyst, and a substituted or unsubstituted C 4-40 Bis-anhydrides and substituted or unsubstituted C 1-40 a functionalized polyetherimide prepared from an organic diamine and optionally an organic compound, the functionalized polyetherimide being present in an amount of 5 to 75 parts by weight per 100 parts by weight of the epoxy resin composition, the functionalized polyetherimide being represented by the formula (C 1-40 hydrocarbylene)-NH2, (C 1-40 hydrocarbylene)-OH, (C 1-40 hydrocarbylene)-SH, (C 4-40 and a reactive end group of 1,2-dimethyl-2,3-dimethyl-1,3 ...

[0006] Another aspect provides a method for producing a curable epoxy composition, the method comprising combining an epoxy resin composition and a functionalized polyetherimide at a temperature of 70 to 200°C to provide a reaction mixture, and adding an epoxy resin curing agent and optionally a curing catalyst to the reaction mixture to provide the curable epoxy composition.

[0007] Other embodiments include epoxy thermosets comprising the cured product of the curable epoxy composition, and articles comprising the epoxy thermoset, preferably in the form of a composite, adhesive, film, layer, coating, encapsulant, sealant, part, prepreg, casing, or combinations thereof.

[0008] The following figures are exemplary embodiments in which like elements are similarly numbered. [Brief explanation of the drawings]

[0009] [Figure 1] 1 is a scanning electron microscope (SEM) image of a fracture surface of a thermoplastic polymer-toughened epoxy sample according to one or more embodiments. [Figure 2] 1 is an SEM image of a surface before and after exposure to a solvent according to one or more embodiments. [Figure 3] 1 is an SEM image of a fracture surface of a thermoplastic polymer-toughened epoxy sample according to one or more embodiments. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present inventors have prepared functionalized polyetherimide oligomers such that epoxy formulations containing the functionalized polyetherimide oligomers have significantly lower viscosities and comparable chemical resistance to polyethersulfone epoxy formulations at similar loading levels. The disclosed lower molecular weight functionalized polyetherimide oligomers can be added to curable epoxy compositions with improved processability while possessing good solubility, yielding curable epoxy compositions with viscosities of 2,000 Pascal seconds (Pa·s) or less. Upon curing, the functionalized polyetherimide oligomers are incorporated into the crosslinked matrix of the cured thermoset, which improves mechanical properties. For example, the cured product exhibits a viscosity of 150 Joules per square meter (J / m) as measured according to ASTM D5045. 2() fracture toughness. Surprisingly, certain cured epoxy formulations containing functionalized polyetherimide oligomers provide higher fracture toughness than cured epoxy formulations containing polyethersulfone. This is contrary to what would be expected when replacing high molecular weight polyethersulfone with lower molecular weight functionalized polyetherimide oligomers.

[0011] Accordingly, certain aspects of the present disclosure provide an epoxy resin composition comprising one or more epoxy resins each independently having at least two epoxy groups per molecule, an epoxy resin curing agent, optionally a curing catalyst, and a substituted or unsubstituted C 4-40 Bis-anhydrides and substituted or unsubstituted C 1-40 1. A curable epoxy composition comprising a functionalized polyetherimide prepared from an organic diamine and optionally an organic compound, the functionalized polyetherimide being present in an amount of 5 to 75 parts by weight per 100 parts by weight of the epoxy resin composition, wherein the functionalized polyetherimide is represented by the formula (C 1-40 hydrocarbylene)-NH2, (C 1-40 hydrocarbylene)-OH, (C 1-40 hydrocarbylene)-SH, (C 4-40a curable epoxy composition comprising a functionalized polyetherimide having a total reactive end group concentration of 50 to 1,500 microequivalents per gram of functionalized polyetherimide, preferably 50 to 1,000 microequivalents per gram, and more preferably 50 to 750 microequivalents per gram; a polyetherimide composition having a residual organic diamine of 0.05 to 1,000 ppm by weight, preferably 0.05 to 500 ppm by weight, and more preferably 0.05 to 250 ppm by weight, based on the total weight of the polyetherimide composition, as determined by ultra-performance liquid chromatography; the functionalized polyetherimide obtained by precipitation or devolatilization from solution using an organic anti-solvent; and an organic compound comprising at least two functional groups per molecule, a first functional group reactive to an anhydride group, an amine group, or a combination thereof, the first functional group being different from the second functional group.

[0012] The epoxy resin composition is a compound represented by the formula (1) [ka] (Wherein A is an inorganic group having a valence of n or C 1-60 is a hydrocarbyl group, X is oxygen or nitrogen, m is 1 or 2 and is consistent with the valence of X, R is hydrogen or methyl, and n is 1 to 100, preferably 1 to 8, more preferably 2 to 4. For example, A is C 6-18 is a hydrocarbyl group, and n is 2, 3, or 4.

[0013] The epoxy resin compound is represented by the formulas (1a) to (1f) [ka] wherein each occurrence of R is independently hydrogen or methyl, and each occurrence of M is independently a C group optionally further comprising oxirane, carboxy, carboxamide, ketone, aldehyde, alcohol, halogen, or nitrile. 1- C18 C is hydrocarbylene, and each occurrence of X is independently hydrogen, chloro, fluoro, bromo, or carboxy, carboxamide, ketone, aldehyde, alcohol, halogen, or nitrile. 1- C 18 hydrocarbyl, and each occurrence of B is independently a carbon-carbon single bond, C 1- C 18 Hydrocarbyl, C 1- C 12 Hydrocarbyloxy, C 1- C 12 Such groups may include hydrocarbylthio, carbonyl, sulfide, sulfonyl, sulfinyl, phosphoryl, silane, or carboxyalkyl, carboxamide, ketone, aldehyde, alcohol, halogen, or nitrile, wherein n is 1-20 and each occurrence of p and q is independently 0-20.

[0014] Epoxy resin compounds include those produced by the reaction of epichlorohydrin or epibromohydrin with phenolic compounds. Exemplary phenolic compounds include resorcinol, catechol, hydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2-(diphenylphosphoryl)hydroquinone, bis(2,6-dimethylphenol), 2,2'-biphenol, 4,4-biphenol, 2,2'-biphenol, 3,4'-biphenol, 3,3'-biphenol, 2,2',6,6'-tetramethylbiphenol, 2,2',3,3',6,6'-hexamethylbiphenol, 3,3',5,5'-tetrabromo -2,2'6,6'-tetramethylbiphenol, 3,3'-dibromo-2,2',6,6'-tetramethylbiphenol, 2,2',6,6'-tetramethyl-3,3'-dibromobiphenol, 4,4'-isopropylidenediphenol (bisphenol A), 4,4'-isopropylidenebis(2,6-dibromophenol) (tetrabromobisphenol A), 4,4'-isopropylidenebis(2,6-dimethylphenol) (tetramethylbisphenol A), 4,4'-isopropylidenebis(2-methyl Phenol), 4,4'-isopropylidenebis(2-allylphenol), 4,4'-(1,3-phenylenediisopropylidene)bisphenol (bisphenol M), 4,4'-isopropylidenebis(3-phenylphenol), 4,4'-(1,4-phenylenediisopropylidenebisphenol (bisphenol P), 4,4'-ethylidenediphenol (bisphenol E), 4,4'-oxydiphenol, 4,4'-thiodiphenol, 4,4'-thiobis(2,6-dimethylphenol), 4,4' -sulfonyldiphenol, 4,4'-sulfonylbis(2,6-dimethylphenol), 4,4'-sulfinyldiphenol, 4,4'-hexafluoroisopropylidene)bisphenol (bisphenol AF), 4,4'-(1-phenylethylidene)bisphenol (bisphenol AP), bis(4-hydroxyphenyl)-2,2-dichloroethylene (bisphenol C), bis(4-hydroxyphenyl)methane (bisphenol F), bis(2,6-dimethyl-4-hydroxyphenyl)methane, 4,4'-(Cyclopentylidene)diphenol, 4,4'-(cyclohexylidene)diphenol (bisphenol Z), 4,4'-(cyclododecylidene)diphenol, 4,4'-(bicyclo[2.2.1]heptylidene)diphenol, 4,4'-(9H-fluorene-9,9-diyl)diphenol, 3,3-bis(4-hydroxyphenyl)isobenzofuran-1(3H)-one, 1-(4-hydroxyphenyl)-3,3-dimethyl-2,3-dihydro-1H-inden-5-ol, 1-(4-hydroxy-3,5-dimethylphenyl)-1,3,3,4,6-pentamethyl-2,3-dihydro-1H-inden-5-ol, 3,3,3',3'-tetramethyl-2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-5,6'-diol ( spirobiindane), dihydroxybenzophenone (bisphenol K), tris(4-hydroxyphenyl)methane, tris(4-hydroxyphenyl)ethane, tris(4-hydroxyphenyl)propane, tris(4-hydroxyphenyl)butane, tris(3-methyl-4-hydroxyphenyl)methane, tris(3,5-dimethyl-4-hydroxyphenyl)methane, tetrakis(4-hydroxyphenyl)ethane, tetrakis(3,5-dimethyl-4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)phenylphosphine oxide, dicyclopentadienylbis(2,6-dimethylphenol), dicyclopentadienylbis(2-methylphenol), dicyclopentadienylbisphenol, or the like, and combinations thereof.

[0015] Examples of epoxy resin compounds include polyepoxides based on aromatic amines such as aniline, e.g., N,N-diglycidylaniline, diaminodiphenylmethane, and alicyclic epoxy compounds such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 4,4'-(1,2-epoxyethyl)biphenyl, 4,4'-di(1,2-epoxyethyl)diphenyl ether, and bis(2,3-epoxycyclopentyl)ether. Other examples of epoxy resin compounds are compounds containing a combination of the above-mentioned functional groups, e.g., mixed multifunctional epoxy compounds obtained from 4-aminophenol.

[0016] Example epoxy resin compounds include glycidyl ethers of phenolic compounds, such as glycidyl ether of phenol-formaldehyde novolac, alkyl-substituted phenol-formaldehyde compounds, including cresol-formaldehyde novolac, t-butylphenol-formaldehyde novolac, sec-butylphenol-formaldehyde novolac, t-octylphenol-formaldehyde novolac, cumylphenol-formaldehyde novolac, and decylphenol-formaldehyde novolac. Other exemplary auxiliary polyepoxide compounds are the glycidyl ethers of bromophenol-formaldehyde novolac, chlorophenol-formaldehyde novolac, phenol-bis(hydroxymethyl)benzene novolac, phenol-bis(hydroxymethylbiphenyl) novolac, phenol-hydroxybenzaldehyde novolac, phenol-dicyclopentadiene novolac, naphthol-formaldehyde novolac, naphthol-bis(hydroxymethyl)benzene novolac, naphthol-bis(hydroxymethylbiphenyl) novolac, naphthol-hydroxybenzaldehyde novolac and naphthol-dicyclopentadiene novolacs or the like and combinations thereof.

[0017] Examples of epoxy resin compounds include those based on heterocyclic ring systems, such as hydantoin epoxy compounds, triglycidyl isocyanurate and its oligomers, N-glycidyl phthalimide, N-glycidyl tetrahydrophthalimide, urazole epoxides, uracil epoxides, and oxazolidinone-modified epoxy compounds. Examples of oxazolidinone-modified epoxide resin compounds include those disclosed in Angew. Makromol. Chem., vol. 44, (1975), pages 151-163 and U.S. Pat. No. 3,334,110 to Schramm. One example is the reaction product of bisphenol A diglycidyl ether with diphenylmethane diisocyanate in the presence of a suitable accelerator.

[0018] Further examples of epoxy resin compounds include polyglycidyl esters obtained by reacting epichlorohydrin or similar epoxy compounds with aliphatic, alicyclic, or aromatic polycarboxylic acids such as oxalic acid, adipic acid, glutaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, or hexahydrophthalic acid, 2,6-naphthalenedicarboxylic acid, and dimerized fatty acids. Examples include diglycidyl terephthalate and diglycidyl hexahydrophthalate. Additionally, polyepoxide compounds containing epoxide groups randomly distributed along the molecular chain and which can be prepared by emulsion copolymerization with olefinically unsaturated compounds containing these epoxide groups, such as the glycidyl esters of acrylic or methacrylic acid, can be used.

[0019] Other exemplary epoxy resin compounds include polyglycidyl ethers of polyhydric aliphatic alcohols, such as 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, polyalkylene glycols, glycerol, trimethylolpropane, 2,2-bis(4-hydroxycyclohexyl)propane, and pentaerythritol.

[0020] Examples of the monofunctional epoxy resin compound include 2-ethylhexyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, t-butyl glycidyl ether, o-cresyl glycidyl ether and nonylphenol glycidyl ether.

[0021] Other exemplary epoxy resin compounds include styrene oxide, neohexene oxide and divinylbenzene dioxide, epoxycyclohexane carboxylates such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, and dicyclopentadiene-type epoxy compounds such as dicyclopentadiene diepoxide.

[0022] Preferably, the epoxy resin compound is N,N-diglycidylaniline, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 4,4'-di(1,2-epoxyethyl)biphenyl, 4,4'-di(1,2-epoxyethyl)diphenyl ether, bis(2,3-epoxycyclopentyl)ether, triglycidyl isocyanurate, triglycidyl-p-aminophenol, triglycidyl-p-aminodiphenyl ether, tetraglycidyldiaminodiphenylmethane, bis[4-(glycidyloxy)phenyl]methane, tetraglycidyldiaminodiphenyl ether, tetrakis(4-glycidyloxyphenyl)ethane, N,N,N',N'-tetraglycidyl-diaminophenyl sulfone, bisphenol A diglycidyl ether, bisphenol F epoxy resin, epoxy phenol novolac resin, epoxy cresol novolac resin, epoxy resin containing a spiro ring, hydantoin epoxy resin, or a combination thereof.

[0023] Epoxy resin compounds can be prepared by further condensation of the epoxy compound with a phenol, such as bisphenol. One example is the condensation of bisphenol A with bisphenol A diglycidyl ether to produce an oligomeric diglycidyl ether. In another example, a different phenol can be used than the one used to derive the epoxy compound. For example, tetrabromobisphenol A can be condensed with bisphenol A diglycidyl ether to produce a halogen-containing oligomeric diglycidyl ether.

[0024] The epoxy resin compound may be a solid at room temperature. Thus, in some embodiments, the epoxy resin compound has a softening point of 25 to 150°C. The softening point can be determined, for example, by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), or a ring and ball test method such as those described in ASTM E28-67, ASTM E28-99, ASTM D36, ASTM D6493-11, and ISO 4625. The epoxy resin compound may be a liquid or a softened solid at room temperature. Thus, in some embodiments, the epoxy resin compound has a softening point of less than 25°C.

[0025] The epoxy resin curing agent is a diamine compound, preferably m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, 3,3'-oxydianiline, 3,4'-oxydianiline, 4,4'-oxydianiline, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-methylenediamine The curing agent may be bis(2,6-diethylaniline), 4,4'-methylenedianiline, diethyltoluenediamine, 4,4'-methylenebis(2,6-dimethylaniline), 2,4-bis(p-aminobenzyl)aniline, 3,5-diethyltoluene-2,4-diamine, 3,5-diethyltoluene-2,6-diamine, m-xylylenediamine, p-xylylenediamine, diethyltoluenediamine, or a combination thereof, more preferably 4,4'-diaminodiphenyl sulfone. The curable epoxy composition may comprise 0.5 to 50 wt%, preferably 2.5 to 25 wt%, more preferably 5 to 15 wt%, of the curing agent based on the total weight of the curable composition.

[0026] The curable epoxy composition optionally includes a curing catalyst. As used herein, the term "curing catalyst" encompasses compounds whose role in the curing of epoxy compounds is variously described as that of a curing agent, accelerator, catalyst, cocatalyst, or the like. The amount of curing catalyst will depend on the type of compound and the identity and amount of the other components of the composition. For example, the curable epoxy composition can include the curing catalyst in an amount of 0.5 to 50 wt %, preferably 2.5 to 25 wt %, and more preferably 5 to 15 wt %, based on the total weight of the curable composition.

[0027] The curing catalyst can be an aromatic dianhydride. Exemplary aromatic dianhydrides include 3,3-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl ether dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)benzophenone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride, 2 ,2-Bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride, 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl ether dianhydride, 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(2,3-dicarboxyphenoxy)benzophenone dianhydride, 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl sulfone dianhydride, 4-(2,3-dicarboxyphenoxy 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl-2,2-propane dianhydride, 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl ether dianhydride, 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)benzophenone dianhydride, 4-(2 ,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride, 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride), 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 4,4'-oxydiphthalic anhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride or the like.

[0028] As used herein, the term "anhydride group" includes carboxylic acids and anhydride derivatives such as carboxylic acid salts.

[0029] The curing catalyst may be a bicyclic anhydride. Examples of bicyclic anhydride compounds include methyl-5-norbornene-2,3-dicarboxylic anhydride, cis-5-norbornene-endo-2,3-dicarboxylic anhydride, or the like.

[0030] Other cure catalysts are heterocyclic compounds including benzotriazoles; triazines; piperazines; imidazoles such as 1-methylimidazole; cyclic amidines such as 4-diazabicyclo(2,2,2)octane, diazabicycloundecene, 2-phenylimidazoline or the like; N,N-dimethylaminopyridine; sulfamidate; or combinations thereof.

[0031] The curable epoxy composition may have a viscosity that is 2,000 Pascal seconds (Pa·s) or less, preferably 1,000 Pa·s or less, and more preferably 500 Pa·s or less, measured at 100° C. according to ASTM D4440-1.

[0032] The functionalized polyetherimide has a total reactive end group concentration of 50 to 1,500 microequivalents per gram of functionalized polyetherimide, preferably 50 to 1,000 microequivalents per gram, and more preferably 50 to 750 microequivalents per gram, as determined by nuclear magnetic resonance spectroscopy. 1-40 The hydrocarbylene may include substituted or unsubstituted C 1-10 Alkylene or substituted or unsubstituted C 6-40 Arylenes are included.

[0033] As used herein, a reactive end group is a group that can interact with another polymer or prepolymer to promote the formation of a crosslinked network through chemical or physical bonds during cure and / or promote the formation of phase-separated polyetherimide domains having a morphology that contributes to toughness in the cured thermoset polymer. The reactive end group is attached to an atom of the polyetherimide chain as a chain end group.

[0034] The total reactive end group concentration is 50 to 1,500 microequivalents per gram (μeq / g) of the functionalized polyetherimide, preferably 50 to 1,000 μeq / g, and more preferably 50 to 750 μeq / g. The end group concentration can be analyzed by various titration and spectroscopic methods well known in the art. In some embodiments, the end group concentration can be determined by nuclear magnetic resonance spectroscopy.

[0035] The concentration of end groups can be analyzed by various titration and spectroscopic methods well known in the art. Spectroscopic methods include infrared, nuclear magnetic resonance, Raman spectroscopy, and fluorescence. An example of an infrared method is described in J.A. Kreuz, et al., and J. Poly. Sci. Part A-1, vol. 4, pp. 2067-2616 (1966). An example of a titration method is described in Y.J. Kim, et al., Macromolecules, vol. 26, pp. 1344-1358 (1993). It may be advantageous to prepare derivatives of the polymer end groups to improve the sensitivity of the measurement, for example, using a variant of the method described in K.P. Chan et al., Macromolecules, vol. 27, p. 6731 (1994) and J.S. Chao, Polymer Bull., vol. 17, p. 397 (1987).

[0036] The polyetherimide may comprise more than one, for example, from 2 to 1000, or from 5 to 500, or from 10 to 100, units of formula (1) [ka] wherein each R is independently the same or different and is a substituted or unsubstituted C 6-20 Aromatic hydrocarbon groups, substituted or unsubstituted, straight or branched chain C 4-20 Alkylene group, substituted or unsubstituted C 3-8 Cycloalkylene groups, particularly substituted or unsubstituted divalent C such as halogenated derivatives of any of the foregoing 1-40In some embodiments, R comprises a structural unit of formula (2): [ka] (In the formula, Q 1 -O-, -S-, -C(O)-, -SO2-, -SO-, -P(R a )(=O)-(where R a is C 1-8 Alkyl or C 6-12 aryl), -C y H 2y - (wherein y is an integer from 1 to 5) or its halogenated derivatives (including perfluoroalkylene groups) or -(CH 10 ) z - (where z is an integer from 1 to 4). In some embodiments, R is m-phenylene, p-phenylene, or diarylene sulfone, particularly bis(4,4'-phenylene) sulfone, bis(3,4'-phenylene) sulfone, bis(3,3'-phenylene) sulfone, or a combination comprising at least one of the foregoing. In some embodiments, at least 10 mole percent or at least 50 mole percent of the R groups comprise sulfone groups; in other embodiments, no R groups are sulfone groups.

[0037] Furthermore, in formula (1), T is -O- or a group of formula -OZO- (wherein the divalent bond of the -O- or -OZO- group is in the 3,3'-position, the 3,4'-position, the 4,3'-position or the 4,4'-position, and Z is 1 to 6 C 1-8 an aromatic C optionally substituted with an alkyl group, 1 to 8 halogen atoms, or a combination comprising at least one of the foregoing; 6-24 (The valence of Z may be a monocyclic or polycyclic moiety, but the valence of Z may not exceed 1.) Exemplary Z groups include those of formula (3): [ka] (In the formula, R a and R b are each independently the same or different and are a halogen atom or a monovalent C1-6 For example, p and q are each independently an integer of 0 to 4, c is an integer of 0 to 4, and X a is a bridging group connecting the hydroxy-substituted aromatic groups, and includes groups in which the bridging group and the hydroxy substituents of each C6 arylene group are arranged ortho, meta, or para (especially para) to each other of the C6 arylene group. a is a single bond, -O-, -S-, -S(O)-, -S(O)2-, -C(O)- or C 1-18 It can be an organic bridging group. 1-18 The organic bridging group may be cyclic or acyclic, aromatic or non-aromatic, and may further contain heteroatoms such as halogen, oxygen, nitrogen, sulfur, silicon, or phosphorus. 1-18 The organic group is a C6 arylene group attached to a common alkylidene carbon or C 1-18 Specific examples of Z groups include those represented by formula (3a): [ka] (Wherein, Q is —O—, —S—, —C(O)—, —SO—, —SO—, —P(R a )(=O)-(where R a is C 1-8 Alkyl or C 6-12 aryl) or -C y H 2y -, where y is an integer from 1 to 5, or a halogenated derivative thereof (including a perfluoroalkylene group). In certain embodiments, Z is derived from bisphenol A, such that Q in formula (3a) is 2,2-isopropylidene.

[0038] In one embodiment, in Formula (1), R is m-phenylene, p-phenylene, or a combination comprising at least one of the foregoing; T is -OZO-, where Z is a divalent radical of Formula (3a). Alternatively, R is m-phenylene, p-phenylene, or a combination comprising at least one of the foregoing; T is -OZO, where Z is a divalent radical of Formula (3a), and Q is 2,2-isopropylidene. Such materials are available from SABIC under the trade name ULTEM. Alternatively, the polyetherimide may be a copolymer containing additional structural polyetherimide units of formula (1), an example of which is commercially available from SABIC under the tradename EXTEM.

[0039] In some embodiments, the polyetherimide is a copolymer, e.g., a copolymer of formula (1) where at least 50 mole percent of the R groups are represented by formula (2) where Q 1 is —SO—, the remaining R groups are independently p-phenylene, m-phenylene or combinations thereof, and Z is 2,2′-(4-phenylene)isopropylidene.

[0040] In some embodiments, the polyetherimide may contain additional structural imide units that are not polyetherimide units, such as those of formula (4): [ka] wherein R is as described in formula (1), and each V is the same or different and is a substituted or unsubstituted C 6-20 Aromatic hydrocarbon groups, such as those of the formula [ka] (Wherein, W represents a single bond, -O-, -S-, -C(O)-, -SO2-, -SO-, C 1-18 Hydrocarbylene group, -P(R a )(=O)-(where R a is C 1-8 Alkyl or C 6-12 aryl) or -C y H 2y - (where y is an integer from 1 to 5) or a halogenated derivative thereof (including perfluoroalkylene groups). The additional structural imide units preferably comprise less than 20 mol % of the total number of units, and more preferably may be present in an amount of 0 to 10 mol % of the total number of units, or 0 to 5 mol % of the total number of units, or 0 to 2 mol % of the total number of units. In some embodiments, no additional imide units are present in the polyetherimide.

[0041] The polyimide or polyetherimide is represented by the formula (6): [ka] H2N-R-NH2(6) (wherein T and R are defined as above) 1-40 C of formula (5) with organic diamine 4-40 They can be prepared by any of the methods known to those skilled in the art, including the reaction of a bis(ether anhydride) or its chemical equivalent. Copolymers of polyetherimides can be made using a combination of an aromatic bis(ether anhydride) of formula (5) and an additional bis(anhydride) that is not a bis(ether anhydride), such as pyromellitic dianhydride or bis(3,4-dicarboxyphenyl)sulfone dianhydride.

[0042] C 4-40Illustrative examples of bisanhydrides include 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (also known as bisphenol A dianhydride or BPADA), 3,3-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl ether dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)benzophenone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride, 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl ether dianhydride, 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl ether dianhydride, 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl ether dianhydride, phenoxy)benzophenone dianhydride, 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl sulfone dianhydride, 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl-2,2-propane dianhydride, 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl ether dianhydride, 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)benzophenone dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride and 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride. Combinations of different aromatic bis(ether anhydrides) can be used.

[0043] Exemplary C 1-40Organic diamines include ethylenediamine, propylenediamine, hexamethylenediamine, polymethylated 1,6-n-hexanediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 1,12-dodecanediamine, 1,18-octadecanediamine, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 4-methylnonamethylenediamine, 5-methylnonamethylenediamine, 2,5-dimethylhexamethylene Diamine, 2,5-dimethylheptamethylenediamine, 2,2-dimethylpropylenediamine, N-methyl-bis(3-aminopropyl)amine, 3-methoxyhexamethylenediamine, 1,2-bis(3-aminopropoxy)ethane, bis(3-aminopropyl)sulfide, 1,4-cyclohexanediamine, bis(4-aminocyclohexyl)methane, m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene , m-xylylenediamine, p-xylylenediamine, 2-methyl-4,6-diethyl-1,3-phenylenediamine, 5-methyl-4,6-diethyl-1,3-phenylenediamine, benzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 1,5-diaminonaphthalene, bis(4-aminophenyl)methane, bis(2-chloro-4-amino-3,5-diethylphenyl)methane, bis(4-aminophenyl)propane, 2,4-bis(p-amino-t-butyl)methane Examples of diaminophenyl sulfones include benzene, bis(p-amino-t-butylphenyl)ether, bis(p-methyl-o-aminophenyl)benzene, bis(p-methyl-o-aminopentyl)benzene, 1,3-diamino-4-isopropylbenzene, oxydianiline, bis(aminophenoxy)phenyl)sulfone, bis(4-aminophenyl)sulfide, bis(4-aminophenyl)sulfone (also known as 4,4'-diaminodiphenylsulfone (DDS)), and bis(4-aminophenyl)ether. 1-40The organic diamine can be m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenyl sulfone, 4,4'-oxydianiline, bis(4-(4-aminophenoxy)phenyl) sulfone, or a combination thereof.

[0044] The functionalized polyetherimide comprises a polyetherimide unit of formula (1) and a polyetherimide unit of formula (8) [ka] wherein E has an average value of 2 to 100, 2 to 31, 5 to 75, 5 to 60, 5 to 15, or 15 to 40; and each R' is independently C 1-13 and siloxane blocks of R', each R' being a monovalent hydrocarbyl group. For example, each R' can independently be an optionally halogenated, C 1-13 Alkyl, C 1-13 Alkoxy, C 2-13 Alkenyl, C 2-13 Alkenyloxy, C 3-6 Cycloalkyl, C 3-6 Cycloalkoxy, C 6-14 Aryl, C 6-10 Aryloxy, C 7-13 Aryl alkyl, C 7-13 Arylalkoxy, C 7-13 Alkylaryl or C 7-13 It can be an alkylaryloxy group. In some embodiments, no bromine or chlorine is present, and in other embodiments, no halogen is present. In some embodiments, the polysiloxane blocks include R' groups with a minimal hydrocarbon moiety, such as a methyl group.

[0045] Poly(siloxane-imide) can be prepared from the bis-anhydride (6) and the organic diamine (6) as described above, or from the organic diamine and the compound of formula (9): [ka] (wherein R′ and E are as defined in formula (8), and R 4 are independently C2-C 20Hydrocarbons, especially C2-C 20 In some embodiments, R 4 is C2-C 20 and E is an alkylene group, and E has an average value of 5 to 100, 5 to 60, 5 to 15, or 15 to 40. The diamine component can contain 10 to 90 mol%, or 20 to 50 mol%, or 25 to 40 mol% of polysiloxane diamine (9) and 10 to 90 mol%, or 50 to 80 mol%, or 60 to 75 mol% of organic diamine (3), as described, for example, in U.S. Pat. No. 4,404,350. The poly(siloxane-imide) copolymer can be a block, random, or graft copolymer.

[0046] Examples of specific poly(siloxane-imides) are described in U.S. Patent Nos. 4,404,350, 4,808,686, and 4,690,997. In some embodiments, the poly(siloxane-imide) is a poly(siloxane-etherimide) and has the formula (10): [ka] (wherein R′ and E of the siloxane are as in formula (8), R and Z of the imide are as in formulas (2) and (3), and R 4 is R in equation (9). 4 and n is an integer from 5 to 100. In certain embodiments, R of the etherimide is phenylene, Z is a residue of bisphenol A, and R 4 is n-propylene, E is 2 to 50, 5 to 30, or 10 to 40, n is 5 to 100, and each R' is methyl.

[0047] The relative amounts of polysiloxane units and imide units in the poly(siloxane-imide) depend on the desired properties and are selected using the guidelines provided herein. In some embodiments, the poly(siloxane-imide) contains 10-50 wt%, 10-40 wt%, or 20-35 wt% polysiloxane units based on the total weight of the poly(siloxane-imide).

[0048] In some embodiments, the functionalized polyetherimide is not a poly(siloxane-imide) copolymer, e.g., in some embodiments, the functionalized polyetherimide does not comprise a poly(siloxane-imide copolymer).

[0049] The optional organic compound comprises at least two functional groups per molecule, where a first functional group is reactive to an anhydride, an amine, or a combination thereof, and the first functional group is different from the second functional group. For example, the organic compound may have the formula (7): R c -L n -Q 2 -L n -R d (7) (In the formula, R c and R d In formula (7), each L may be the same or different and each independently represent a substituted or unsubstituted C 1-10 Alkylene or substituted or unsubstituted C 6-20 is an arylene, and Q 2 is -O-, -S-, -S(O)-, -SO2-, -C(O)- or C 1-20 an organic bridging group, preferably substituted or unsubstituted C 1-10 Alkylene or substituted or unsubstituted C 6-20 arylene, and each n is independently 0 or 1. Formula (7) should be understood to be limited to chemically feasible organic compounds, as would be understood by one skilled in the art. For example, the organic compound cannot be HO-O-OH, and therefore, in formula (7), when Q is -O-, n is 1.

[0050] Exemplary organic compounds include para-aminophenol, meta-aminophenol, ortho-aminophenol, 4-hydroxy-4'-aminodiphenylpropane, 4-hydroxy-4'-aminodiphenylmethane, 4-amino-4'-hydroxydiphenylsulfone, 4-hydroxy-4'-aminodiphenylether, 2-hydroxy-4-aminotoluene, 4-aminothiophenol, 3-aminothiophenol, 2-aminothiophenol, 4-hydroxyphthalic anhydride, 3-hydroxyphthalic anhydride, 6-amino-2-naphthol, 5-amino-2-naphthol, 8-amino-2-naphthol, and 3-amino-2-naphthol, or the like. One or more organic compounds can be used.

[0051] The functionalized polyetherimides may be prepared by reacting a substituted or unsubstituted C under reaction conditions effective to provide the functionalized polyetherimide. 4-40 Bis-anhydrides and substituted or unsubstituted C 1-40 They can be prepared by reacting an organic diamine with, optionally, an organic compound. For example, functionalized polyetherimides can be prepared by polycondensation of a bis-anhydride and an organic diamine. Alternatively, the reaction can be carried out with a substituted or unsubstituted C under conditions effective to give a polyetherimide oligomer. 4-40 Bis-anhydrides and substituted or unsubstituted C 1-40 and melt mixing the polyetherimide oligomer with an organic compound under conditions effective to provide a functionalized polyetherimide.

[0052] In certain embodiments, the functionalized polyetherimides are prepared without the use of solvents.

[0053] The bis-anhydride and organic diamine can be reacted in substantially equimolar amounts or in a molar excess of the amine or bis-anhydride. The term "substantially equimolar amounts" refers to a molar ratio of bis-anhydride to organic diamine of 0.9 to 1.1, preferably 0.95 to 1.05, and more preferably 0.98 to 1.02. Exemplary molar excesses are represented by molar ratios of bis-anhydride to organic diamine of 26 or less, or 20 or less, more preferably 15 or less, or 2 to 26, preferably 5 to 26, and more preferably 10 to 26.

[0054] Conditions effective for providing polyetherimides include a temperature of 170 to 380°C and a solids content of 1 to 50 wt%, preferably 20 to 40 wt%, and more preferably 25 to 35 wt%. The polymerization can be carried out for 2 to 24 hours, preferably 3 to 16 hours. The polymerization can be carried out at reduced, atmospheric, or elevated pressure.

[0055] Endblocking agents, particularly monofunctional compounds capable of reacting with amines or anhydrides, may be present during polymerization. Exemplary compounds include monofunctional aromatic anhydrides such as phthalic anhydride, aliphatic monoanhydrides such as maleic anhydride, or monofunctional aldehydes, ketones, esters, isocyanates, aromatic monoamines such as anilines, or C1-C 18 Linear or cyclic aliphatic monoamines are included. The amount of end-capping agent that can be added depends on the desired amount of chain terminator and can be, for example, greater than 0 to 10 mole percent (mol%), or 0.1 to 10 mol%, or 0.1 to 6 mol%, based on the moles of end-capping agent and diamine or bis-anhydride reactant. In certain embodiments, no additional end-capping agent is used.

[0056] In some embodiments, the functionalized polyetherimide has more than 0.05 ppm by weight, preferably more than 100 ppm, more preferably more than 500 ppm, and even more preferably more than 1,000 ppm by weight of non-reactive end groups based on the total weight of the functionalized polyetherimide.

[0057] An imidization catalyst may be present during the reaction. Exemplary imidization catalysts include sodium arylphosphinates, guanidinium salts, pyridinium salts, imidazolium salts, tetra(C 7-24 aryl alkylene) ammonium salts, dialkyl heteroalicyclic ammonium salts, bis-alkyl quaternary ammonium salts, (C 7-24 Aryl alkylene)(C 1-16 alkyl)phosphonium salts, (C 6-24 Aryl)(C 1-16 Examples of suitable anionic salts include (alkyl)phosphonium salts, phosphazenium salts, and combinations thereof. The anionic component of the salt is not particularly limited and can be, for example, chloride, bromide, iodide, sulfate, phosphate, acetate, macrate, tosylate, and the like. The catalytically active amount of the catalyst can be determined by one of ordinary skill in the art without undue experimentation and can be, for example, greater than 0 to 5 mol%, or 0.01 to 2 mol%, or 0.1 to 1.5 mol%, or 0.2 to 1.0 mol%, based on the number of moles of organic diamine.

[0058] In one embodiment, the functionalized polyetherimide comprises 50 to 90 wt %, preferably 60 to 90 wt %, and more preferably 70 to 90 wt % of substituted or unsubstituted C based on the total weight of the bis-anhydride, organic diamine, and organic compound. 4-40 Bis-anhydride and 5 to 50 wt%, preferably 15 to 50 wt%, more preferably 15 to 35 wt% of substituted or unsubstituted C 1-40 It is prepared from a reaction mixture containing an organic diamine and 0 to 45 wt %, preferably 0 to 35 wt %, more preferably 0 to 25 wt % of an organic compound.

[0059] In another embodiment, the functionalized polyetherimide comprises 50 to 90 wt %, preferably 60 to 90 wt %, more preferably 70 to 90 wt % of substituted or unsubstituted C based on the total weight of the bis-anhydride, organic diamine, and organic compound. 4-40 Bis-anhydride and 5 to 50 wt%, preferably 15 to 50 wt%, more preferably 15 to 35 wt% of substituted or unsubstituted C 1-40It is prepared from a reaction mixture containing an organic diamine and 1 to 45 wt %, preferably 3 to 45 wt %, more preferably 5 to 45 wt % of an organic compound.

[0060] The functionalized polyetherimide has a weight average molecular weight (M) of 5,000 to 45,000 grams / mole (g / mol), preferably 10,000 to 45,000 g / mol, and more preferably 15,000 to 35,000 g / mol, as determined by gel permeation chromatography (GPC) using polystyrene standards. w The polydispersity index (PDI) may be less than 4.5, preferably less than 4.0, more preferably less than 3.0, and even more preferably less than 2.8.

[0061] The functionalized polyetherimide can have a maximum absolute particle size of 1 to 1,000 micrometers (μm), preferably 1 to 500 μm, even 1 to 100 μm, and even more preferably 1 to 75 μm. The maximum absolute particle size is defined by the pore size of the sieve used to isolate the functionalized polyetherimide particles and does not represent an average particle size.

[0062] The functionalized polyetherimide can have an average reactive end group functionality greater than 0.75, preferably greater than 0.9, more preferably greater than 1.1, and even more preferably greater than 1.5, where average reactive end group functionality is defined as the average number of hydroxyl, amino, and carboxylic acid end groups per polyetherimide chain.

[0063] The functionalized polyetherimide has a glass transition temperature (T) greater than 155°C, preferably greater than 175°C, and more preferably greater than 190°C. g ) can have, for example, T g The temperature may be 155 to 280°C, preferably 175 to 280°C, more preferably 190 to 280°C, as determined by differential scanning calorimetry according to ASTM D3418.

[0064] The functionalized polyetherimide can have an amide-acid concentration, as determined by nuclear magnetic resonance spectroscopy, of 0.5 to 5000 microequivalents per gram of functionalized polyetherimide, preferably 0.5 to 1000 microequivalents per gram, and more preferably 0.5 to 500 microequivalents per gram.

[0065] The curable composition can contain less than 0.05 to 5,000 ppm by weight, preferably 0.05 to 1000 ppm by weight, more preferably 0.05 to 500 ppm by weight, and even more preferably 0.05 to 250 ppm by weight of residual solvent based on the total weight of the functionalized polyetherimide.

[0066] The curable composition can contain 0.05 to 1,000 ppm by weight, preferably 0.05 to 750 ppm by weight, and more preferably 0.05 to 500 ppm by weight, of residual bis-anhydride and residual organic compound, respectively, used to prepare the functionalized polyetherimide, based on the total weight of the curable composition.

[0067] The curable composition may have a total content of residual bis-anhydrides, residual diamines, and residual organic compounds used to prepare the functionalized polyetherimide of 0.05 to 3,000 ppm by weight, preferably 0.05 to 2,000 ppm by weight, more preferably 0.05 to 1,000 ppm by weight, and even more preferably 0.05 to 500 ppm by weight, based on the total weight of the curable composition.

[0068] As used herein, "residual bis-anhydride" refers to the substituted or unsubstituted C bis-anhydride remaining from the preparation of the functionalized polyimide. 4-40 As used herein, "residual organic compounds" refers to organic compounds, if any, remaining from the preparation of a functionalized polyimide. As used herein, "residual diamines" refers to substituted or unsubstituted C2H3O4 remaining from the preparation of a functionalized polyimide. 1-40 It means an organic diamine.

[0069] The curable composition may contain 0.1 to 100 ppm by weight, 0.1 to 75 ppm by weight, or 0.1 to 25 ppm by weight of metal ions, based on the total weight of the curable composition. Examples of metal ions may include, but are not limited to, Na, K, Ca, Zn, Al, Cu, Ni, P, Ti, Mg, Mn, Si, Cr, Mo, Co, and Fe.

[0070] The curable composition may have a total metal ion content of 0.1 to 200 ppm by weight, 0.1 to 100 ppm by weight, 0.1 to 50 ppm by weight, or 0.1 to 25 ppm by weight, based on the total weight of the curable composition. Examples of metal ions may include, but are not limited to, Na, K, Ca, Zn, Al, Cu, Ni, P, Ti, Mg, Mn, Si, Cr, Mo, Co, and Fe.

[0071] The curable composition may contain anions in an amount of 0.3 to 500 ppm by weight, or 0.3 to 250 ppm by weight, based on the total weight of the curable composition. Examples of anions may include, but are not limited to, phosphate ions, nitrate ions, nitrite ions, sulfate ions, bromide ions, fluoride ions, and chloride ions.

[0072] The curable composition can further contain additives generally known in the art for polyetherimide compositions, provided that the additive(s) are selected so as not to significantly adversely affect the desired properties of the composition, particularly the formation of the poly(imide). Such additives include particulate fillers, fibrous fillers, antioxidants, heat stabilizers, light stabilizers, ultraviolet light stabilizers, ultraviolet light absorbing compounds, near-infrared light absorbing compounds, infrared light absorbing compounds, plasticizers, lubricants, mold release agents, antistatic agents, storage stabilizers, antiozonants, optical stabilizers, thickeners, conductivity affecting agents, radiation interceptors, nucleating agents, antifogging agents, antimicrobial agents, metal deactivators, colorants, surface effect additives, radiation stabilizers, flame retardants, anti-drip agents, fragrances, adhesion promoters, flow improvers, coating additives, one or more polymers different from the epoxy resin, or combinations thereof. The total amount of the additive composition can be 0.001 to 20 wt %, or 0.01 to 10 wt %, based on the total weight of the curable composition.

[0073] The functionalized polyetherimide can be further processed to obtain a powder having a specified maximum particle size. Processing includes grinding, milling, cryogenic grinding, sieving, and combinations thereof. Because the processing does not affect the weight average molecular weight, PDI, and reactive end group content, the treated polyetherimide powder possesses these properties consistent with the functionalized polyetherimide. The treated powder can be sieved to obtain the desired maximum particle size. In one embodiment, the maximum particle size is 1,000 micrometers. In another embodiment, the maximum absolute particle size is 1 to 1,000 micrometers, preferably 1 to 500 micrometers, more preferably 1 to 100 micrometers, and even more preferably 1 to 75 micrometers, as determined by the pore size of the sieve used to isolate the functionalized polyetherimide.

[0074] The functionalized polyetherimide can also be combined with, e.g., blended with, other polymers to form polymer blends, which can be used in curable epoxy compositions. Polymers that can be used include polyacetal, poly(meth)acrylates, poly(meth)acrylonitriles, polyamides, polycarbonates, polydienes, polyesters, polyethers, polyetheretherketones, polyetherimides, polyethersulfones, polyfluorocarbons, polyfluorochlorocarbons, polyimides, poly(phenylene ethers), polyketones, polyolefins, polyoxazoles, polyphosphazenes, polysiloxanes, polystyrenes, polysulfones, polyurethanes, polyvinyl acetates, polyvinyl chlorides, polyvinylidene chlorides, polyvinyl esters, polyvinyl ethers, polyvinyl ketones, polyvinylpyridines, polyvinylpyrrolidones, and copolymers thereof, such as polyetherimidesiloxane, ethylene vinyl acetates, acrylonitrile butadiene styrene, or combinations thereof. Preferably, the functionalized polyetherimide can be combined with another polymer such as polyarylate, polyamide, polyimide, polyetherimide, poly(amideimide), poly(aryl ether), phenoxy resin, poly(arylsulfone), poly(ether sulfone), poly(phenylene sulfone), poly(ether ketone), poly(ether ether ketone), poly(ether ketone ketone), poly(aryl ketone), poly(phenylene ether), polycarbonate, carboxyl-terminated butadiene-acrylonitrile (CTBN), amine-terminated butadiene-acrylonitrile (ATBN), epoxy-terminated butadiene-acrylonitrile (ETBN), core-shell rubber particles, or combinations thereof.

[0075] Also provided is a method for producing a curable epoxy composition, comprising combining an epoxy resin composition with a functionalized polyetherimide at a temperature of 70-200°C to provide a reaction mixture, and adding an epoxy resin curing agent, and optionally a curing catalyst, to the reaction mixture to provide the curable epoxy composition. The thermoplastic polymer(s), including the functionalized polyetherimide, can be added to the epoxy resin composition as insoluble particles and dissolved in the resin mixture by heating prior to adding the epoxy curing agent. Once the thermoplastic polymer(s) is substantially dissolved in the hot matrix resin precursor (i.e., the epoxy resin blend), the precursor can be cooled, and the remaining components (e.g., epoxy curing agent, insoluble thermoplastic, other additives, or combinations thereof) are added.

[0076] The process for producing epoxy thermosets involves polymerizing and crosslinking a curable epoxy composition. Curing can be accomplished using any method known in the art, such as heat, UV-visible radiation, microwave radiation, electron beam, gamma radiation, or a combination thereof.

[0077] The cured epoxy thermoset may have a glass transition temperature of 50-300°C, preferably 150-300°C, more preferably 190-300°C, even more preferably 210-300°C or even more preferably 230-300°C.

[0078] Cured epoxy thermosets have a thermal resistance of 150 Joules per square meter (J / m) measured in accordance with ASTM D5045. 2 ) or more, preferably 200 J / m 2 More than 250 J / m 2 The fracture toughness can be equal to or higher than that.

[0079] Cured epoxy thermosets can be solvent-resistant to methylene chloride, tetrachloroethane, dichlorobenzene, chloroform, dichloroethane, methyl ethyl ketone, acetone, methyl isobutyl ketone, methyl isopropyl ketone, ethyl acetate, N-methylpyrrolidone, dimethylacetamide, dimethylformamide, dimethyl sulfoxide, or combinations thereof. Cured epoxy thermosets can be solvent-resistant to less aggressive solvents, including hydraulic fluids, jet fuel, gasoline, alcohol, and other organic solvents. As used herein, "solvent-resistant" means that the cured epoxy thermoset exhibits no substantial loss of thermoplastic material as observed by microscope (no etching) when immersed in the solvent at 20-25°C for more than 30 minutes, preferably more than 24 hours, and more preferably 2-7 days.

[0080] Epoxy thermosets can be used in a variety of forms for a variety of purposes, including composites (e.g., composites using carbon fiber and glass fiber reinforcement), foams, fibers, layers, coatings, encapsulants, adhesives, sealants, sizing resins, prepregs, casings, parts, or combinations thereof. Epoxy thermosets can be used to produce many articles in aerospace, automotive, rail, marine, electronics, industrial, oil and gas, sports equipment, infrastructure, energy, and other industries where improved toughness, higher heat resistance, and good solvent resistance are needed. In certain embodiments, the composite is a glass fiber-based composite, a carbon fiber-based composite, or a combination thereof.

[0081] A method of producing a composite can include impregnating a reinforcing structure with a curable epoxy composition, partially curing the curable composition to produce a prepreg, and laminating a plurality of prepregs, the curable epoxy composition optionally including a supplemental comonomer and, optionally, one or more additional additives.

[0082] Exemplary uses for the curable epoxy compositions include, for example, acid bath vessels; neutralization tanks; aircraft parts; bridge girders; bridge decks; electrolytic cells; exhaust stacks; scrubbers; athletic equipment; stairs; walkways; automotive exterior panels such as hoods and trunk lids; floor pans; air scoops; pipes and ducts, including heater ducts; industrial fans, fan housings and blowers; industrial mixers; boat hulls and decks; pier fenders; tiles and coatings; architectural panels; business machine housings; trays, including cable trays; concrete modifiers; dishwasher and refrigerator parts; and electrical sealants. ;Electrical panels;Tanks and tank linings, including electrorefining tanks, water softener tanks, fuel tanks and various filament wound tanks;Furniture;Garage doors;Gratings;Protective body gear;Luggage;Outdoor motor vehicles;Pressure tanks;Printed circuit boards;Optical waveguides;Radomes;Fences;Railroad components such as tank cars;Hopper car covers;Car doors;Truck bed liners;Satellite dish antennas;Signage;Solar energy panels;Telephone switch housings;Tractor parts;Transformer covers;Fenders, hoods, bodies, cabs and beds truck parts such as; rotating machinery insulation including ground insulation, turn insulation and phase separation insulation; rectifiers; core insulation and cord and lacing tape; drive shaft couplings; propeller blades; missile parts; rocket motor cases; wings; sucker rods; fuselage sections; wing skins and flares; engine nacelles; cargo hatches; tennis rackets; golf club shafts; fishing rods; skis and ski poles; bicycle parts; transverse leaf springs; pumps such as automotive smog pumps; electrical components, embeddings and tools such as electrical cable joints; wound wire and high density solids multi-element assemblies; sealing of electromechanical devices; battery cases; resistors; fuses and thermal cut-off devices; coatings for printed wiring boards; castings such as capacitors, transformers, and crankcase heaters; small molded electronic components including coils, capacitors, resistors, and semiconductors; steel replacement in chemical processing, pulp and paper, power generation, and wastewater treatment; scrubbing towers; drawn parts for structural applications including structural members, gratings, and guardrails; swimming pools, swimming pool slides, hot tubs, and saunas; drive shafts for under-the-hood applications;Applications include dry toner for copiers; marine tools and composites; heat shields; submarine hulls; prototype production; experimental model development; laminate trim; drilling fixtures; joining fixtures; inspection fixtures; industrial metal forming dies; aircraft stretch block and hammer dies; vacuum forming tools; flooring, including flooring for production and assembly areas, clean rooms, machine shops, control rooms, laboratories, parking lots, freezers, coolers and outdoor loading docks; conductive compositions for antistatic applications; decorative flooring; bridge expansion joints; injection mortars for repairing and repairing cracks in structural concrete; tile grouting; machine rails; metal dowels; bolts and columns; repair of oil and fuel storage tanks, and many other applications.

[0083] The present disclosure is further illustrated by the following non-limiting examples. [Example]

[0084] Examples 1-8 were prepared using the ingredients in Table 1. [Table 1]

[0085] viscosity Viscosity measurements were performed using an ARES G2 strain controller rheometer according to ASTM D4440-1 at a constant gap of 1 mm and a constant frequency (15 rad / s) of 10% strain using disposable 8 mm plates. The sample was packed between the two plates of a parallel plate rheometer equilibrated to 140°C. Complex viscosity was measured as a function of temperature as the plates and sample cooled to 70°C.

[0086] fracture toughness After curing, the samples were removed from the molds and milled to obtain a substantially flat, uniform surface. The sample castings were dry-sanded on both sides with 600-grit sandpaper to a final thickness of 8 mm. Using the razor tap method, a sharp pre-crack was generated from the tip of the notch by applying a small impact force to a sharp razor blade placed on the test sample. After pre-crack, the samples were mounted in a tensile test clevis and tested under opening mode I loading applied by a universal testing machine (Zwick Z2.5). The load was applied at 1 mm / min under displacement control. The post-test fracture surfaces of the samples were imaged under an optical microscope to measure the crack length generated by the tapping method according to ASTM D5045. Crack lengths were measured at five equally spaced intervals on the fracture surface and averaged to obtain the average crack length for each specimen. The fracture load, along with the specimen geometry and average crack length, was recorded and used to determine the fracture toughness (K) of the epoxy materials according to ASTM D5045. IC ) was calculated. The critical strain energy release rate (G IC ) was also calculated.

[0087] Glass transition temperature Differential scanning calorimetry (DSC) was performed according to ASTM D3418 using a TA Q1000 DSC instrument. Samples were scanned from 40°C to 325°C at a heating rate of 20°C / min under nitrogen atmosphere. The glass transition temperature (T g ) and melting temperature (T m ) was decided.

[0088] SEM imaging of the samples was performed using a JEOL JSM-IT500 HR scanning electron microscope. Images were taken in secondary electron mode at an operating voltage of 10–15 kV. Prior to imaging, the samples were air-cleaned and sputter-coated with 10 nm gold / palladium. Secondary electron and backscattered electron detectors were used for morphology and Z-contrast imaging.

[0089] Table 2 shows the cure profiles for the samples. Times are listed as the amount of equilibration or hold time at the specified temperature. After the final step, the samples were slowly cooled to ambient temperature to minimize thermal stress. [Table 2]

[0090] Example 1 Synthesis of amine-terminated PEI oligomers To an oven-dried 500 mL three-neck round-bottom flask equipped with a mechanical stirrer, nitrogen adapter, and Dean-Stark condenser, 50.06 grams (g) of BPA-DA (94.6 mmol), 14.6 g of mPD (134.5 mmol), and 200 g of oDCB were added. The oil bath temperature was increased to 180°C, and the reaction was refluxed at this temperature for 3-4 hours. A small sample was removed for molecular weight determination. The target M w The reaction was stoichiometrically corrected with DA or amine to obtain M w Once this was achieved, the reaction mixture was slowly cooled to room temperature (approximately 25 °C), and then 150 g of DCM was added to it, and the contents were vigorously mixed with stirring to obtain an oligomer solution. The oligomer solution was slowly added under high shear mixing conditions to a 2 L beaker containing 800-850 mL of MeOH, resulting in the formation of a precipitate. The resulting fine off-white powder was filtered and washed with MeOH (2 × 50 mL). The isolated solid was dried in a vacuum oven at 130-135 °C for 12 h to obtain an M of 5,766 g / mol. w The amine-terminated PEI oligomer was obtained as a powder with a polydispersity index (PDI) of 2.37.

[0091] Example 2 Synthesis of amine-terminated PEI oligomers 50 g of BPA-DA (94.17 mmol), 12.40 g of mPD (114 mmol) and 200 g of oDCB gave a M of 9,872 g / mol. w The same procedure as in Example 1 was followed, except that an amine-terminated PEI oligomer powder with a PDI of 2.12 was obtained.

[0092] Example 3 Synthesis of hydroxy-terminated PEI oligomers 56.10 g of BPA-DA (107.74 mmol), 7.80 g of mPD (72.13 mmol), 8.01 g of PAP (73.31 mmol), and 200 g of oDCB gave a M of 4,598 g / mol. w The same procedure as in Example 1 was followed, except that a hydroxy-terminated PEI oligomer powder was obtained with a PDI of 2.32.

[0093] Example 4 Synthesis of hydroxy-terminated PEI oligomers 52.20 g of BPA-DA (97.47 mmol), 8.97 g of mPD (82.95 mmol), 3.50 g of PAP (32.07 mmol), and 200 g of oDCB gave a M of 9,214 g / mol. w The same procedure as in Example 1 was followed, except that a hydroxy-terminated PEI oligomer powder was obtained with a PDI of 2.42.

[0094] Example 5 Preparation of additive-free epoxy castings The following procedure was used to prepare epoxy castings containing liquid epoxy compounds (e.g., TGAP, TGDDM, BFDGE, or DGEBA) but no thermoplastic additives. 80 g of liquid epoxy was poured into a 500 mL reaction kettle equipped with a mechanical stirrer and N2 gas inlet. The kettle was purged with N2 gas for approximately 5 minutes and then immersed in an oil bath maintained at 140 °C. After approximately 15–20 minutes of heating under N2, 24 g (15% excess epoxy per NH group) of DDS was carefully added to the kettle. The solid DDS was allowed to dissolve in the liquid epoxy for approximately 15 minutes. After the DDS was completely dissolved, the contents of the kettle were then placed under vacuum for 5 minutes, followed by a N2 purge. This process was repeated for a total of three cycles, and the resulting mixture was then poured into a preheated silicone mold in a 140 °C oven. Samples were cured according to the thermal curing procedure in Table 2.

[0095] Example 6 Preparation of epoxy castings containing additives The following procedure was used to prepare epoxy castings containing a liquid epoxy compound (e.g., TGAP, TGDDM, BFDGE, or DGEBA) and a thermoplastic additive (e.g., the PEI oligomer, PEI, or PESU of Examples 1-4). For each sample, 15, 30, or 50 wt. % of the thermoplastic additive (based on the total weight of the liquid epoxy compound) was combined with the liquid epoxy compound in a kettle and heated to 140°C. After the thermoplastic additive was completely dissolved in the liquid epoxy compound (as determined visually by the formation of a clear mixture), DDS was added to the resulting epoxy mixture. The remaining steps were carried out according to the method of Example 5.

[0096] To enhance solubility in liquid epoxy compounds, the thermoplastic additives were prepared as powders and sieved using a 300 μm sieve to remove larger particles. Visual monitoring indicated that the thermoplastic additives of Examples 1-4 dissolved in the liquid epoxy compounds in approximately 20-25 minutes, compared to the 45-60 minutes required to dissolve PEI or PESU. For Examples 1-4, the nature of the reactive functional group (amine vs. hydroxy) and molecular weight (5 vs. 10 kg / mol) did not significantly alter the dissolution time.

[0097] Example 7 Synthesis of amine-terminated PEI oligomers Following the same procedure as in Example 1, 65 g of BPA-DA (121.56 mmol), 14.83 g of mPD (137.14 mmol), and 230 g of oDCB gave a M w and gave an amine-terminated PEI oligomer powder with a PDI of 2.42.

[0098] Example 8 Synthesis of amine-terminated PEI oligomers Following the same procedure as in Example 1, 65 g of BPA-DA (121.37 mmol), 14.12 g of mPD (130.57 mmol), and 230 g of oDCB gave a 26,180 g / mol M wand gave an amine-terminated PEI oligomer powder with a PDI of 2.36.

[0099] Example 9 Synthesis of amine-terminated PEI oligomers Following the same procedure as in Example 1, 64.8 g of BPA-DA (121.00 mmol), 13.84 g of mPD (127.99 mmol), and 230 g of oDCB gave a 32,968 g / mol M w and gave an amine-terminated PEI oligomer powder with a PDI of 2.35.

[0100] The viscosity of the curable epoxy compositions and the critical strain energy release rates of the cured samples of BISF and thermoplastic additives (0–50 wt%) are shown in Table 4 . [Table 3]

[0101] The viscosity of the curable epoxy compositions and the critical strain energy release rates of the cured samples of DGEBA and thermoplastic additives (0–50 wt%) are shown in Table 5 . [Table 4]

[0102] The viscosity of the curable epoxy composition and the critical strain energy release rate of the cured samples of TGAP and thermoplastic additives (0–50 wt%) are shown in Table 6. [Table 5]

[0103] The viscosity of the curable epoxy composition, the critical strain energy release rate of the cured samples, and the T of the cured samples containing TGDDM and thermoplastic additives (0-50 wt%) were measured. g is shown in Table 7. [Table 6]

[0104] The results in Tables 4-7 show that at 70°C, the viscosities of curable epoxy compositions containing the thermoplastic additives of Examples 2 and 4 at 50 wt% loadings were higher than the viscosities of curable epoxy compositions containing PESU, but at 100°C, some curable epoxy compositions had lower viscosities compared to PESU. At a loading level of 30 wt%, the curable epoxy compositions containing the thermoplastic additives of Examples 1 and 3 at 70°C had higher viscosities compared to the curable epoxy compositions containing the thermoplastic additives of Examples 2 and 4.

[0105] Samples derived from curable epoxy compositions containing the thermoplastic additives of Examples 2 and 4 showed significant improvements in fracture toughness, e.g., up to a 160% increase in fracture toughness, compared to curable compositions without the thermoplastic additive. The fracture toughness of samples containing the thermoplastic additives of Examples 2 and 4 improved with higher loadings until reaching a maximum at a loading of 30 wt% (except for the BISF epoxy formulation). Further increases in loading to 50 wt% did not result in any further improvement in fracture toughness. Overall, samples containing the thermoplastic additives of Examples 2 and 4 showed greater improvements in fracture toughness compared to samples using the thermoplastic additives of Examples 1 and 3.

[0106] At lower molecular weight thermoplastic additives, the mechanical properties of the cured thermoset, especially fracture toughness, are expected to be significantly reduced. Surprisingly, at 30 wt% thermoplastic additive loadings in Examples 2 and 4, the DGEBA and TGDDM cured samples had a higher critical strain energy release rate than the DGEBA and TGDDM cured samples containing 30 wt% PESU loadings with higher molecular weights.

[0107] As shown in Table 7, the T of the cured samples containing the thermoplastic additive of either Example 2 or 4 g is the T of cured samples containing PEI or PESU g All samples were treated with a single T gThese results indicate that functionalized polyetherimides can be used in applications involving long-term exposure to high temperatures. The incorporation of lower molecular weight thermoplastics into curable epoxy compositions is expected to reduce the thermal performance of the resulting cured epoxy thermoset. Surprisingly, DSC measurements show that TGDDM resins can be formulated with amine- or hydroxyl-terminated PEI oligomers with molecular weights of 5 or 10 kg / mol without impairing high-temperature performance.

[0108] Figure 1 shows an SEM micrograph of the fracture surface of a thermoplastic polymer-reinforced TGDDM epoxy sample obtained from fracture toughness evaluation. At a PEI loading of 15 wt%, clear phase separation (spherical features) is observed in the SEM image of the fracture surface. In addition, phase inversion regions containing spherical particles of crosslinked epoxy bound by PEI are also shown. The cured compositions of Examples 2 and 4 exhibit a two-phase morphology with smaller thermoplastic domains (0.1–0.2 μm) uniformly distributed throughout the epoxy matrix. Without being limited by theory, it is believed that the PEI oligomers of Examples 2 and 4 react with the epoxy resin and are incorporated into the epoxy network, thereby increasing the average molecular weight between crosslinks. Surprisingly, this feature was not observed for the cured compositions of Examples 1 and 3. Therefore, the higher fracture toughness of the samples containing the thermoplastic additive of Examples 2 and 4 can be explained by this difference in phase morphology. Furthermore, as the molecular weight increased to 33,000 g / mol and the loading level increased to 30 wt%, a two-phase morphology with intermittent co-continuous phases was observed for both 26,000 g / mol and 30,000 g / mol molecular weight amine-terminated PEI oligomers.

[0109] Chemical resistance was evaluated by immersing the cured thermosets in methylene chloride for 30 minutes to 1 hour. Figure 2 shows SEM images of the surfaces before and after exposure to methylene chloride. For the samples containing PEI, etched areas were observed on the surface due to dissolution of the PEI in the methylene chloride. The cured thermosets containing PEI oligomers of Examples 2 and 4 showed no surface damage by visual observation and SEM imaging, indicating improved chemical resistance.

[0110] The present disclosure further includes the following non-limiting aspects.

[0111] Embodiment 1. An epoxy resin composition comprising one or more epoxy resins each independently having at least two epoxy groups per molecule, an epoxy resin curing agent, optionally a curing catalyst, and a substituted or unsubstituted C 4-40 Bis-anhydrides and substituted or unsubstituted C 1-40 1. A curable epoxy composition comprising a functionalized polyetherimide prepared from an organic diamine and optionally an organic compound, the functionalized polyetherimide being present in an amount of 5 to 75 parts by weight per 100 parts by weight of the epoxy resin composition, wherein the functionalized polyetherimide is represented by the formula (C 1-40 hydrocarbylene)-NH2, (C 1-40 hydrocarbylene)-OH, (C 1-40 hydrocarbylene)-SH, (C 4-40a curable epoxy composition comprising a functionalized polyetherimide having a total reactive end group concentration of 50 to 1,500 μeq / g, preferably 50 to 1,000 μeq / g, and more preferably 50 to 750 μeq / g of the functionalized polyetherimide; the polyetherimide composition having a residual organic diamine of 0.05 to 1,000 ppm by weight, preferably 0.05 to 500 ppm by weight, and more preferably 0.05 to 250 ppm by weight, based on the total weight of the polyetherimide composition; the functionalized polyetherimide obtained by precipitation or devolatilization from solution using an organic anti-solvent; the organic compound comprising at least two functional groups per molecule, a first functional group reactive to an anhydride group, an amine group, or a combination thereof, the first functional group being different from the second functional group.

[0112] Embodiment 2. The curable epoxy composition of embodiment 1, wherein the epoxy resin composition comprises a compound of Formula (1) described herein.

[0113] Aspect 3. The curable epoxy composition of Aspect 1 or 2, wherein the epoxy resin curing agent is a diamine compound, preferably m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, 3,3'-oxydianiline, 3,4'-oxydianiline, 4,4'-oxydianiline, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone. and a curable epoxy composition in which the curable epoxy composition is selected from the group consisting of 4,4'-diaminodiphenyl sulfone, 4,4'-methylenebis(2,6-diethylaniline), 4,4'-methylenedianiline, diethyltoluenediamine, 4,4'-methylenebis(2,6-dimethylaniline), 2,4-bis(p-aminobenzyl)aniline, 3,5-diethyltoluene-2,4-diamine, 3,5-diethyltoluene-2,6-diamine, m-xylylenediamine, p-xylylenediamine, diethyltoluenediamine or combinations thereof, more preferably 4,4'-diaminodiphenyl sulfone.

[0114] Aspect 4. The curable epoxy composition of any one of Aspects 1 to 3, wherein the functionalized polyetherimide has a weight average molecular weight, as determined by GPC, of ​​5,000 to 45,000 g / mol, preferably 10,000 to 45,000 g / mol, and more preferably 15,000 to 35,000 g / mol; a maximum absolute particle size of 1 to 1,000 micrometers, preferably 1 to 500 micrometers, more preferably 1 to 100 micrometers, and even more preferably 1 to 75 micrometers; an average reactive end group functionality, defined as the average number of reactive end groups per polyetherimide chain, greater than 0.75, preferably greater than 0.9, more preferably greater than 1.1, and even more preferably greater than 1.5; an ASTM a glass transition temperature of 155°C to 280°C, preferably 175°C to 280°C, more preferably 190°C to 280°C, as determined by differential scanning calorimetry in accordance with D341; an amide-acid concentration of 0.5 to 5000 microequivalents per gram, preferably 0.5 to 1000 microequivalents per gram, more preferably 0.5 to 500 microequivalents per gram, as determined by nuclear magnetic resonance spectroscopy; greater than 0.05 ppm by weight, preferably greater than 100 ppm by weight, more preferably greater than 500 ppm by weight, as determined by nuclear magnetic resonance spectroscopy; a residual organic diamine of 0.05 to 1,000 ppm by weight, preferably 0.05 to 500 ppm by weight, and more preferably 0.05 to 250 ppm by weight, based on the total weight of the polyetherimide composition, as determined by ultra-performance liquid chromatography; and a polydispersity of less than 4.5, preferably less than 4.0, more preferably less than 3.0, and even more preferably less than 2.8, as determined by gel permeation chromatography using polystyrene standards.

[0115] Embodiment 5. The curable epoxy composition of any one of embodiments 1 to 4, wherein the functionalized polyetherimide powder has the formula: [ka] wherein T and R are as described herein.

[0116] Embodiment 6. The curable epoxy composition of embodiment 5, wherein each R is independently represented by the formula [ka] (In the formula, Q 1 -O-, -S-, -C(O)-, -SO2-, -SO-, -P(R ’ )(=O)-(where R ’ is C 1-8 Alkyl or C 6-12 aryl), -C y H 2y - and its halogenated derivatives (wherein y is an integer from 1 to 5) or -(CH 10 ) z - (wherein z is an integer from 1 to 4), and Z is a divalent group of the formula [ka] (In the formula, R a and R b are each independently a halogen atom or a monovalent C 1-6 is an alkyl group, p and q are each independently an integer of 0 to 4, c is an integer of 0 to 4, and X a represents a single bond, -O-, -S-, -S(O)-, -SO2-, -C(O)-, -P(R a )(=O)-(where R a is C 1-8 Alkyl or C 6-12 aryl) or C 1-18 wherein each R is independently meta-phenylene, ortho-phenylene, para-phenylene, bis(4,4'-phenylene)sulfonyl, bis(3,4'-phenylene)sulfonyl, bis(3,3'-phenylene)sulfonyl, bis(4,4'-phenylene)oxy, bis(3,4'-phenylene)oxy, bis(3,3'-phenylene)oxy, or a combination thereof; and each Z is 4,4'-diphenyleneisopropylidene.

[0117] Embodiment 7. The functionalized polyetherimide of any one of embodiments 1 to 6, wherein the polyetherimide has the formula [ka] wherein R and Z are as defined herein.

[0118] Embodiment 8. The curable epoxy composition of any one of embodiments 1 to 6, wherein the organic compound is represented by the formula R c -L n -Q 2 -L n -R d (In the formula, R c and R d are different and each independently represent -OH, -NH, -SH, or an anhydride group, a carboxylic acid, or a carboxylic acid ester group; each L is the same or different and each independently represent a substituted or unsubstituted C 1-10 Alkylene or substituted or unsubstituted C 6-20 is an arylene, and Q 2 is -O-, -S-, -S(O)-, -SO2-, -C(O)- or C 1-40 an organic bridging group, preferably substituted or unsubstituted C 1-10 Alkylene or substituted or unsubstituted C 6-20and each n is independently 0 or 1), more preferably the curable epoxy composition wherein the organic compound is para-aminophenol, meta-aminophenol, ortho-aminophenol, 4-hydroxy-4'-aminodiphenylpropane, 4-hydroxy-4'-aminodiphenylmethane, 4-amino-4'-hydroxydiphenylsulfone, 4-hydroxy-4'-aminodiphenylether, 2-hydroxy-4-aminotoluene, 4-aminothiophenol, 3-aminothiophenol, 2-aminothiophenol, 4-hydroxyphthalic anhydride, 3-hydroxyphthalic anhydride, 6-amino-2-naphthol, 5-amino-2-naphthol, 8-amino-2-naphthol, 3-amino-2-naphthol, or a combination thereof.

[0119] Embodiment 9. The curable epoxy composition of any one of embodiments 1 to 8, wherein the viscosity of the curable epoxy composition is 2,000 Pa·s or less, preferably 1,000 Pa·s or less, and more preferably 500 Pa·s or less, measured at 100°C according to ASTM D4440-1.

[0120] Embodiment 10. The curable epoxy composition of any one of Embodiments 1 to 9, further comprising a particulate filler, a fibrous filler, an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet light stabilizer, an ultraviolet light absorbing compound, a near-infrared light absorbing compound, an infrared light absorbing compound, a plasticizer, a lubricant, a mold release agent, an antistatic agent, a storage stabilizer, an antiozonant, an optical stabilizer, a thickener, a conductivity affecting agent, a radiation interceptor, a nucleating agent, an antifogging agent, an antibacterial agent, a metal deactivator, a colorant, a surface effect additive, a radiation stabilizer, a flame retardant, an anti-drip agent, a fragrance, an adhesion promoter, a flow improver, a coating additive, one or more polymers different from the epoxy resin, or a combination thereof.

[0121] Embodiment 11. The curable epoxy composition of any one of embodiments 1 to 10, further comprising a polyarylate, a polyamide, a polyimide, a polyetherimide, a poly(amideimide), a poly(aryl ether), a phenoxy resin, a poly(aryl sulfone), a poly(ether sulfone), a poly(phenylene sulfone), a poly(ether ketone), a poly(ether ether ketone), a poly(ether ketone ketone), a poly(aryl ketone), a poly(phenylene ether), a polycarbonate, a carboxyl-terminated butadiene-acrylonitrile rubber (CTBN), an amine-terminated butadiene-acrylonitrile rubber (ATBN), an epoxy-terminated butadiene-acrylonitrile rubber (ETBN), a core-shell rubber, or a combination thereof.

[0122] Embodiment 12. A process for making a curable epoxy composition according to any one of embodiments 1 to 11, comprising: combining an epoxy resin composition and a functionalized polyetherimide at a temperature between 70 and 200°C to provide a reaction mixture; and adding an epoxy resin curing agent, and optionally a curing catalyst, to the reaction mixture to provide the curable epoxy composition.

[0123] Embodiment 13. An epoxy thermoset comprising the cured product of the curable epoxy composition of any one of embodiments 1 to 11.

[0124] Embodiment 14. The epoxy thermoset of embodiment 13, having, after curing, a glass transition temperature of 50 to 300°C, preferably 150 to 300°C, more preferably 190 to 300°C, even more preferably 210 to 300°C, or even more preferably 230 to 300°C, as determined by DSC according to ASTM D3418; or 150 J / m according to ASTM D5045. 2 More than 200 J / m 2 More than 250 J / m 2or a solvent resistance to methylene chloride, tetrachloroethane, dichlorobenzene, chloroform, dichloroethane, methyl ethyl ketone, acetone, methyl isobutyl ketone, methyl isopropyl ketone, ethyl acetate, N-methylpyrrolidone, dimethylacetamide, dimethylformamide, dimethyl sulfoxide, hydraulic fluids, jet fuel, gasoline, alcohol, or a combination thereof.

[0125] Embodiment 15. An article comprising the epoxy thermoset of embodiment 13 or 14, preferably in the form of a composite, adhesive, film, layer, coating, encapsulant, sealant, part, prepreg, casing, or combination thereof.

[0126] The compositions, methods and articles can alternatively comprise, consist of, or consist essentially of any suitable component or step disclosed herein. The compositions, methods and articles can additionally or alternatively be constructed to be free of, or substantially free of, any step, component, material, ingredient, adjuvant, or chemical species that is not otherwise necessary to achieve the function or purpose of the compositions, methods and articles.

[0127] The singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. "Or" means "and / or" unless the context clearly dictates otherwise. Terms such as "first," "second," and the like do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. References throughout this specification to "an embodiment" mean that a particular element described in connection with this embodiment is included in at least one embodiment described herein and may or may not be present in other embodiments. The described elements can be combined in any suitable manner in various embodiments. "Combinations" include blends, mixtures, alloys, reaction products, and the like. As used herein, "combinations thereof" is open-ended and refers to combinations including one or more of the listed items, optionally with one or more similar items not listed.

[0128] All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other. The endpoints of all ranges directed to the same component or property are inclusive and independently combinable. The disclosure of narrower ranges or more specific groups in addition to broader ranges does not disclaim the broader range or larger group.

[0129] Unless otherwise defined, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if a term in this application contradicts or conflicts with a term in an incorporated reference, the term in this application shall take precedence over the conflicting term in the incorporated reference.

[0130] As used herein, the term "hydrocarbyl" includes groups containing carbon, hydrogen, and optionally one or more heteroatoms (e.g., 1, 2, 3, or 4 atoms such as halogen, O, N, S, P, or Si). "Alkyl" means a branched or straight-chain saturated monovalent hydrocarbon group, e.g., methyl, ethyl, i-propyl, and n-butyl. "Alkylene" means a straight-chain or branched saturated divalent hydrocarbon group, e.g., methylene (-CH-) or propylene (-(CH)-). "Alkenyl" and "alkenylene" mean a monovalent or divalent straight or branched chain hydrocarbon radical having at least one carbon-carbon double bond (e.g., ethenyl (-HC=CH2) or propenylene (-HC(CH3)=CH2-), respectively). "Alkynyl" means a straight or branched chain monovalent hydrocarbon radical having at least one carbon-carbon triple bond (e.g., ethynyl). "Alkoxy" means an alkyl group attached through oxygen (i.e., alkyl-O-), such as methoxy, ethoxy, and sec-butyloxy. "Cycloalkyl" and "cycloalkylene" mean a cycloalkyl group of the formula -C n H 2n-x and -C n H 2n-2x - (where x is the number of cyclizations), respectively. "Aryl" means a monovalent monocyclic or polycyclic aromatic group (e.g., phenyl or naphthyl). "Arylene" means a divalent aryl group. "Alkylaryl" means an aryl group substituted with an alkyl group. "Arylalkyl" means an alkyl group substituted with an aryl group (e.g., benzyl). The prefix "halo" means a group or compound containing one or more halogen (F, Cl, Br, or I) substituents, which may be the same or different. The prefix "hetero" means a group or compound containing at least one ring member that is a heteroatom (e.g., 1, 2, or 3 heteroatoms), where each heteroatom is independently N, O, S, or P.

[0131] Unless a substituent is otherwise specifically indicated, each of the foregoing groups may be unsubstituted or substituted, provided that the substitution does not significantly adversely affect the synthesis, stability, or use of the compound. "Substituted" means that the compound, group, or atom is substituted in place of hydrogen with at least one (e.g., 1, 2, 3, or 4) substituent, where each substituent is independently selected from the group consisting of nitro (-NO), cyano (-CN), hydroxy (-OH), halogen, thiol (-SH), thiocyano (-SCN), C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 1-6 Haloalkyl, C 1-9 Alkoxy, C 1-6 Haloalkoxy, C 3-12 Cycloalkyl, C 5-18 Cycloalkenyl, C 6-12 Aryl, C 7-13 Arylalkyl (e.g., benzyl), C 7-12 Alkylaryl (e.g., toluyl), C 4-12 Heterocycloalkyl, C 3-12 Heteroaryl, C 1-6 Alkylsulfonyl (-S(=O)2-alkyl), C 6-12 Arylsulfonyl (-S(=O)-aryl) or tosyl (CHCHSO-), provided that the normal valence of the substituted atom is not exceeded and the substitution does not significantly adversely affect the preparation, stability, or desired properties of the compound. The number of carbon atoms shown in the group is exclusive of all substituents. For example, -CHCHCN is a C alkyl group substituted with a nitrile.

[0132] While particular embodiments have been described, presently not foreseen or presently unforeseeable alternatives, modifications, variations, improvements, and substantial equivalents will occur to applicant or those skilled in the art. Accordingly, the appended claims, as filed and as they may be amended, are intended to cover all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

1. an epoxy resin composition comprising one or more epoxy resins each independently having at least two epoxy groups per molecule, wherein at least one of the epoxy resins comprises N,N-diglycidylaniline and / or a derivative thereof; an epoxy resin hardener; optionally a curing catalyst; Substituted or unsubstituted C ４－４０ Bis-anhydrides and substituted or unsubstituted C １－４０ a functionalized polyetherimide prepared from an organic diamine and, optionally, a monofunctional end-capping agent, the functionalized polyetherimide being present in an amount of 5 to 75 parts by weight per 100 parts by weight of the epoxy resin composition; 1. A curable epoxy composition comprising: The functionalized polyetherimide has the formula 【Chemical 1】 (In the formula, T is a group of formula -O-Z-O-, where Z is 1 to 6 C １－８ an aromatic C optionally substituted with an alkyl group, 1 to 8 halogen atoms, or a combination thereof; ６－２４ a monocyclic or polycyclic moiety, provided that the valency of Z does not exceed Each R independently represents a group of formula 【Chemistry 2】 (In the formula, Q １ is -O-, -S-, -C(O)-, -SO ２ -, -SO-, -P(R ’ )(=O)-(wherein, R ’ is C １－８ Alkyl or C ６－１２ aryl), —C ｙ H ２ｙ - and its halogenated derivatives, where y is an integer from 1 to 5, or -(C ６ H １０ ) ｚ -(wherein z is an integer from 1 to 4) Contains units of The functionalized polyetherimide has the formula (C １－４０ Hydrocarbylene)-NH ２ , (C １－４０ hydrocarbylene)-OH, (C １－４０ hydrocarbylene)-SH, (C ４－４０ hydrocarbylene)-G or combinations thereof, wherein G is an anhydride group, a carboxylic acid, or a carboxylic acid ester; or (C ４－４０ hydrocarbylene)-G is 4-hydroxyphthalic anhydride or 3-hydroxyphthalic anhydride, the functionalized polyetherimide has a total reactive end group concentration of 50 to 1,500 microequivalents per gram as determined by nuclear magnetic resonance spectroscopy; the curable epoxy composition having a residual organic diamine of 0.05 to 1,000 ppm by weight, based on the total weight of the curable epoxy composition, as determined by ultra-performance liquid chromatography; A curable epoxy composition wherein the functionalized polyetherimide is obtained by precipitation or devolatilization from a solution using an organic antisolvent.

2. 10. The curable epoxy composition of claim 1, wherein the epoxy resin composition further comprises a compound represented by the formula 【Chemistry 3】 (In the formula, A is an inorganic group having a valence of n or C １－６０ is a hydrocarbyl group; X is oxygen or nitrogen; m is 1 or 2 and is consistent with the valence of X; R is hydrogen or methyl; and n is 1 to 100.

3. 3. The curable epoxy composition of claim 2, wherein the epoxy resin curing agent is a diamine compound, and A is C ６－１８ A curable epoxy composition characterized in that: n is a hydrocarbyl group; and n is 2, 3, or 4.

4. 4. The curable epoxy composition according to claim 3, wherein the epoxy resin composition comprises N,N-diglycidylaniline, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 4,4'-di(1,2-epoxyethyl)biphenyl, 4,4'-di(1,2-epoxyethyl)diphenyl ether, bis(2,3-epoxycyclopentyl)ether, triglycidyl isocyanurate, triglycidyl-p-aminophenol, triglycidyl-p-aminodiphenyl ether, tetraglycidyldiaminodiphenylmethane, bis[4-(glycidyloxy)phenyl]methane, tetraglycidyldiaminodiphenyl ether, tetrakis(4-glycidyloxyphenyl)ethane, N,N,N',N'-tetraglycidyl-diaminophenyl sulfone, bisphenol A diglycidyl ether, bisphenol F epoxy resin, epoxy phenol novolac resin, epoxy cresol novolac resin, or a spiro ring-containing epoxy resin. , hydantoin epoxy resin, or a combination thereof, wherein the epoxy resin curing agent comprises m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, 3,3'-oxydianiline, 3,4'-oxydianiline, 4,4'-oxydianiline, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4 ... and a curable epoxy composition comprising: methylpropanol, 4,4'-methylenebis(2,6-diethylaniline), 4,4'-methylenedianiline, diethyltoluenediamine, 4,4'-methylenebis(2,6-dimethylaniline), 2,4-bis(p-aminobenzyl)aniline, 3,5-diethyltoluene-2,4-diamine, 3,5-diethyltoluene-2,6-diamine, m-xylylenediamine, p-xylylenediamine, diethyltoluenediamine, or a combination thereof.

5. 5. The curable epoxy composition of claim 1, wherein the functionalized polyetherimide is: a weight average molecular weight of 5,000 to 45,000 grams / mole as determined by gel permeation chromatography using polystyrene standards; a maximum absolute particle size of 1 to 1,000 micrometers as determined by the pore size of the sieve used to isolate said functionalized polyetherimide; an average reactive end group functionality greater than 0.75, defined as the average number of reactive end groups per polyetherimide chain; a glass transition temperature of 155°C to 280°C as determined by differential scanning calorimetry according to ASTM D341; an amide-acid concentration of the functionalized polyetherimide of 0.5 to 5000 microequivalents per gram as determined by nuclear magnetic resonance spectroscopy; greater than 0.05 ppm by weight of non-reactive end groups as determined by nuclear magnetic resonance spectroscopy; 0.05 to 1,000 ppm by weight of residual organic diamine, based on the total weight of the functionalized polyetherimide, as determined by ultra-performance liquid chromatography; and Polydispersity less than 4.5 as determined by gel permeation chromatography using polystyrene standards A curable epoxy composition comprising one or more of:

6. 10. The curable epoxy composition of claim 1, Z is a compound of the formula 【Chemistry 4】 (In the formula, R ａ and R ｂ are each independently a halogen atom or a monovalent C １－６ is an alkyl group, p and q each independently represent an integer of 0 to 4; c is 0 to 4; X ａ represents a single bond, —O—, —S—, —S(O)—, or —SO ２ -, -C(O)-, -P(R ａ )(=O)-(wherein, R ａ is C １－８ Alkyl or C ６－１２ aryl) or C １－１８ a curable epoxy composition characterized in that the group is an organic crosslinking group.

7. 7. The curable epoxy composition of claim 1, Z is 1 to 6 C １－８ an aromatic C optionally substituted with an alkyl group, 1 to 8 halogen atoms, or a combination thereof; ６－２４ A curable epoxy composition characterized by a monocyclic or polycyclic moiety, but not exceeding the valence of Z.

8. 8. The curable epoxy composition of claim 1, wherein the functionalized polyetherimide is a functionalized polyetherimide prepared from the substituted or unsubstituted C 4-40 bisanhydride, the substituted or unsubstituted C 1-40 organic diamine, the optional monofunctional end-capping agent, and an organic compound; 1. A curable epoxy composition, wherein the organic compound is para-aminophenol, meta-aminophenol, ortho-aminophenol, 4-hydroxy-4'-aminodiphenylpropane, 4-hydroxy-4'-aminodiphenylmethane, 4-amino-4'-hydroxydiphenylsulfone, 4-hydroxy-4'-aminodiphenylether, 2-hydroxy-4-aminotoluene, 4-aminothiophenol, 3-aminothiophenol, 2-aminothiophenol, 4-hydroxyphthalic anhydride, 3-hydroxyphthalic anhydride, 6-amino-2-naphthol, 5-amino-2-naphthol, 8-amino-2-naphthol, 3-amino-2-naphthol, or a combination thereof.

9. 9. The curable epoxy composition of any one of claims 1 to 8, wherein the viscosity of the curable epoxy composition is 2,000 Pa s or less, measured at 100°C according to ASTM D4440-1.

10. 10. The curable epoxy composition of any one of claims 1 to 9, further comprising a particulate filler, a fibrous filler, an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet light stabilizer, an ultraviolet light absorbing compound, a near-infrared light absorbing compound, an infrared light absorbing compound, a plasticizer, a lubricant, a mold release agent, an antistatic agent, a storage stabilizer, an antiozonant, an optical stabilizer, a thickener, a radiation interceptor, a nucleating agent, an antifogging agent, an antibacterial agent, a metal deactivator, a colorant, a radiation stabilizer, a flame retardant, an anti-drip agent, a fragrance, an adhesion promoter, a flow improver, a coating additive, a polymer different from the one or more epoxy resins, or a combination thereof.

11. 11. The curable epoxy composition of any one of claims 1 to 10, further comprising polyarylate, polyamide, polyimide, polyetherimide, poly(amideimide), poly(aryl ether), phenoxy resin, poly(aryl sulfone), poly(ether sulfone), poly(phenylene sulfone), poly(ether ketone), poly(ether ether ketone), poly(ether ketone ketone), poly(aryl ketone), poly(phenylene ether), polycarbonate, carboxyl-terminated butadiene-acrylonitrile rubber (CTBN), amine-terminated butadiene-acrylonitrile rubber (ATBN), epoxy-terminated butadiene-acrylonitrile rubber (ETBN), core-shell rubber, or a combination thereof.

12. 12. A process for the preparation of the curable epoxy composition of any one of claims 1 to 11, comprising: combining the epoxy resin composition with the functionalized polyetherimide at a temperature of 70 to 200°C to provide a reaction mixture; adding the epoxy resin hardener and, optionally, the curing catalyst to the reaction mixture to provide the curable epoxy composition; A method comprising:

13. An epoxy thermoset, characterized in that it is a cured product of the curable epoxy composition according to any one of claims 1 to 11.

14. 14. The epoxy thermoset of claim 13, which, after curing, a glass transition temperature of 50 to 300°C as determined by differential scanning calorimetry in accordance with ASTM D3418; or a fracture toughness of 150 Joules per square meter or greater as measured in accordance with ASTM D5045; or Solvent resistance to methylene chloride, tetrachloroethane, dichlorobenzene, chloroform, dichloroethane, methyl ethyl ketone, acetone, methyl isobutyl ketone, methyl isopropyl ketone, ethyl acetate, N-methylpyrrolidone, dimethylacetamide, dimethylformamide, dimethyl sulfoxide, jet fuel, gasoline, alcohol, or combinations thereof An epoxy thermoset comprising at least one of the following:

15. An article comprising the epoxy thermoset of claim 13 or 14.

16. 16. The article of claim 15, in the form of a composite, adhesive, film, layer, coating, encapsulant, sealant, part, prepreg, casing, or combination thereof.

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