Cross-linkable network from functionalized polyetherimide and thermosetting polymer resulting therefrom

Abstract

To provide a curable epoxy composition with improved properties.SOLUTION: There is provided a curable epoxy composition, comprising: 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; and a functionalized polyetherimide prepared from a substituted or unsubstituted C4-40 bisanhydride, a substituted or unsubstituted C1-40 organic diamine, wherein the functionalized polyetherimide includes a reactive end group of the formula (C1-40 hydrocarbylene)-NH2, (C1-40 hydrocarbylene)-OH, (C1-40 hydrocarbylene)-SH, (C4-40 hydrocarbylene)-G, wherein G is an anhydride group, a carboxylic acid, a carboxylic ester, or a combination thereof, wherein the functionalized polyetherimide has a total reactive end group concentration of 50 to 1,500 μeq / g and 0.05 to 1,000 wt.ppm of residual organic diamine.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to crosslinked networks derived from functionalized polyetherimides and methods for preparing such networks. The present invention relates to a thermosetting polymer. [Background technology]

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

[0003] Polyimides, especially polyetherimides (PEI), have a glass transition temperature (T g Polyetherimides are amorphous, transparent, high-performance thermoplastic polymers with high They further have high strength, toughness, heat resistance and modulus, as well as broad chemical resistance, and therefore Diverse industries such as automotive, telecommunications, aerospace, electrical / electronics, transportation and healthcare Polyetherimides are widely used in the manufacturing industry. In the manufacturing process, it has been shown that it can be applied to techniques including injection molding, extrusion and thermoforming. However, it has demonstrated versatility. Summary of the Invention [Problem to be solved by the invention]

[0004] Polyetherimides can be incorporated into curable epoxy compositions as well as into cured thermosets. However, polyetherimides are typically High viscosity material with high T g High viscosity combined with Cured thermosets tend to have poor chemical resistance to commonly used solvents. It is therefore suitable for use in the manufacture of thermosetting materials with improved properties. There remains a need for polyetherimides that are [Means for solving the problem]

[0005] According to one embodiment, the curable epoxy composition has at least two epoxy groups per molecule. and an epoxy resin composition comprising one or more epoxy resins each having independently A silicone resin hardener, optionally a curing catalyst, and a substituted or unsubstituted C 4-40 Bis-anhydride and Substituted or unsubstituted C 1-40 A functional compound prepared from an organic diamine and, optionally, an organic compound. 5 to 75 parts by weight of substituted polyetherimide per 100 parts by weight of the epoxy resin composition. and a functionalized polyetherimide present in an amount of C 1-40 hydrocarbylene)-NH2, (C 1-40 hydrocarbylene)-OH, (C 1-40 hydrocarbylene)-SH, (C 4-40 Hydrocarbylene)-G or wherein G is an anhydride group, a carboxylic acid, a carboxylic acid ester, or a combination thereof, and the functionalized polyetherimide is a functionalized polyetherimide 50 to 1,500 microequivalents per gram, preferably 50 to 1,000 microequivalents More preferably, the total reactive end group concentration is 50 to 750 microequivalents / gram. and the polyetherimide composition is determined by ultra-performance liquid chromatography. 0.05 to 1,000 ppm by weight based on the total weight of the polyetherimide composition, preferably Residual content is preferably 0.05 to 500 ppm by weight, more preferably 0.05 to 250 ppm by weight. The functionalized polyetherimide having an organic diamine can be precipitated from solution using an organic antisolvent. or by devolatilization, the organic compound containing at least two functional groups per molecule; The first functional group is reactive to an anhydride group, an amine group, or a combination thereof, and the first The functional group of the first group is different from the second functional group.

[0006] Another aspect is a method for the preparation of a curable epoxy composition, comprising the steps of: and a functionalized polyetherimide at a temperature of 70 to 200° C. to form a reaction mixture. and adding an epoxy resin hardener and, optionally, a curing catalyst to the reaction mixture to harden the epoxy resin. providing a reactive epoxy composition.

[0007] Other embodiments include an epoxy thermoset comprising the cured product of a curable epoxy composition; and Includes epoxy thermosets, preferably composites, adhesives, films, layers, coatings, sealants Articles in the form of materials, sealants, parts, prepregs, casings or combinations thereof. Includes.

[0008] The following figures are exemplary embodiments in which like elements are similarly numbered. [Brief description 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. [Diagram 2] 1 is a SEM image of a surface before and after exposure to a solvent according to one or more embodiments. [Diagram 3] 1 is a SEM image of a fracture surface of a thermoplastic polymer toughened epoxy sample according to one or more embodiments. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The inventors have demonstrated that epoxy formulations containing functionalized polyetherimide oligomers provide similar Viscosity and polymorphism were significantly lower than polyethersulfone epoxy formulations at the dosage level. Functionalized polyether ethersulfone epoxy formulations to have chemical resistance equivalent to that of ethersulfone epoxy formulations. Mido oligomers were prepared. Lower molecular weight functionalized polyetherimides were disclosed. The oligomers are curable epoxy compounds with viscosities below 2,000 Pascal seconds (Pa·s). The present invention provides a method for adding an epoxy compound to a curable epoxy composition with improved processability while having good solubility to give a composition having improved processability. Upon curing, the functionalized polyetherimide oligomers form cured thermosets. It is incorporated into the crosslinked matrix of the resin, which improves the mechanical properties, e.g. The product has a thermal conductivity of 150 Joules / square meter when measured according to ASTM D5045. Torr (J / m 2 Surprisingly, the functionalized polyester can have a fracture toughness of greater than 10 ... Certain cured epoxy formulations containing terimide oligomers are This gives the epoxy formulations higher fracture toughness compared to cured epoxy formulations containing high molecular weight polyethylene. When replacing ethersulfone with lower molecular weight functionalized polyetherimide oligomers This is contrary to what would be expected.

[0011] Thus, certain embodiments of the present disclosure provide a method for preparing a polymerizable composition comprising at least two epoxy groups per molecule. An epoxy resin composition comprising one or more epoxy resins having independently, and an epoxy resin curing method agent, and optionally a curing catalyst, and substituted or unsubstituted C 4-40 Bis-anhydrides and substituted or non-substituted substitution C 1-40 A functionalized polyether prepared from an organic diamine and, optionally, an organic compound. Thermiimide is present in an amount of 5 to 75 parts by weight per 100 parts by weight of the epoxy resin composition. and a functionalized polyetherimide having a functional group corresponding to said functionalized polyetherimide. Thermiimide has the formula (C 1-40 hydrocarbylene)-NH2, (C 1-40 Hydrocarbohydrates (C 1-40 hydrocarbylene)-SH, (C 4-40 Hydrocarbylene )-G or combinations thereof, wherein G is an anhydride group, a carboxylic acid group, , carboxylic acid esters or combinations thereof, and the functionalized polyetherimide is 50 to 1,500 microequivalents per gram of substituted polyetherimide, preferably 50 to 1, 000 micro equivalents / gram, more preferably 50 to 750 micro equivalents / gram and the polyetherimide composition is chromatographically analyzed by ultra-performance liquid chromatography. 0.05 to 1,000 based on the total weight of the polyetherimide composition, ppm by weight, preferably 0.05 to 500 ppm by weight, more preferably 0.05 to 250 ppm by weight A functionalized polyetherimide having residual organic diamines in ppm by weight was prepared using an organic anti-solvent. The organic compounds are obtained by precipitation or devolatilization from a solution containing at least 2 a first functional group being an anhydride group, an amine group, or a combination thereof; A curable epoxy composition that is reactive and has a first functional group that is different from a second functional group.

[0012] The epoxy resin composition is 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, and X is oxygen or nitrogen, m is 1 or 2 and consistent with the valency of X, and R is hydrogen. or methyl, and n is an integer of 1 to 100, preferably 1 to 8, and more preferably 2 to 4. For example, A is C 6-18 is a hydrocarbyl group, n is 2 or It is either 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 o Xylan, carboxy, carboxamide, ketone, aldehyde, alcohol, halogen or or nitrile. 1- C 18 is hydrocarbylene, and each occurrence of X are independently hydrogen, chloro, fluoro, bromo, or carboxy, carboxamido, ketone. C1 optionally further comprising toluene, aldehyde, alcohol, halogen or nitrile - C 18 each occurrence of B is independently a carbon-carbon single bond, C 1- C1 8 Hydrocarbyl, C 1- C 12 Hydrocarbyloxy, C 1- C 12 Hydrocarbyl O, carbonyl, sulfide, sulfonyl, sulfinyl, phosphoryl, silane, or Carboxyalkyl, carboxamide, ketone, aldehyde, alcohol, halogen or and n is 1 to 20, and each of p and q is preferably such a group further comprising a nitrile. The occurrences may include those that are independently 0 to 20.

[0014] Epoxy resin compounds include epichlorohydrin or epibromo with phenolic compounds. Exemplary phenolic compounds include those produced by the reaction of mohydrins. 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 Phenol, 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'-isopropylidenedi Phenol (bisphenol A), 4,4'-isopropylidenebis(2,6-dibromo Phenol) (Tetrabromobisphenol A), 4,4'-isopropylidenebis(2 ,6-Dimethylphenol) (Tetramethylbisphenol A), 4,4'-Isopropyl 4,4'-isopropylidenebis(2-arylphenol) phenol), 4,4'-(1,3-phenylenediisopropylidene)bisphenol (bis Sphenol M), 4,4'-isopropylidenebis(3-phenylphenol), 4, 4'-(1,4-phenylenediisopropylidenebisphenol (bisphenol P), 4,4'-Ethylidene diphenol (bisphenol E), 4,4'-oxydiphenol 4,4'-thiodiphenol, 4,4'-thiobis(2,6-dimethylphenol) , 4,4'-sulfonyldiphenol, 4,4'-sulfonylbis(2,6-dimethylphenyl) phenol), 4,4'-sulfinyldiphenol, 4,4'-hexafluoroisopropanol pyridene)bisphenol (bisphenol AF), 4,4'-(1-phenylethylidene Bisphenol (Bisphenol AP), Bis(4-hydroxyphenyl)-2,2 -Dichloroethylene (bisphenol C), bis(4-hydroxyphenyl)methane (bis Sphenol 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 3,3-bis(4-hydroxyphenyl)isobenzofuran Zofuran-1(3H)-one, 1-(4-hydroxyphenyl)-3,3-dimethyl-2 ,3-Dihydro-1H-inden-5-ol, 1-(4-hydroxy-3,5-dimethyl (phenyl)-1,3,3,4,6-pentamethyl-2,3-dihydro-1H-indene -5-ol, 3,3,3',3'-tetramethyl-2,2',3,3'-tetrahydro -1,1'-Spirobi[indene]-5,6'-diol (spirobiindane), dihydr Bisphenol K (oxybenzophenone), tris(4-hydroxyphenyl)methane , tris(4-hydroxyphenyl)ethane, tris(4-hydroxyphenyl)propane tris(4-hydroxyphenyl)butane, tris(3-methyl-4-hydroxyphenyl)butane (phenyl)methane, tris(3,5-dimethyl-4-hydroxyphenyl)methane, tetra tetrakis(3,5-dimethyl-4-hydroxyphenyl)ethane Bis(4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)phenylphosphine oxide, Cyclopentadienylbis(2,6-dimethylphenol), dicyclopentadienylbis (2-methylphenol), dicyclopentadienyl bisphenol or similar and combinations thereof.

[0015] Examples of epoxy resin compounds include polyepoxides based on aromatic amines such as aniline, For example, N,N-diglycidylaniline, diaminodiphenylmethane, and 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 include those having a combination of the above-mentioned functional groups. Compounds containing, for example, mixed polyfunctional epoxy compounds derived from 4-aminophenol. be.

[0016] Example epoxy resin compounds include glycidyl phenol-formaldehyde novolac. Glycidyl ethers of phenolic compounds such as ethers, cresol-formaldehyde t-Butylphenol-formaldehyde novolac, sec-Butylphenol-formaldehyde novolac phenol-formaldehyde novolac, t-octylphenol-formaldehyde novolac Volac, cumylphenol-formaldehyde novolac, decylphenol-formaldehyde Alkyl-substituted phenol-formaldehyde compounds, including aldehyde novolacs, are included. Other exemplary auxiliary polyepoxide compounds are bromophenol-formaldehyde Novolac, Chlorophenol Formaldehyde Novolac, Phenol-bis(hydo (hydroxymethyl)benzene novolac, phenol-bis(hydroxymethylbiphenyl) Novolac, Phenol-Hydroxybenzaldehyde Novolac, Phenol-Dihydroxy Naphthol-formaldehyde novolac, naphthol-bis(trimethylsilyl) Bis(hydroxymethyl)benzene novolac, naphthol-bis(hydroxymethylbiphenyl) (phenyl) novolak, naphthol-hydroxybenzaldehyde novolak and naphthol Groups of cyclopentadiene novolaks or the like, and combinations thereof It is a lysidyl ether.

[0017] Examples of epoxy resin compounds include those based on heterocyclic ring systems, such as hydantoin epoxies. Compounds, triglycidyl isocyanurate and its oligomers, N-glycidyl phthalate glycidyl tetrahydrophthalimide, urazole epoxides, uracil These include oxazolidinone-modified epoxy compounds as well as oxazolidinone-modified epoxides. For non-modified epoxide resin compounds, see Angew. Makromol. Chem., vol. l.44, (1975), pages 151-163 and Schramm One example is disclosed in U.S. Pat. No. 3,334,110 to Bisphenol A diglycidyl ester with diphenylmethane diisocyanate in the presence of an additive. It is a reaction product of ether.

[0018] Further examples of epoxy resin compounds include epichlorohydrin or similar epoxy compounds. The substances are oxalic acid, adipic acid, glutaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrofuran, Trihydrophthalic acid or hexahydrophthalic acid, 2,6-naphthalenedicarboxylic acid and By reacting with an aliphatic, alicyclic or aromatic polycarboxylic acid such as dimerized fatty acid The resulting polyglycidyl esters include diglycidyl terephthalate and and diglycidyl hexahydrophthalate. In addition, olefinically unsaturated compounds containing epoxide groups in a distribution, such as For example, by emulsion copolymerization using glycidyl esters of acrylic acid or methacrylic acid. Any polyepoxide compound that can be prepared can be used.

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

[0020] Examples of monofunctional epoxy resin compounds include 2-ethylhexyl glycidyl ether, butyric acid glycidyl ether, phenyl glycidyl ether, t-butyl glycidyl ether, Includes o-cresyl glycidyl ether and nonylphenol glycidyl ether .

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

[0022] Preferably, the epoxy resin compound is N,N-diglycidylaniline, 3,4-epoxy Cyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 4,4' -Di(1,2-epoxyethyl)biphenyl, 4,4'-di(1,2-epoxyethyl) Diphenyl ether, bis(2,3-epoxycyclopentyl) ether, triglyceride isocyanurate, triglycidyl-p-aminophenol, triglycidyl-p-amino Aminodiphenyl ether, tetraglycidyldiaminodiphenylmethane, bis[4-(glycidyl (glycidyloxy)phenyl]methane, tetraglycidyldiaminodiphenyl ether, Tetrakis(4-glycidyloxyphenyl)ethane, N,N,N',N'-tetraglycidyl Diglycidyl-diaminophenyl sulfone, bisphenol A diglycidyl ether, bisphenol Epoxy resin, epoxy phenol novolac resin, epoxy cresol novolac epoxy resins, spiro ring-containing epoxy resins, hydantoin epoxy resins or combinations thereof It is.

[0023] Epoxy resin compounds are further epoxy compounds with phenols such as bisphenol. One example is the condensation of diglycidyl ethers of oligomers. Another example is the condensation of bisphenol A with bisphenol A diglycidyl ether. In this study, we used a different phenol than that used to derive the epoxy compound. For example, tetrabromobisphenol A can be converted into bisphenol A diglycidyl ether. It can be condensed with glycidyl ethers to form halogen-containing oligomeric diglycidyl ethers. can.

[0024] The epoxy resin compound may be 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. Differential Scanning Calorimetry (DSC), Dynamic Mechanical Analysis (DMA), or ASTM E28-67, A STM E28-99, ASTM D36, ASTM D6493-11 and ISO The epoxy resins may be determined by the ring and ball test method as described in 4625. The compound may be a liquid or a softened solid at room temperature. Thus, in some embodiments, In this case, the epoxy resin compound has a softening point of less than 25°C.

[0025] The epoxy resin hardener is a diamine compound, preferably m-phenylenediamine, p-phenylenediamine, 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 Diphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-methylenebis(2,6-diethylaniline), 4,4'-methylene dianiline, diethyltoluenediamine, 4,4'-methylenebis(2,6-dimethyl aniline), 2,4-bis(p-aminobenzyl)aniline, 3,5-diethyltoluene -2,4-diamine, 3,5-diethyltoluene-2,6-diamine, m-xylylenediamine amine, p-xylylenediamine, diethyltoluenediamine or combinations thereof, More preferably, it may be 4,4'-diaminodiphenyl sulfone. is 0.5 to 50 wt%, preferably 2.5 to 25 wt%, based on the total weight of the curable composition. %, and more preferably 5 to 15 wt % of the curing agent.

[0026] The curable epoxy composition optionally includes a curing catalyst. The term "curing catalyst" refers to the type of agent whose role in the curing of epoxy compounds is as a curing agent, accelerator, These include compounds variously described as acting as catalysts, cocatalysts, or the like. The amount of solvent will depend on the type of compound and the identity and amounts of the other components of the composition. For example, the curable epoxy composition may be 0.5 to 5 based on the total weight of the curable composition. 0 wt%, preferably 2.5 to 25 wt%, more preferably 5 to 15 wt% of the hardened catalyst. The catalyst may include a solvent.

[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)benzophenone dianhydride 2,2-bis[4-(2,3-dicarboxyphenoxy)diphenylsulfone dianhydride 4,4'-bis(2,3-dicarboxyphenoxy)phenyl]propane dianhydride xyphenoxy)diphenyl ether dianhydride, 4,4'-bis(2,3-dicarboxy phenoxy)diphenyl sulfide dianhydride, 4,4'-bis(2,3-dicarboxyf 4,4'-Bis(2,3-dicarboxyphenoxy)benzophenone dianhydride ) Diphenylsulfone dianhydride, 4-(2,3-dicarboxyphenoxy)-4'-(3 ,4-dicarboxyphenoxy)diphenyl-2,2-propane dianhydride, 4-(2,3 -dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxylic acid Diphenyl sulfide dianhydride, 4-(2,3-dicarboxyphenoxy) 4'-(3,4-dicarboxyphenoxy)benzophenone dianhydride, 4-(2, 3-Dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl Sulfone dianhydride, 4,4'-(4,4'-isopropylidenediphenoxy)bis(anhydride Phthalic acid), 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 4,4 '-Oxydiphthalic anhydride, Benzophenone-3,3',4,4'-tetracarboxylic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride or similar Includes:

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

[0029] The curing catalyst may be a bicyclic anhydride. Examples of bicyclic anhydride compounds include methyl-5-nor Bornene-2,3-dicarboxylic anhydride, cis-5-norbornene-endo-2,3 -dicarboxylic acid anhydrides or the like.

[0030] Other curing catalysts include benzotriazoles; triazines; piperazines; 1-methylisothiazolyl; Imidazoles such as midazole; 4-diazabicyclo(2,2,2)octane, diaza Cyclic amidines such as bicycloundecene, 2-phenylimidazoline or similar N,N-dimethylaminopyridine; sulfamidate; or a combination thereof It is a monocyclic compound.

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

[0032] The functionalized polyetherimides are characterized by the presence of functionalized polyetherimides as determined by nuclear magnetic resonance spectroscopy. 50 to 1,500 microequivalents per gram of dimethyl amide, preferably 50 to 1,000 microequivalents per gram and more preferably, the total reactive end group concentration is 50 to 750 microequivalents / gram. Exemplary C 1-40 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 refers to a polymer that is a polymer that is a part of another polymer or prepolymer. interact with the polymer to promote the formation of a crosslinked network through chemical or physical bonds during curing. morphology that can promote and / or contribute to providing toughness to the cured thermoset polymer is a group capable of promoting the formation of phase-separated polyetherimide domains having The reactive end groups are attached to atoms of the polyetherimide chain as chain end groups.

[0034] The total reactive end group concentration ranges from 50 to 1,500 microequivalents / µg of functionalized polyetherimide. grams (μeq / g), preferably 50 to 1,000 μeq / g, more preferably 50 to 1,000 μeq / g. The end group concentration is 750 μeq / g. The end group concentration can be determined by various titration and analysis methods well known in the art. In some embodiments, the concentration of end groups can be analyzed by nuclear magnetic resonance (NMR) or optical spectroscopy. It can be determined by resonance spectroscopy.

[0035] The concentration of end groups can be analyzed by various titration and spectroscopic techniques well known in the art. Spectroscopic techniques include infrared, nuclear magnetic resonance, Raman spectroscopy and fluorescence. Examples of this are J. A. Kreuz, et al., and J. Pol y.Sci.Part A-1, vol. 4, pp. 2067-2616 (1966) An example of a titration method is described in YJ Kim, et al., Ma Cromolecules, vol. 26, pp. 1344-1358 (1993) Derivatization of the polymer end groups has been described, for example, by KP Chan ( Chan) et al.,Macromolecules,vol.27,p.673 1 (1994) and J.S. Chao, Polymer Bull. ., vol. 17, p. 397 (1987). In some cases, it may be advantageous to improve the sensitivity of the measurement.

[0036] The polyetherimide may have more than 1, for example, 2 to 1000 or 5 to 500 or 10 ~100 formulas(1) [ka] wherein each R is independently the same or different and is a substituted or unsubstituted C 6-20 aroma Aromatic hydrocarbon groups, substituted or unsubstituted straight or branched chain C 4-20 Alkylene groups, substituted or unsubstituted is unsubstituted C 3-8 Cycloalkylene groups, particularly halogenated derivatives of any of the foregoing. Substituted or unsubstituted divalent C 1-40 In some embodiments, the structural unit is an organic group. In the above, R is expressed by the following formula (2): [ka] (In the formula, Q 1 -O-, -S-, -C(O)-, -SO2-, -SO-, -P(R a )(=O)-(wherein, 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 (perylene, fluoroalkylene group) or -(CH 10 ) z (wherein z is an integer from 1 to 4) In some embodiments, R is one or more divalent groups selected from the group consisting of m-fluoro, m-fluoro, and m-fluoro. p-phenylene or diarylylene sulfone, in particular bis(4,4'-phenylene bis(3,4'-phenylene)sulfone, bis(3,3'-phenylene) sulfone or a combination comprising at least one of the foregoing. At least 10 mole percent or at least 50 mole percent of the R groups are In other embodiments, the R group does not include a sulfone group.

[0037] Furthermore, in formula (1), T is -O- or a group of the formula -OZO- (wherein -O- or The divalent bond of the -OZO- group is in the 3,3', 3,4', 4,3' or 4,4' position. Z is 1 to 6 C 1-8 an alkyl group, 1 to 8 halogen atoms or Aromatic C optionally substituted with a combination including at least one of the following: 6-24 Monocyclic or Exemplary Z groups include those of the formula: 3) [ka] (In the formula, R a and R b are each independently the same or different and each independently represents a halogen atom. or monovalent C 1-6 For example, p and q each independently represent an alkyl group having an integer of 0 to 4. is an integer from 0 to 4, and X a is a bridging group that connects hydroxy-substituted aromatic groups and the bridging group and the hydroxy substituents of each C6 arylene group are C6 arylene groups relative to each other. The crosslinked groups include those which are ortho, meta or para (especially para) to the olefin group. Group X a is a single bond, -O-, -S-, -S(O)-, -S(O)2-, -C(O)- or is C 1-18 It may be an organic bridging group. 1-18 The organic bridging group may be a cyclic or acyclic aromatic It may be aromatic or non-aromatic and may contain halogens such as oxygen, nitrogen, sulfur, silicon or phosphorus. It may further contain heteroatoms. 1-18 The organic group has a C6 aryl group attached to it. The olefin group is a common alkylidene carbon or C 1-18 Each carbon atom of the organic bridging group is Specific examples of Z groups include those of formula (3a): [ka] (Wherein, Q is -O-, -S-, -C(O)-, -SO2-, -SO-, -P(R a ) (=O)-(wherein, R a is C 1-8 Alkyl or C 6-12 aryl) or -C y H 2y - (wherein y is an integer from 1 to 5) or its halogenated derivative (pe In certain embodiments, the divalent group is a fluoroalkylene group. Z is bisphenol A such that Q in formula (3a) is 2,2-isopropylidene. is derived from.

[0038] In one embodiment, in formula (1), R is m-phenylene, p-phenylene or wherein T is -OZO- (wherein Z is a group represented by the formula ( 3a) is a divalent radical of formula (1). Alternatively, R is m-phenylene, p-phenylene or is a combination containing at least one of the above, T is -OZO (wherein Z is a group of the formula (3a) is a divalent group, and Q is 2,2-isopropylidene. The material is available from SABIC under the trade name ULTEM. Alternatively, polyetherimides are Formula (1) (wherein at least 50 mole percent (mol%) of the R groups are bis(4,4 '-phenylene)sulfone, bis(3,4'-phenylene)sulfone, bis(3,3'- phenylene)sulfone or a combination containing at least one of the above, and the remaining R The group is p-phenylene, m-phenylene, or a combination comprising at least one of the foregoing. and Z is 2,2-(4-phenylene)isopropylidene, i.e., bisphenol and the copolymer may contain additional structural polyetherimide units, which are the A moieties, One example is available from SABIC under the trade name EXTEM.

[0039] In some embodiments, the polyetherimide is a copolymer, e.g., a copolymer of formula (1) ( In which at least 50 mol % of the R groups are of formula (2) 1 is -SO2-) and the remaining R groups are independently p-phenylene, m-phenylene, or combinations thereof. and Z is 2,2'-(4-phenylene)isopropylidene. It may be a trietherimide sulfone copolymer.

[0040] In some embodiments, the polyetherimide is a Additional structural imide 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 substituted. or unsubstituted C 6-20 Aromatic hydrocarbon groups, for example those of the formula [ka] (Wherein, W is a single bond, -O-, -S-, -C(O)-, -SO2-, -SO-, C1 -18 Hydrocarbylene group, -P(R a )(=O)-(wherein, R a is C 1-8 Alkyl or C 6-12 aryl) or -C y H 2y (wherein y is an integer from 1 to 5) or its halogenated derivatives (including perfluoroalkylene groups) The copolymer is optionally comprised of an imide unit of the formula (I), which is a valent linker. The mido units preferably comprise less than 20 mol % of the total number of units, more preferably the units 0 to 10 mol% of the total number of units, or 0 to 5 mol% of the total number of units, or 0 In some embodiments, the additional imide units may be present in an amount of up to 2 mol %. Not present in terimides.

[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 The formula (5 )C 4-40 of methods known to those skilled in the art, including the reaction of a bis-anhydride or its chemical equivalent. The polyetherimide copolymer can be prepared by either of the following methods: Aromatic bis(ether anhydrides) and additional bis(anhydrides) that are not bis(ether anhydrides pyromellitic dianhydride or bis(3,4-dicarboxyphenyl)sulfonyl A combination of dianhydrides may be used.

[0042] C 4-40 Illustrative examples of bis-anhydrides include 2,2-bis[4-(3,4-dicarboxyphenyl)-2,2-dihydro ... Phenoxy)phenyl]propane dianhydride (Bisphenol A dianhydride or BPADA Also known as 3,3-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane Propanedianhydride, 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)diphenylsulfone 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)diphenylsulfone dianhydride, 4-(2,3-dicarboxyphenoxy)diphenylsulfone dianhydride 4'-(3,4-dicarboxyphenoxy)diphenyl-2,2- Propanedianhydride, 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxy 4-(2,3-dicarboxyphenoxy)diphenyl ether dianhydride 4'-(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4- (2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)benzene Zofenone dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride and 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy) The different aromatic bis(ether anhydrides) Combinations may be used.

[0043] Exemplary C 1-40 Organic diamines include ethylenediamine, propylenediamine, hexaamine, Samethylenediamine, Polymethylated 1,6-n-Hexanediamine, Heptamethylenediamine amine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 1,1 2-Dodecanediamine, 1,18-Octadecanediamine, 3-Methylheptamethylenediamine Amines, 4,4-dimethylheptamethylenediamine, 4-methylnonamethylenediamine, 5-Methylnonamethylenediamine, 2,5-Dimethylhexamethylenediamine, 2,5- Dimethylheptamethylenediamine, 2,2-dimethylpropylenediamine, N-methyl- Bis(3-aminopropyl)amine, 3-methoxyhexamethylenediamine, 1,2-bi Bis(3-aminopropoxy)ethane, Bis(3-aminopropyl)sulfide, 1,4- Cyclohexanediamine, bis(4-aminocyclohexyl)methane, m-phenylenediamine Amines, 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)toluene, 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)sulfur , bis(4-aminophenyl)sulfide, bis(4-aminophenyl)sulfone ( Also known as 4,4'-diaminodiphenyl sulfone (DDS) and bis(4-amino C 1-40 The organic diamine is m-phenylenediamine. , p-phenylenediamine, 4,4'-diaminodiphenyl sulfone, 4,4'-oxy Dianiline, bis(4-(4-aminophenoxy)phenyl)sulfone or combinations thereof It may be a combination.

[0044] The functionalized polyetherimide comprises a polyetherimide unit of formula (1) and a cyclic alkyl group of formula (8) [ka] (In the formula, E is 2 to 100, 2 to 31, 5 to 75, 5 to 60, 5 to 15, or 15 to 4 0, and each R' is independently 1-13 monovalent hydrocarbyl group) Also included are poly(siloxane-etherimide) copolymers containing siloxane blocks. For example, each R' is independently an optionally halogenated group; C 1-13 Alkyl, C 1-13 a Lukoxi, C 2-13 Alkenyl, C 2-13 Alkenyloxy, C 3-6 Cycloalkane Lu, C 3-6 Cycloalkoxy, C 6-14 Aryl, C6-10 Aryloxy, C7 -13 Aryl alkyl, C 7-13 Arylalkoxy, C 7-13 Alkyl aryl or C 7-13 In some embodiments, the aryloxy group may be an alkylaryloxy group. In one embodiment, the chlorine is absent, and in another embodiment, the halogen is absent. The alkane block contains an R' group that has a minimal hydrocarbon moiety, such as a methyl group.

[0045] Poly(siloxane-imide) is prepared by the reaction of bis(anhydride) (6) and organic diamine (6) as described above. or from an organic diamine and a compound represented by the formula (9) [ka] (In the formula, R′ and E are as defined in formula (8), and R 4 are each independently C 2-C 20 Hydrocarbons, especially C2-C 20 Arylene, alkylene or arylene alkyl The polysiloxane diamine may be prepared from a mixture of polysiloxane diamines, each of which is a silane group. In R 4 is C2-C 20 is an alkylene group, and E is 5 to 100, 5 to 60, 5 to The diamine component has an average value of 15 or 15 to 40. 50, 10-90 mol%, or 20-50 mol%, or is 25-40 mol% of polysiloxane diamine (9) and 10-90 mol%, can contain 50-80 mol % or 60-75 mol % of organic diamine (3). Poly(siloxane-imide) copolymers can be block, random or graft copolymers. It may be a polymer.

[0046] Examples of specific poly(siloxane-imides) are described in U.S. Pat. Nos. 4,404,350 and 4,808,932. 686 and 4690997. In one embodiment, poly(siloxane) Poly(siloxane-ether imide) is a poly(siloxane-ether imide) and has the formula (10): [ka] (wherein R′ and E of the siloxane are as in formula (8), and R and Z of the imide are as in formula (8). is as in equations (2) and (3), and R 4 is R in equation (9). 4 Same as In a particular embodiment, the ether R of the phenylimide is phenylene, Z is a residue of bisphenol A, and R 4 n-p propylene, E is 2 to 50, 5 to 30, or 10 to 40, and n is 5 to 100. and each R' is methyl.

[0047] The relative amounts of polysiloxane units and imide units in a poly(siloxane-imide) are The selection will depend on the desired properties and is made using the guidelines provided herein. The poly(siloxane-imide) may be used in an amount of from 10 to 150 based on the total weight of the poly(siloxane-imide). Contains 50wt%, 10-40wt%, or 20-35wt% of polysiloxane units.

[0048] In some embodiments, the functionalized polyetherimide is a poly(siloxane-imide) copolymer. For example, in some embodiments, the functionalized polyetherimide is a poly (Siloxane-imide copolymer) free.

[0049] The optional organic compound contains at least two functional groups per molecule. The first functional group is , anhydrides, amines or combinations thereof, and the first functional group is reactive to a second For example, an organic compound having the formula (7) R c -L n -Q 2 -L n -R d (7) (In the formula, R c and R d are different and each independently represents -OH, -NH2, -SH or or an anhydride group, a carboxylic acid or a carboxylic acid ester). In the formula (I), each L is the same or different and each L is independently substituted or unsubstituted C 1-1 0 alkylene or substituted or unsubstituted C 6-20 Arylene, Q 2 is -O-, -S-, -S(O)-, -SO2-, -C(O)- or C 1-20 Organic bridging groups, preferably or substituted or unsubstituted C 1-10 Alkylene or substituted or unsubstituted C 6-20 Ants where each n is independently 0 or 1. Formula (7) is understood by those of ordinary skill in the art to As one would expect, it should be understood that the invention is limited to chemically feasible organic compounds. For example, the organic compound cannot be HO-O-OH, and therefore, in formula (7), Q is -O-. In some cases, n is 1.

[0050] Exemplary organic compounds include para-aminophenol, meta-aminophenol, ortho -Aminophenol, 4-hydroxy-4'-aminodiphenylpropane, 4-hydroxy 4-amino-4'-hydroxydiphenylsulfone , 4-hydroxy-4'-aminodiphenyl ether, 2-hydroxy-4-aminotoluene Ene, 4-aminothiophenol, 3-aminothiophenol, 2-aminothiophenol phthalic anhydride, 4-hydroxyphthalic anhydride, 3-hydroxyphthalic anhydride, 6-amino-2- Naphthol, 5-amino-2-naphthol, 8-amino-2-naphthol and 3-amino No-2-naphthol or similar. Use of one or more organic compounds. can be done.

[0051] The functionalized polyetherimide can be prepared by reacting the functionalized polyetherimide under reaction conditions effective to provide the functionalized polyetherimide. Substituted or unsubstituted C under the condition 4-40 Bis-anhydrides and substituted or unsubstituted C 1-40 Organic Zia It can be prepared by reacting amine with, optionally, an organic compound. For example, , functionalized polyetherimides are prepared by polycondensation of bis-anhydrides and organic diamines. Alternatively, the reaction can be carried out in a manner effective to provide a polyetherimide oligomer. Substituted or unsubstituted C under conditions 4-40 Bis-anhydrides and substituted or unsubstituted C 1-40 Organic and polymerizing the polyetherimide under conditions effective to provide a functionalized polyetherimide. and melt mixing the polyetherimide oligomer with an organic compound.

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

[0053] The bis-anhydride and the organic diamine may be used in substantially equimolar amounts or in a molar excess of the amine or can be reacted with a bis-anhydride. The term "substantially equimolar amount" means 0.9 to 100% by weight of the compound. 1.1, preferably 0.95 to 1.05, more preferably 0.98 to 1.02. The molar ratio of bis-anhydride to amine is 26 or less. 20 or less, more preferably 15 or less, or 2 to 26, preferably 5 to 26, more preferably The molar ratio of the bis-anhydride to the organic diamine is generally 10 to 26.

[0054] The effective conditions for obtaining polyetherimide are a temperature of 170 to 380°C and 1 Solid content of up to 50 wt%, preferably 20 to 40 wt%, 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, are used to prepare polyolefins. Exemplary compounds include monofunctional aromatic anhydrides, such as phthalic anhydride, Aliphatic monoanhydrides such as water, maleic acid, or monofunctional aldehydes, ketones, esters, isomers, etc. Aromatic monoamines such as socyanates, anilines, or C1-C 18 Linear or cyclic The amount of endblocking agent that can be added depends on the desired amount of chain length. Dependent on the terminating agent, e.g., the molar number of endblocking agent and diamine or bis-anhydride reactants, greater than 0 to 10 mole percent (mol%), or 0.1 to 10 mol%, based on In certain embodiments, an additional end-capping agent is not used. do not have.

[0056] In some embodiments, the functionalized polyetherimide is a More than 0.05 ppm by weight based on the total weight, preferably more than 100 ppm, more preferably more than 5 00 ppm, and even more preferably, 1,000 ppm by weight of non-reactive end groups. .

[0057] An imidization catalyst may be present during the reaction. Exemplary imidization catalysts include aryl phosphi Sodium phosphate, guanidinium salt, pyridinium salt, imidazolium salt, tetra(C7 -24 arylalkylene)ammonium salts, dialkylheteroalicyclic ammonium salts, Bis-alkyl quaternary ammonium salts, (C 7-24 Aryl alkylene) (C 1-16 a alkyl)phosphonium salts, (C 6-24 Aryl)(C 1-16 (alkyl)phosphonium The anionic component of the salt is not particularly limited. Not limited, for example, chloride ion, bromide ion, iodide ion, sulfate ion, phosphate ion ions, acetate, maculate, tosylate and the like The catalytically active amount of a catalyst can be determined by one of ordinary skill in the art without undue experimentation. For example, greater than 0 to 5 mol % based on the moles of organic diamine, or 0. 0.1 to 2 mol%, or 0.1 to 1.5 mol%, or 0.2 to 1.0 mol% It is possible.

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

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

[0060] The functionalized polyetherimides were analyzed by gel permeation chromatography using polystyrene standards. - 5,000 to 45,000 grams per mole (g / mol) as determined by gel permeation chromatography (GPC), Preferably, it is 10,000 to 45,000 g / mol, more preferably, it is 15,000 to 35 Weight average molecular weight (M w ) Polydispersity (PDI) ) is less than 4.5, preferably less than 4.0, more preferably less than 3.0, even more preferably or may be less than 2.8.

[0061] The functionalized polyetherimide has a diameter of 1 to 1,000 micrometers (μm), preferably A maximum absolute value of 1 to 500 μm, more preferably 1 to 100 μm, and even more preferably 1 to 75 μm. The maximum absolute particle size can be determined by isolating the functionalized polyetherimide particles. The particle size is defined by the hole size of the sieve used to screen the particle and does not represent an average particle size.

[0062] The functionalized polyetherimide has a molecular weight of greater than 0.75, preferably greater than 0.9, and more preferably greater than 1. It can have an average reactive end group functionality of greater than 1, and even more preferably greater than 1.5. The average reactive end group functionality is determined by the number of hydroxyl, amino and tert-butyl groups per polyetherimide chain. and the average number of carboxylic acid end groups.

[0063] The functionalized polyetherimide has a melting point of greater than 155°C, preferably greater than 175°C, and more preferably greater than 1 Glass transition temperature (T g ) can be used. For example, T g ASTM 155 to 280°C as determined by differential scanning calorimetry in accordance with D3418, preferably The temperature may be preferably 175 to 280°C, and more preferably 190 to 280°C.

[0064] The functionalized polyetherimides are characterized by the presence of functionalized polyetherimides as determined by nuclear magnetic resonance spectroscopy. 0.5 to 5000 microequivalents per gram of dimethyl amide, preferably 0.5 to 1000 microequivalents per gram Amide-acid concentrations of 0.2 equivalents / gram, more preferably 0.5 to 500 microequivalents / gram may have the following structure:

[0065] The curable composition comprises less than 0.05 to 5.0 wt. % based on the total weight of the functionalized polyetherimide. 00 ppm by weight, preferably 0.05 to 1000 ppm by weight, more preferably 0.05 to Contains 500 ppm by weight of residual solvent, and even more preferably 0.05 to 250 ppm can be done.

[0066] The curable composition was used to prepare the functionalized polyetherimide. Based on the total weight of the product, each of them is 0.05 to 1,000 ppm by weight, preferably 0.05 to 1,000 ppm by weight. 750 ppm by weight, more preferably 0.05 to 500 ppm by weight of residual bis(anhydride) and May contain residual organic compounds.

[0067] The curable composition was used to prepare the functionalized polyetherimide. 0.05 to 3,000 ppm by weight, preferably 0.05 to 2,000 ppm by weight, based on the total weight of the product. 0 ppm by weight, more preferably 0.05 to 1,000 ppm by weight, and even more preferably Total residual bis-anhydrides, residual diamines and residual organic compounds of 0.05 to 500 ppm by weight It may include the content.

[0068] As used herein, "residual bis-anhydride" refers to a compound that is useful in the preparation of functionalized polyimides. Substituted or unsubstituted C remaining from 4-40 In this specification, bis-anhydride is used. As used herein, "residual organic compounds" refers to those compounds remaining from the preparation of a functionalized polyimide. As used herein, "residual diphenyl ether" refers to the organic compounds (if any) that "Amine" refers to the substituted or unsubstituted C groups remaining from the preparation of the functionalized polyimide. 1-40 It means an organic diamine.

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

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

[0071] The curable composition may contain from 0.3 to 500 ppm by weight, based on the total weight of the curable composition. The anion may include up to 250 ppm by weight. Examples of the anion include phosphate ion, Nitrate, nitrite, sulfate, bromide, fluoride and chloride ions These may include, but are not limited to, on.

[0072] The curable compositions may further comprise additives for polyetherimide compositions generally known in the art. However, the additive(s) may be present in order to improve the desired properties of the composition. , and particularly should be selected so as not to significantly adversely affect 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, release agents, antistatic agents, storage stabilizers, antiozonants, optical stabilizers, thickeners, conductive shadow agents Acoustic agents, radiation blocking agents, nucleating agents, anti-fog agents, antibacterial agents, metal deactivators, colorants, surface effect additives, Radiation stabilizer, flame retardant, anti-drip agent, fragrance, adhesion promoter, flow improver, coating The additives include one or more epoxy resins and different polymers or combinations thereof. The total amount of the additive composition is 0.001 to 20 wt % based on the total weight of the curable composition, or Alternatively, the content may be 0.01 to 10 wt %.

[0073] The functionalized polyetherimide is further processed to obtain a powder having a specified maximum particle size. Processing can include grinding, milling, cryogenic grinding, sieving and combinations thereof. The treatment does not affect the weight average molecular weight, PDI and reactive end group content. The treated polyetherimide powder exhibits these characteristics consistent with functionalized polyetherimides. The processed powder can be sieved to obtain the maximum particle size desired. In an embodiment, the maximum particle size is 1,000 micrometers. 1 to 1.0, as determined by the pore size of the sieve used to isolate the oxidized polyetherimide. 00 micrometers, preferably 1 to 500 micrometers, more preferably 1 to 1 00 micrometers, and even more preferably 1 to 75 micrometers maximum absolute particle size .

[0074] The functionalized polyetherimides can be combined, e.g., blended, with other polymers to form polyetherimides. Polymer blends can also be produced and the polymer blends can be used in curable epoxy compositions. Polymers that can be used include polyacetal, poly(meth)acrylate ... ) Acrylates, poly(meth)acrylonitriles, polyamides, polycarbonates , polydiene, polyester, polyether, polyetheretherketones, polyether Terimide, polyethersulfone, polyfluorocarbon, polyfluorochlorocarbon Polyimides, poly(phenylene ethers), polyketones, polyolefins, polyoxyethylenes Sasols, polyphosphazenes, polysiloxanes, polystyrenes, polysulfones, poly Urethane, polyvinyl acetates, polyvinyl chlorides, polyvinylidene chlorides, polyvinyl ethers esters, polyvinyl ethers, polyvinyl ketones, polyvinyl pyridines, polyvinyl pyridines Rolidones and their copolymers, such as polyetherimide siloxane, ethylene These include vinyl acetates, acrylonitrile butadiene styrene or combinations thereof. Preferably, the functionalized polyetherimide is a polyarylate, a polyamide, a polyimide, Polyetherimide, poly(amide imide), poly(aryl ether), phenoxy resin Poly(aryl sulfone), poly(ether sulfone), poly(phenylene sulfone) ), poly(ether ketone), poly(ether ether ketone), poly(ether ketone) ketones), poly(aryl ketones), poly(phenylene ethers), polycarbonates, Carboxyl-terminated butadiene-acrylonitrile (CTBN), amine-terminated butadiene- Acrylonitrile (ATBN), Epoxy-terminated butadiene-acrylonitrile (ETBN ), core-shell rubber particles, or a combination thereof. can be done.

[0075] Also provided is a method for the preparation of a curable epoxy composition, comprising the steps of: The resin composition is combined with a functionalized polyetherimide at a temperature of 70 to 200°C and reacted. providing a reaction mixture; and adding an epoxy resin hardener and, optionally, a curing catalyst to the reaction mixture. and b) reacting the insoluble particles and the epoxy to provide a curable epoxy composition. The functionalized polyimide is provided as particles that are dissolved in the resin mixture by heating prior to adding the polyimide hardener. A thermoplastic polymer (or polymers) containing polyetherimide is added to an epoxy resin composition. The thermoplastic polymer(s) can be added to the high temperature matrix. Once substantially dissolved in the resin precursor (i.e., the epoxy resin blend), the precursor is cooled. The remaining ingredients (e.g., epoxy hardeners, insoluble thermoplastics, other additives) can be mixed together. additives or combinations thereof) are added.

[0076] The method for producing an epoxy thermoset comprises polymerizing and crosslinking a curable epoxy composition. Curing can be by any method known in the art, such as heating, UV-visible radiation, etc. This is accomplished using radiation, microwave radiation, electron beam, gamma radiation, or a combination thereof. It is possible.

[0077] The cured epoxy thermoset may be heated to a temperature between 50 and 300°C, preferably between 150 and 300°C, more preferably between 150 and 300°C. Preferably, the temperature is 190 to 300°C, more preferably 210 to 300°C or even more preferably Preferably, the glass transition temperature is 230 to 300°C.

[0078] The cured epoxy thermoset has a hardness of 150 g / mol / L as measured in accordance with ASTM D5045. Joules per square meter (J / m 2 ) or more, preferably 200 J / m 2 More preferably, is 250 J / m 2 The fracture toughness of the steel sheet can be equal to or higher than that of the steel sheet.

[0079] Cured epoxy thermosets are made with methylene chloride, tetrachloroethane, and dichlorobenzene. , chloroform, dichloroethane, methyl ethyl ketone, acetone, methyl isobutyl ketone , methyl isopropyl ketone, ethyl acetate, N-methylpyrrolidone, dimethylacetone Resistance to amides, dimethylformamide, dimethylsulfoxide, or combinations thereof Cured epoxy thermosets can be used in a wide variety of applications, including hydraulic fluids, jet fuel, and oil-based applications. Resistant to less aggressive solvents including gasoline, alcohol and other organic solvents As used herein, "solvent resistance" refers to the ability of a cured epoxy to The oxy thermoset is allowed to stand for more than 30 minutes, preferably more than 24 hours, more preferably 2 to 7 days. Substantial change in the thermoplastic material observed by microscope when immersed in a solvent at 20-25°C It means no reduction (no etching).

[0080] Epoxy thermosets are used in composites (e.g., carbon and glass fiber reinforcements). composites, foams, fibers, layers, coatings, encapsulants, adhesives, sealants Various types of materials, including casings, sizing resins, prepregs, casings, parts or combinations thereof, Epoxy thermosets can be used in a variety of forms for a variety of purposes. Aerospace, Automotive, Rail, Marine, Electronics, Industrial, Oil & Gas, Sporting Goods, Infrastructure, energy, and improved toughness, higher heat resistance and solvent resistance Many articles can be produced in other industries where good resistance is required. In the above, the composite material may be a glass fiber-based composite material, a carbon fiber-based composite material, or the like. It is a combination of these.

[0081] The method of producing the composite includes the steps of impregnating a reinforcement structure with a curable epoxy composition; A step of partially curing the curable composition to produce a prepreg, and a step of stacking a plurality of prepregs. and layering the curable epoxy composition with an auxiliary comonomer and, optionally, and optionally one or more additional additives.

[0082] Exemplary applications of the curable epoxy compositions include, for example, acid bath vessels; neutralization tanks; aircraft parts; products; bridge girders; bridge decks; electrolytic cells; exhaust stacks; scrubbers; sports equipment; stairs; walkways; bonnets Automotive exterior panels such as seats and trunk lids; floor pans; air scoops; heater ducts Pipes and ducts including fans; industrial fans, fan housings and blowers; industrial mills Kisers;Boat Hulls & Decks;Wharf Fenders;Tiles & Coatings;Architectural Panels;Office Machine housings; trays including cable trays; concrete modifiers; dishwashers and Storage parts; Electrical seals; Electrical panels; Electrical refining tanks, water softener tanks, fuel tanks and Tanks and tank linings, including various filament wound tanks; equipment;garage doors;grilles;protective body gear;bags;outdoor motor vehicles;pressure tanks;pressure Lint circuit boards; optical waveguides; radomes; railroad parts such as tank cars; hopper car covers ;Car doors;Truck bed liners;Satellite dishes;Signs;Solar energy Energy panels; telephone switch housings; tractor parts; transformer covers; fenders, Truck parts such as tunnels, bodies, cabs and beds; ground insulation, turn insulation Insulation materials for rotating machinery, including insulating materials and phase-separating insulating materials; rectifiers; core insulation materials and cords and Racing tape; drive shaft couplings; propeller blades; missile parts; rocket motor cases ;wing section;sucker rod;fuselage section;wing skin and flare;engine nacelle;cargo port;teni Slatquets; golf club shafts; fishing rods; skis and ski poles; bicycle parts ;Transverse leaf springs;Pumps such as automotive smog pumps;Electric cable joysticks electrical components, potting materials and tools; wirewound and high density multi-element assemblies; Machinery sealing; battery cases; resistors; fuses and thermal cutoffs Devices; Coatings for printed wiring boards; Capacitors, transformers, crankcase heaters Cast products such as coils, capacitors, resistors and semiconductors; small molded electronic components as a replacement for steel in chemical processing, pulp and paper, power generation and wastewater treatment; scrubbing Towers; structural members, gratings and pulled parts for structural applications including guardrails; swimming pools, swimming Pool slides, hot tubs and saunas; drive shafts for under hood applications; reproductions Dry toner for aircraft;Marine tools and composites;Heat shields;Submarine hulls;Prototype generation; Development of experimental models;Laminated trim;Drilling fixture;Joining fixture;Inspection fixture;Industrial metal forming mold;Aviation Aircraft stretch blocks and hammer moulds; vacuum forming tools; production and assembly areas; Clean rooms, machine shops, control rooms, laboratories, parking lots, freezers, coolers and outdoor storage Flooring, including landing floors; Conductive compositions for antistatic applications; For decorative floors; Expansion joints for bridges; Structural components Injectable mortar for repairing and repairing cracks in concrete; grouting for tiles Machine rails; metal dowels; bolts and posts; repair of oil and fuel storage tanks; has many other uses.

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

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

[0085] viscosity Using the ARES G2 Strain Controller Rheometer, ASTM D4440- According to 1, a disposable 8 mm plate was used to create a constant gap of 1 mm and a constant Viscosity measurements were performed at a frequency of 15 rad / s and a strain of 10%. The material was equilibrated at 140°C. The sample was packed between the two plates of the parallel plate rheometer. The complex viscosity was measured as a function of temperature as the sample cooled to 70°C.

[0086] Fracture toughness After curing, the samples were removed from the mold and milled to obtain a substantially flat and uniform surface. The sample castings were dry sanded on both sides with 600 grit sandpaper to a final thickness of 8 mm. The razor tap method was used to apply a small impact force to a sharp razor blade placed on the test sample. By applying a pressure to the notch, a sharp pre-crack was generated at the tip of the notch. The sample was attached to the labile and the openings were measured using a universal testing machine (Zwick Z2.5). The samples were tested under mode I loading. The load was applied at 1 mm / min under displacement control. The fracture surfaces after the test were imaged under an optical microscope and tapped according to ASTM D5045. The length of the crack generated by the method was measured. The length of the crack was measured at five equal intervals on the fracture surface. , and averaged to obtain the average crack length for each specimen. The fracture load was determined according to the specimen geometry and the average The crack length was recorded and used to measure the epoxy material in accordance with ASTM D5045. Fracture toughness (K IC) was calculated. The critical strain energy release rate (G IC ) was also calculated.

[0087] Glass transition temperature Differential scanning according to ASTM D3418 using a TA Q1000 DSC instrument Calorimetry (DSC) was performed. The temperature was increased from 40°C to 325°C at 20°C / min under nitrogen atmosphere. The sample was scanned at a heating rate of 100°C. The glass transition temperature (T g ) and Melting temperature (T m ) was decided.

[0088] SEM images of the samples were taken using a JEOL JSM-IT500 HR scanning electron microscope. SEM images were taken at an operating voltage of 10-15 kV under secondary electron mode. Prior to oxidation, the samples were air cleaned and sputter coated with 10 nm gold / palladium. Use secondary and backscattered electron detectors for morphological and Z-contrast imaging. Used.

[0089] Table 2 shows the cure profile of the samples. The times are the equilibrium time at the specified temperatures. After the final step, the heating step is usually repeated to minimize thermal stress. The sample was then slowly cooled to ambient temperature. [Table 2]

[0090] Example 1 Synthesis of amine-terminated PEI oligomers An oven equipped with a mechanical stirrer, nitrogen adapter, and Dean-Stark condenser was used. Into a dry 500 mL three-neck round-bottom flask, add 50.06 grams (g) of BPA-DA (9 4.6 mmol), 14.6 g of mPD (134.5 mmol) and 200 g of oDC. B was added. The oil bath temperature was increased to 180° C. and the reaction was refluxed at this temperature for 3-4 h. A small sample was removed for molecular weight determination. Target M w To obtain the DA or was stoichiometrically corrected with amine. w Once this is achieved, the reaction mixture is cooled to room temperature (approximately 25°C). Then 150 g of DCM was added to it and the contents were mixed vigorously while stirring. The oligomer solution was obtained by adding 800-850 mL of MeOH to a 2 L beaker. The ligomer solution was added slowly under high shear mixing conditions, resulting in the formation of a precipitate. The resulting fine off-white powder was filtered and washed with MeOH (2×50 mL). The solid was dried in a vacuum oven at 130-135°C for 12 hours to obtain a mass of 5,766 g / mol. M of l w and amine-terminated PEI as a powder with a polydispersity index (PDI) of 2.37. Oligomers were obtained.

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

[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 has an M of 4,598 g / mol w and hydroxy-terminated PEI with a PDI of 2.32. The same procedure was followed as in Example 1, except that oligomer powder was given.

[0093] Example 4 Synthesis of hydroxy-terminated PEI oligomers 52.20 g of BPA-DA (97.47 mmol), 8.97 g of mPD (82.9 5 mmol), 3.50 g of PAP (32.07 mmol) and 200 g of oDCB , M of 9,214 g / mol w and hydroxy-terminated PEI with a PDI of 2.42. The same procedure was followed as in Example 1, except that ligomer powder was given.

[0094] Example 5 Preparation of additive-free epoxy castings Liquid epoxy compounds (e.g., TGAP, TGDDM, BFDGE, or DGEBA) To prepare an epoxy casting containing no thermoplastic additives, the following procedure was used: 80 g of liquid epoxy was placed in a 500 mL reaction kettle equipped with a mechanical stirrer and a N2 gas inlet. The kettle was purged with N2 gas for about 5 minutes and then immersed in an oil bath maintained at 140°C. After heating for about 15 to 20 minutes under N2 atmosphere, 24 g (15% excess ethylene per NH group) was The DDS (in liquid epoxy) 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 N This process was repeated for a total of three cycles, and the resulting mixture was then purged for 14 The silicone was poured into a preheated silicone mold in a 0°C oven. The curing procedure in Table 2 was followed. The sample was then cured.

[0095] Example 6 Preparation of epoxy castings containing additives Liquid epoxy compounds (e.g., TGAP, TGDDM, BFDGE, or DGEBA) and thermoplastic additives (e.g., PEI oligomers, PEI or PES of Examples 1 to 4). The following procedure was used to prepare epoxy castings containing U. , 15, 30 or 50 wt% 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 complete dissolution in the epoxy compound (as determined by visual inspection by the formation of a transparent mixture), the obtained DDS was added to the epoxy mixture. The remaining steps were carried out according to the method of Example 5. Ta.

[0096] To increase solubility in liquid epoxy compounds, thermoplastic additives were prepared as powders and A 0.00 μm sieve was used to remove larger particles. The thermoplastic resins of Examples 1 to 4 required 45 to 60 minutes to dissolve PESU. It was shown that the additive dissolved in the liquid epoxy compound in about 20 to 25 minutes. For 4, the nature of the reactive functional group (amine vs. hydroxy) and the molecular weight (5 vs. 10 kg / mol) did not significantly change 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 were M of 19 g / mol w and amine-terminated PEI oligomer powder with a PDI of 2.42 was given.

[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 were M of 80g / mol w and amine-terminated PEI oligomer powder with a PDI of 2.36 was given.

[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) was ), 13.84 g of mPD (127.99 mmol) and 230 g of oDCB were mixed for 32 , 968g / mol M w and an amine-terminated PEI oligomer with a PDI of 2.35. Powder was given.

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

[0101] Viscosity of curable epoxy compositions and the effects of DGEBA and thermoplastic additives (0-50 wt %) hardened samples are shown in Table 5. [Table 4]

[0102] Viscosity of curable epoxy compositions and TGAP and thermoplastic additives (0-50 wt%) The critical strain energy release rates of the hardened samples are shown in Table 6. [Table 5]

[0103] Viscosity of curable epoxy compositions, critical strain energy release rate and TG of cured samples T of cured samples with DDM and thermoplastic additives (0–50 wt%) g is shown in Table 7. [Table 6]

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

[0105] Sump samples derived from the curable epoxy compositions containing the thermoplastic additives of Examples 2 and 4 The copolymer exhibits significant improvements in fracture toughness, e.g., compared to curable compositions without thermoplastic additives. The thermoplastic additives of Examples 2 and 4 showed an increase in fracture toughness of up to 160%. The fracture toughness of the pulley decreased with increasing addition amount until it reached a maximum value at 30 wt% addition. The results were improved by increasing the additive amount to 50 wt% (except for the BISF epoxy formulation). Overall, the thermoplastic additives in Examples 2 and 4 did not further improve fracture toughness. The samples containing the agent showed a higher thermal conductivity than the samples using the thermoplastic additives of Examples 1 and 3. A greater improvement in fracture toughness was observed.

[0106] When the molecular weight of the thermoplastic additive is lower, the mechanical properties of the cured thermoset, especially the fracture toughness, Surprisingly, the thermoplastic additives of Examples 2 and 4 are At 30 wt% additive loading, the DGEBA and TGDDM cured samples showed higher molecular weights. DGEBA and TGDDM cured samples containing 30 wt% PESU had a critical strain energy release rate greater than

[0107] As shown in Table 7, the cured samples containing either the thermoplastic additive of Examples 2 or 4 T g is the T of the cured samples containing PEI or PESU g All of the San Single pull T g These results suggest that the fluororesin may be useful in applications involving long-term exposure to high temperatures. This shows that functionalized polyetherimides can be used in curable epoxy compositions. The incorporation of lower molecular weight thermoplastics improves the thermal performance of the resulting cured epoxy thermoset. Surprisingly, DSC measurements show that the 5% reduction in EDTA is achieved without compromising high temperature performance. or amine-terminated or hydroxyl-terminated PEI oligomers having a molecular weight of 10 kg / mol. This shows that it is possible to blend TGDDM resin with glycerol.

[0108] Figure 1 shows the fracture toughness of the thermoplastic polymer-reinforced TGDDM epoxy sump. The SEM micrograph of the fracture surface of the polymer is shown. At a PEI content of 15 wt%, clear phase separation (spherical) was observed. In addition, the cross-linked epoxy bonded by PEI was observed in the SEM image of the fracture surface. Also shown here are the phase inversion regions in which the spherical particles contain. The cured compositions of Examples 2 and 4 are Smaller thermoplastic domains (0.1-0.2) uniformly distributed in the epoxy matrix. Without being limited by theory, the P in Examples 2 and 4 The EI oligomer reacts with the epoxy resin and is incorporated into the epoxy network, thereby Thus, the average molecular weight between the crosslinks is increased. Surprisingly, the characteristics of Examples 1 and 3 This was not observed for the cured compositions. Therefore, the thermoplastic additives of Examples 2 and 4 The higher fracture toughness of the samples containing the additive can be explained by this difference in phase morphology. Furthermore, the molecular weight increases to 33,000 g / mol and the loading level increases to 30 wt%. As the temperature rises, a two-phase morphology with intermittent bicontinuous phases appears at molecular weights of 26,000 g / mol and This was observed for both the 30,000 and 30,000 g / mol amine-terminated PEI oligomers.

[0109] The chemical resistance of the cured thermosetting material was evaluated by immersing it in methylene chloride for 30 minutes to 1 hour. Figure 2 shows SEM images of the surface before and after exposure to methylene chloride. For the pull, the etched area was removed from the surface because the PEI was dissolved in methylene chloride. The cured thermosets containing the PEI oligomers of Examples 2 and 4 were observed to be Inspection and SEM imaging showed no surface damage, indicating improved chemical resistance.

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

[0111] Aspect 1. One or more epoxy groups each independently having at least two epoxy groups per molecule. an epoxy resin composition comprising an epoxy resin, an epoxy resin curing agent, and optionally a curing catalyst; , substituted or unsubstituted C 4-40 Bis-anhydrides and substituted or unsubstituted C 1-40 Organic Diamine and optionally an organic compound, The functionalized polyetherimide is present in an amount of 5 to 75 parts by weight per 100 parts by weight of the resin composition. and a functionalized polyetherimide having the formula (C 1-4 0 hydrocarbylene)-NH2, (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, a carboxylic acid ester or and a combination thereof, wherein the functionalized polyetherimide is 50% by weight of the functionalized polyetherimide. ~1,500μeq / g, preferably 50~1,000μeq / g, more preferably 50 and the polyetherimide composition has a total reactive end group concentration of about 750 μeq / g. 0.05 to 1,000 ppm by weight, preferably 0.05 to 1,000 ppm by weight, based on the total weight of the terimide composition. Residual organic diazonium salts of 0.05 to 500 ppm by weight, more preferably 0.05 to 250 ppm by weight The functionalized polyetherimide having an amine is precipitated from solution using an organic antisolvent or The organic compound obtained by devolatilization contains at least two functional groups per molecule, and the first The functional groups are reactive to anhydride groups, amine groups, or a combination thereof, and the first functional The curable epoxy composition, wherein the functional group is different from the second functional group.

[0112] Aspect 2. The curable epoxy composition of aspect 1, wherein the epoxy resin composition is a curable epoxy resin composition as described herein. A curable epoxy composition comprising a compound of formula (1) as described herein.

[0113] Aspect 3. The curable epoxy composition of aspect 1 or 2, wherein the epoxy resin hardener is , diamine compounds, preferably m-phenylenediamine, p-phenylenediamine, o- Phenylenediamine, 3,3'-oxydianiline, 3,4'-oxydianiline, 4, 4'-Oxydianiline, 1,3-Bis(4-aminophenoxy)benzene, 1,3-Bi (3-aminophenoxy)benzene, 4,4'-diaminodiphenyl sulfone, 3,3 '-Diaminodiphenyl sulfone, 3,4'-Diaminodiphenyl sulfone, 4,4'- Methylenebis(2,6-diethylaniline), 4,4'-methylenedianiline, diethyl Toluene diamine, 4,4'-methylenebis(2,6-dimethylaniline), 2,4-bi p-aminobenzylaniline, 3,5-diethyltoluene-2,4-diamine, 3 ,5-Diethyltoluene-2,6-diamine, m-xylylenediamine, p-xylylene diamine, diethyltoluenediamine or a combination thereof, more preferably 4,4'- A curable epoxy composition which is a diaminodiphenyl sulfone.

[0114] Aspect 4. The curable epoxy composition of any one of aspects 1 to 3, comprising a functionalized polyether. The trietherimide has a molecular weight of 5,000 to 45,000 g / mol as determined by GPC, preferably Preferably, the molecular weight is 10,000 to 45,000 g / mol, more preferably, 15,000 to 35, 000 g / mol; weight average molecular weight of 1 to 1,000 micrometers, preferably 1 to 1,000 micrometers 500 micrometers, more preferably 1 to 100 micrometers, and even more preferably or maximum absolute particle size from 1 to 75 micrometers; reactivity per polyetherimide chain greater than 0.75, defined as the average number of end groups, preferably greater than 0.9, more preferably greater than 1.1 and even more preferably an average reactive end group functionality of greater than 1.5; Therefore, the temperature is 155°C to 280°C, preferably 175°C, as determined by differential scanning calorimetry. A glass transition temperature of 190°C to 280°C, preferably 190°C to 280°C; 0.5 to 5000 microequivalents per gram of functionalized polyetherimide, as determined by Preferably, the amount is 0.5 to 1000 microequivalents / gram, more preferably 0.5 to 500 microequivalents / gram. Amide-acid concentration in chloroequivalents / gram; 0.05 wt. p as determined by nuclear magnetic resonance spectroscopy pm, preferably more than 100 ppm by weight, more preferably more than 500 ppm by weight, and even more preferably More preferably, greater than 1000 ppm by weight of non-reactive end groups; ultra-high performance liquid chromatography 0.05 to 1,000 based on the total weight of the polyetherimide composition, ppm by weight, preferably 0.05 to 500 ppm by weight, more preferably 0.05 to 250 ppm by weight Residual organic diamines in ppm by weight; and gel permeation chromatography using polystyrene standards. Roughness is less than 4.5, preferably less than 4.0, more preferably less than 3.0. and even more preferably a curable epoxy having a polydispersity of less than 2.8. composition.

[0115] Aspect 5. The curable epoxy composition according to any one of aspects 1 to 4, further comprising a functionalized polyether. The trietherimide powder has the formula: [ka] wherein T and R are as defined herein. Composition.

[0116] Aspect 6. The curable epoxy composition of aspect 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)-(wherein, 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 (C6H 10 ) z - (wherein z is an integer from 1 to 4), and Z is ,formula [ka] (In the formula, R a and R b are each independently a halogen atom or a monovalent C 1-6 Alki p and q each independently represent an integer of 0 to 4, and c represents an integer of 0 to 4; X a is a single bond, -O-, -S-, -S(O)-, -SO2-, -C(O)-, -P(R a )(=O)-(wherein, R a is C 1-8 Alkyl or C 6-12 Aryl Or C 1-18an organic bridging group), preferably each R is independently a meta-phenylene group; Nylene, ortho-phenylene, para-phenylene, bis(4,4'-phenylene)sulfonate nyl, bis(3,4'-phenylene)sulfonyl, bis(3,3'-phenylene)sulfonyl , bis(4,4'-phenylene)oxy, bis(3,4'-phenylene)oxy, bi 4,4'-diphenyloxy or combinations thereof, A curable epoxy composition in which the epoxy group is phenylene isopropylidene.

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

[0118] Aspect 8. The curable epoxy composition according to any one of aspects 1 to 6, comprising an organic compound. The object is of formula R c -L n -Q 2 -L n -R d (In the formula, R c and R d are different and Independently, -OH, -NH2, -SH, or an anhydride group, a carboxylic acid or a carboxylic acid ester each L is the same or different and each L is independently substituted or unsubstituted. C 1-10 Alkylene or substituted or unsubstituted C 6-20 Arylene, Q 2 teeth, -O-, -S-, -S(O)-, -SO2-, -C(O)- or C 1-40 organic crosslinking 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, more preferably The organic compounds are para-aminophenol, meta-aminophenol, ortho-aminophenol, Phenol, 4-hydroxy-4'-aminodiphenylpropane, 4-hydroxy-4' -Aminodiphenylmethane, 4-amino-4'-hydroxydiphenylsulfone, 4-hydroxy hydroxy-4'-aminodiphenyl ether, 2-hydroxy-4-aminotoluene, 4 -Aminothiophenol, 3-aminothiophenol, 2-aminothiophenol, 4- Hydroxyphthalic anhydride, 3-hydroxyphthalic anhydride, 6-amino-2-naphtho 5-amino-2-naphthol, 8-amino-2-naphthol, 3-amino-2-naphthol tol or a combination thereof.

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

[0120] Aspect 10. The curable epoxy composition according to any one of aspects 1 to 9, comprising a particulate Fillers, fibrous fillers, antioxidants, heat stabilizers, light stabilizers, ultraviolet light stabilizers, ultraviolet light absorbers compounds, near infrared light absorbing compounds, infrared light absorbing compounds, plasticizers, lubricants, release agents, antistatic agents, storage Storage stabilizer, antiozonant, optical stabilizer, thickener, conductivity affecting agent, radiation blocking agent, nucleating agent, anti-fogging agent agents, antibacterial agents, metal deactivators, colorants, surface effect additives, radiation stabilizers, flame retardants, antidotes Lip additives, fragrances, adhesion promoters, flow improvers, coating additives, one or more epoxy The curable epoxy composition further comprises a polymer different from the silicone resin or a combination thereof.

[0121] Aspect 11. The curable epoxy composition of any one of aspects 1 to 10, comprising: Arylate, polyamide, polyimide, polyetherimide, poly(amideimide), poly Poly(aryl ether), phenoxy resin, poly(aryl sulfone), poly(ether sulfone), poly(phenylene sulfone), poly(ether ketone), poly(ether ether Poly(ether ketone), poly(aryl ketone), poly(phenyl ketone) Nylene ether), polycarbonate, carboxyl-terminated butadiene-acrylonitrile Rubber (CTBN), amine-terminated butadiene-acrylonitrile rubber (ATBN), epoxy ETBN, core-shell rubber or their equivalents The curable epoxy composition further comprising a combination of:

[0122] Aspect 12. For the preparation of a curable epoxy composition according to any one of aspects 1 to 11 The method includes mixing an epoxy resin composition and a functionalized polyetherimide at a temperature of 70 to 200°C. Combining at temperature to provide a reaction mixture, an epoxy resin hardener and optionally a hardener. and adding a curing catalyst to the reaction mixture to provide a curable epoxy composition.

[0123] Aspect 13. A cured product of the curable epoxy composition according to any one of aspects 1 to 11. Epoxy thermosets including:

[0124] Aspect 14. The epoxy thermoset of aspect 13, wherein after curing, the epoxy thermoset meets ASTM D34 50 to 300°C, preferably 150 to 300°C, as determined by DSC according to 18. More preferably, the temperature is 190 to 300° C., and even more preferably, the temperature is 210 to 300° C. or less. More preferably, the glass transition temperature is 230 to 300°C; or ASTM D5045 150J / m 2 More than 200 J / m 2 More than 250 J / m 2 or greater fracture toughness; or methylene chloride, tetrachloroethane, dichlorobenzene, chloro 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, Resistance to at least one of alcohol or a combination thereof Poxy thermoset.

[0125] Aspect 15. A composite material comprising the epoxy thermoset of aspect 13 or 14. , adhesives, films, layers, coatings, encapsulants, sealants, components, prepregs, casings or an article in the form of a combination thereof.

[0126] The compositions, methods and articles may include any suitable components or steps disclosed herein. Alternatively, the composition may comprise, consist of, or consist essentially of. The methods and articles may additionally or alternatively be directed to the function of the compositions, methods and articles in other cases. or any step, component, material, ingredient, adjuvant or other ingredient that is not necessary to accomplish the purpose. It can be constructed to be free or substantially free of chemical species.

[0127] The singular forms "a," "an," and "the" are used unless the context clearly dictates "Or" includes plural referents unless the context clearly indicates otherwise. "and / or" means "and / or" in any order. It does not denote quantity or importance, but rather is used to distinguish one element from another. Throughout the specification, references to "an embodiment" refer to a particular An element may be included in at least one embodiment described herein and may be present in other embodiments. The described elements may be used in any suitable manner in various embodiments. A "combination" includes blends, mixtures, alloys, reaction products, and the like. As used herein, "combinations thereof" is an open term and includes One or more of the listed items and, optionally, one or more similar items not listed This refers to a combination that includes the eyes.

[0128] All ranges disclosed herein are inclusive of the endpoints, and the endpoints are combinable independently of each other. The endpoints of all ranges directed to the same component or characteristic are inclusive and independently combinable. In addition to a broader range, a disclosure of a narrower range or a more specific group may be used to This does not disclaim any broader or larger scope.

[0129] Unless otherwise defined, technical and scientific terms used herein include All terms have the same meaning as commonly understood by a person skilled in the art to which this application pertains. All cited patents, patent applications and other references are incorporated herein by reference in their entirety. If a term in this application conflicts or contradicts a term in an incorporated reference, the term in this application shall prevail. takes precedence over any conflicting term in the incorporated references.

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

[0131] Unless a substituent is specifically indicated otherwise, each of the foregoing groups can be unsubstituted or substituted. Substitutions may be made provided that they do not significantly adversely affect the synthesis, stability or use of the compound. "Substituted" means that a compound, group, or atom has at least one hydrogen atom (e.g. , 1, 2, 3 or 4) substituents, where each substituent is The substituents are independently nitro (-NO2), cyano (-CN), hydroxy (-OH), halo Gen, thiol (-SH), thiocyano (-SCN), C 1-6 Alkyl, C 2-6 Al Kenil, C. 2-6 Alkynyl, C 1-6 Haloalkyl, C 1-9 Alkoxy, C 1-6 Ha Roalkok, C 3-12 Cycloalkyl, C 5-18 Cycloalkenyl, C 6-12 a Lille, 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 Arylsul aryl (-S(=O)2-aryl) or tosyl (CH3C6H4SO2-) The normal valence of the substituted atom is not exceeded, and the substitution does not affect the preparation, stability or desired properties of the compound. The number of carbon atoms shown in the group shall not significantly adversely affect the properties of the For example, -CH2CH2CN is a C2 alkyl group substituted with a nitrile. be.

[0132] Certain aspects have been described that are not or cannot be currently foreseen. Alternatives, modifications, variations, improvements, and substantial equivalents may occur to the applicant or those skilled in the art. Accordingly, the appended claims, as filed and as may be amended, are It is intended to embrace all such alternatives, modifications, variations, improvements, and substantial equivalents. can be.

Claims

1. One or more epoxy groups each independently having at least two epoxy groups per molecule. an epoxy resin composition comprising a resin; An epoxy resin hardener; Optionally, a curing catalyst; Substituted or unsubstituted C ４－４０ Bis-anhydrides and substituted or unsubstituted C １－４０ Organic Diamine and optionally an organic compound, The functionalized polyether is present in an amount of 5 to 75 parts by weight per 100 parts by weight of the epoxy resin composition. Imide and 1. A curable epoxy composition comprising: 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, a carboxylic acid ester, or a combination thereof; 、 The functionalized polyetherimide is a cationically linked polyetherimide having ... 50 to 1,500 microequivalents per gram of trietherimide, preferably 50 to 1,000 0 microequivalents / gram, more preferably 50 to 750 microequivalents / gram total reactivity having an end group concentration, The polyetherimide composition is determined by ultra-performance liquid chromatography. The amount of the polyetherimide compound is preferably 0.05 to 1,000 ppm by weight based on the total weight of the polyetherimide composition. or 0.05 to 500 ppm by weight, more preferably 0.05 to 250 ppm by weight of residual Contains an organic diamine, The functionalized polyetherimide is precipitated or devolatized from solution using an organic antisolvent. is obtained by The organic compound contains at least two functional groups per molecule, the first functional group being an anhydride. a first functional group reactive to a second functional group, an amine group, or a combination thereof; A curable epoxy composition, characterized in that the functional group is different from that of

2. 2. The curable epoxy composition of claim 1, wherein the epoxy resin composition comprises a compound represented by the formula 【Chemistry 1】 (In the formula, A is an inorganic group having a valence of n or C １－６０ is a hydrocarbyl group, and 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. Compounds, Preferably, A is C ６－１８ is a hydrocarbyl group, n is 2 or 3 or 4 、 More preferably, 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)biphenyl Bis(2,3-epoxycyclopentyl) ether, triglyceride Lysidyl isocyanurate, triglycidyl-p-aminophenol, triglycidyl- p-Aminodiphenyl ether, tetraglycidyldiaminodiphenylmethane, bis[4 -(glycidyloxy)phenyl]methane, tetraglycidyldiaminodiphenyl ether tetrakis(4-glycidyloxyphenyl)ethane, N,N,N',N'-tetrakis(4-glycidyloxyphenyl)ethane Glycidyl-diaminophenyl sulfone, Bisphenol A diglycidyl ether, Bis Phenol F epoxy resin, epoxy phenol novolac resin, epoxy cresol novolac Borac resin, spiro ring-containing epoxy resin, hydantoin epoxy resin or their 1. A curable epoxy composition comprising:

3. 3. The curable epoxy composition according to claim 1 or 2, wherein the epoxy resin curing agent is , diamine compounds, preferably m-phenylenediamine, p-phenylenediamine, o- Phenylenediamine, 3,3'-oxydianiline, 3,4'-oxydianiline, 4, 4'-oxydianiline, 1,3-bis(4-aminophenoxy)benzene, 1,3-bi (3-aminophenoxy)benzene, 4,4'-diaminodiphenyl sulfone, 3,3 '-Diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'- Methylenebis(2,6-diethylaniline), 4,4'-methylenedianiline, diethyl Toluene diamine, 4,4'-methylenebis(2,6-dimethylaniline), 2,4-bi p-aminobenzylaniline, 3,5-diethyltoluene-2,4-diamine, 3 , 5-diethyltoluene-2,6-diamine, m-xylylenediamine, p-xylylene diamine, diethyltoluenediamine or a combination thereof, more preferably 4,4'- A curable epoxy composition comprising diaminodiphenyl sulfone.

4. 4. The curable epoxy composition of claim 1, wherein the functionalized polymer is The trietherimide is 5,000 as determined by gel permeation chromatography using polystyrene standards up to 45,000 grams / mol, preferably 10,000 to 45,000 grams / mol, more preferably More preferably a weight average molecular weight of 15,000 to 35,000 grams / mole; Determined by the pore size of the sieve used to isolate the functionalized polyetherimide 1 to 1,000 micrometers, preferably 1 to 500 micrometers, more preferably The maximum thickness is preferably 1 to 100 micrometers, and even more preferably 1 to 75 micrometers. Large absolute particle size; More than 0.75, defined as the average number of reactive end groups per polyetherimide chain, is preferred. More preferably, the average reactive end point is greater than 0.9, more preferably greater than 1.1, and even more preferably greater than 1.

5. End group functionality; 155°C to 28°C as determined by differential scanning calorimetry according to ASTM D341 Glass transition at 0°C, preferably 175°C to 280°C, more preferably 190°C to 280°C temperature; The functionalized polyetherimide has a molecular weight of 0.5 to 500 nm as determined by nuclear magnetic resonance spectroscopy. 0 microequivalents / gram, preferably 0.5 to 1000 microequivalents / gram, more preferably or an amide-acid concentration of 0.5 to 500 microequivalents per gram; More than 0.05 ppm by weight, preferably 100 ppm by weight, as determined by nuclear magnetic resonance spectroscopy m, more preferably greater than 500 ppm by weight, even more preferably greater than 1000 ppm by weight non-reactive end groups; of the polyetherimide composition as determined by ultra-performance liquid chromatography. 0.05 to 1,000 ppm by weight, preferably 0.05 to 500 ppm by weight, based on the total weight of the compound. ppm by weight of residual organic diamine, more preferably 0.05 to 250 ppm by weight; and Less than 4.5 as determined by gel permeation chromatography using polystyrene standards , preferably less than 4.0, more preferably less than 3.0, even more preferably less than 2.8 Polydispersity of A curable epoxy composition comprising one or more of:

5. 5. The curable epoxy composition of claim 1, wherein the functionalized polymer is The polyetherimide powder has the formula 【Chemistry 2】 (In the formula, Each R is the same or different and independently represents a substituted or unsubstituted divalent C １－４０ organic group , preferably substituted or unsubstituted divalent C ６－２０ Aromatic hydrocarbon groups, substituted or unsubstituted C ４－２０ Alkylene group or substituted or unsubstituted C ３－８ is a cycloalkylene group, T is -O- or a group of the formula -O-Z-O-, where Z is 1 to 6 C １－８ Alkyl an aromatic C optionally substituted with a group, 1 to 8 halogen atoms, or a combination thereof; ６－ ２４ a monocyclic or polycyclic moiety, but the valency of Z shall not exceed A curable epoxy composition comprising units of:

6. 6. The curable epoxy composition of claim 5, Each R independently represents the formula 【Chemistry 3】 (In the formula, Q １ Yes, -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 ２ ｙ - and its halogenated derivatives, where y is an integer from 1 to 5, or -(C ６ H １０ ) ｚ -, where z is an integer from 1 to 4; Z is 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 It is an alkyl group. the law of nature, p and q each independently represent an integer from 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 is aryl) Or C １－１８ an organic bridging group; Preferably, each R is independently meta-phenylene, ortho-phenylene, or 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 the like and each Z is 4,4'-diphenyleneisopropylidene. A curable epoxy composition.

7. 7. The curable epoxy composition of claim 1, wherein the polyether is hydroxyethyl ether. The telluride has the formula 【Chemistry 5】 (In the formula, Each R is the same or different and independently represents a substituted or unsubstituted divalent C １－４０ organic group , preferably substituted or unsubstituted divalent C ６－２０ Aromatic hydrocarbon groups, substituted or unsubstituted C ４－２０ Alkylene group or substituted or unsubstituted C ３－８ is a cycloalkylene group, Z is 1 to 6 C １－８ an alkyl group, 1 to 8 halogen atoms, or a combination thereof Aromatic C optionally substituted with ６－２４ The valency of Z is (Not to exceed) A curable epoxy composition comprising units of:

8. The curable epoxy composition according to any one of claims 1 to 7, wherein the organic compound is The thing is, 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 represents -OH, -NH ２ , -SH or anhydrous a substituent or a carboxylic acid or a carboxylic acid ester, Each L is the same or different and each independently is a substituted or unsubstituted C １－１０ a alkylene or substituted or unsubstituted C ６－２０ is an arylene, Q ２ -O-, -S-, -S(O)-, -SO ２ -, -C(O)- or C １－４０ an organic bridging group, preferably substituted or unsubstituted C １－１０ Alkylene or substituted or unsubstituted Substitution C ６－２０ is an arylene, each n is independently 0 or 1; More preferably, the organic compound is para-aminophenol, meta-aminophenol. , ortho-aminophenol, 4-hydroxy-4'-aminodiphenylpropane, 4- Hydroxy-4'-aminodiphenylmethane, 4-amino-4'-hydroxydiphenyl Sulfone, 4-hydroxy-4'-aminodiphenyl ether, 2-hydroxy-4-amino Aminotoluene, 4-aminothiophenol, 3-aminothiophenol, 2-aminothio Phenol, 4-hydroxyphthalic anhydride, 3-hydroxyphthalic anhydride, 6-amino No-2-naphthol, 5-amino-2-naphthol, 8-amino-2-naphthol, 3- Curable epoxy compositions characterized in that they are amino-2-naphthols or combinations thereof. Composition.

9. The curable epoxy composition according to any one of claims 1 to 8, wherein the curable epoxy The viscosity of the epoxy composition is measured at 100° C. according to ASTM D4440-1. ,000 Pa·s or less, preferably 1,000 Pa·s or less, more preferably 500 Pa·s or less A curable epoxy composition, characterized in that the viscosity is 0.05 to 1.0 s.

10. 10. The curable epoxy composition of claim 1, further comprising a particulate filler. , fibrous fillers, antioxidants, heat stabilizers, light stabilizers, ultraviolet light stabilizers, ultraviolet light absorbing compounds, Near infrared absorbing compounds, infrared absorbing compounds, plasticizers, lubricants, release agents, antistatic agents, storage stability agents, antiozonants, optical stabilizers, thickeners, conductivity affecting agents, radiation blocking agents, nucleating agents, anti-fogging agents, anti Antibacterial agents, metal deactivators, colorants, surface effect additives, radiation stabilizers, flame retardants, anti-drip agents, fragrances, adhesion promoters, flow improvers, coating additives, one or more of the above epoxies A curable epoxy resin further comprising a polymer different from the resin or a combination thereof. Si composition.

11. 11. The curable epoxy composition according to claim 1, wherein the polyarylether is Polyamides, polyimides, polyetherimides, poly(amideimides), poly(amideimides), Poly(aryl ether), phenoxy resin, poly(aryl sulfone), poly(ether sulfonate) 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 combinations thereof The curable epoxy composition further comprising:

12. A method for the preparation of a curable epoxy composition according to any one of claims 1 to 11. There was, The epoxy resin composition and the functionalized polyetherimide are mixed at a temperature of 70 to 200° C. to provide a reaction mixture; The epoxy resin hardener and, optionally, the curing catalyst are added to the reaction mixture, providing a curable epoxy composition; The method according to claim 1, further comprising:

13. A cured product of the curable epoxy composition according to any one of claims 1 to 11. An epoxy thermosetting material characterized by:

14. 14. The epoxy thermoset of claim 13, which after curing: 50-300 as determined by differential scanning calorimetry according to ASTM D3418 ° C., preferably 150 to 300 ° C., more preferably 190 to 300 ° C., and even more preferably Preferably, the glass transition temperature is between 210 and 300° C., or even more preferably between 230 and 300° C. ;or 150 Joules / m2 or greater as measured in accordance with ASTM D5045, preferably Preferably, the radiation intensity is 200 joules / m2 or more, more preferably 250 joules / m2 or more. a fracture toughness of at least 1000 MPa; or 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 Solvent resistance to combinations of Epoxy thermoset material comprising at least one of:

15. The epoxy thermoset according to claim 13 or 14 is preferably used as a composite, adhesive, etc. agents, films, layers, coatings, encapsulants, sealants, components, prepregs, casings or An article characterized in that it is in the form of a combination thereof.

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