Method of making functionalized polyimide and polyimide resulting therefrom

Abstract

To provide functionalized polyimides having high Tg and low viscosity, and having reduced levels of byproducts, including residual solvent and monomer.SOLUTION: There is provided a polyimide composition, comprising a functionalized polyimide prepared from a substituted or unsubstituted C4-40 bisanhydride; a substituted or unsubstituted C1-40 organic diamine; and optionally an organic compound comprising at least two functional groups per molecule, wherein a first functional group is reactive with an anhydride group, an amine group, or a combination thereof, and the first functional group is different from a second functional group, wherein the functionalized polyimide comprises a reactive end group, wherein the functionalized polyimide has a total reactive end group concentration of 50 to 1,500 μeq / g of the functionalized polyimide, and wherein the polyimide composition has 0.05 to 1,000 ppm of residual organic diamine, wherein the functionalized polyimide is obtained by precipitation from a solution using an organic anti-solvent or by devolatilization.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to methods for preparing functionalized polyimides and the resulting polyimides. [Background technology]

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of European Patent Application Publication No. 19159165.0, filed February 25, 2019, the contents of which are incorporated herein by reference in their entirety.

[0003] Polyimides, especially polyetherimides (PEI), have a glass transition temperature (T g Polyetherimides are amorphous, transparent, high performance polymers having high strength, toughness, heat resistance and modulus, as well as broad chemical resistance, and are therefore widely used in such diverse industries as automotive, telecommunications, aerospace, electrical / electronics, transportation, and healthcare. Polyetherimides have demonstrated versatility, demonstrating their applicability in a variety of manufacturing processes to prepare a variety of articles, including techniques including injection molding, extrusion, and thermoforming.

[0004] However, polyimides are typically high viscosity materials and have high T g The high viscosity combined with the high viscosity of polyimide can prevent its use in certain manufacturing operations, such as the manufacture of composites and coatings. For example, the high T gBecause of this, the formation of complex parts or highly conformal coatings requires high temperatures that may not be compatible with other components. In addition, the higher viscosity limits the wetting performance of the polymer melt when applied to a substrate, which can result in coatings with voids or inadequate adhesion. Composites, coatings and thin films are currently produced using polymer solutions that contain organic solvents, which add removal and reclamation costs. Residual solvents can be an additional problem in certain applications, especially in the electronics industry. Residual levels of monomers such as amines, thiols and anhydrides are generally not favorable for further material handling and disposal. Additionally, thermoset materials with polyimide additives suffer from poor stability in organic solvents. Summary of the Invention [Problem to be solved by the invention]

[0005] Thus, there is a need for polyimides and polyetherimides having improved properties, particularly high T g There remains a need for functionalized polyimides that have low viscosity and low levels of by-products, including residual solvents and monomers. [Means for solving the problem]

[0006] According to one embodiment, the polyimide composition comprises a substituted or unsubstituted C 4-40 Bis-anhydrides and substituted or unsubstituted C 1-40 and a functionalized polyimide prepared from an organic diamine and, optionally, an organic compound comprising at least two functional groups per molecule, the first functional group being reactive to an anhydride group, an amine group, or a combination thereof, the first functional group being different from the second functional group, the functionalized polyimide having a structure represented by the formula (C 1-40 Hydrocarbylene)-NH 2 , (C 1-40 hydrocarbylene)-OH, (C 1-40 hydrocarbylene)-SH, (C 4-40and the functionalized polyimide comprises reactive end groups of 50 to 1,500 microequivalents per gram (μeq / g), preferably 50 to 1,000 μeq / g, and more preferably 50 to 750 μeq / g of the functionalized polyimide, and the polyimide composition has a residual organic diamine of 0.05 to 1,000 ppm by weight, preferably 0.05 to 500 ppm by weight, and more preferably 0.05 to 250 ppm by weight, based on the total weight of the polyimide composition, and the functionalized polyimide is obtained by precipitation or devolatilization from solution using an organic antisolvent.

[0007] Another embodiment is a substituted or unsubstituted C 4-40 Bis-anhydrides and substituted or unsubstituted C 1-40 A functionalized polyimide prepared from an organic diamine and, optionally, an organic compound, the organic compound comprising at least two functional groups per molecule, a first functional group being reactive towards an anhydride group, an amine group or a combination thereof, the first functional group being different from the second functional group, the functionalized polyimide being represented by the formula (C 1-40 Hydrocarbylene)-NH 2 , (C 1-40 hydrocarbylene)-OH, (C 1-40 hydrocarbylene)-SH, (C 4-40 and the polyimide composition has a residual organic diamine of 0.05 to 1,000 ppm by weight, preferably 0.05 to 500 ppm by weight, more preferably 0.05 to 250 ppm by weight, based on the total weight of the polyimide composition.

[0008] In another embodiment, a method for producing a functionalized polyimide comprises reacting a substituted or unsubstituted C under reaction conditions effective to provide a functionalized polyimide. 4-40 Bis-anhydrides and substituted or unsubstituted C 1-40 The method includes reacting an organic diamine and, optionally, an organic compound.

[0009] In yet another aspect, a curable composition includes a functionalized polyimide and a thermosetting component. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The inventors have discovered that lower molecular weight functionalized polyimide oligomers can be prepared that incorporate a certain amount of functionalized end groups. The reactive functional groups allow the use of functionalized polyimides in cured thermosets, for example, by incorporation into the thermoset matrix, thereby improving the chemical resistance of the cured thermoset. The lower molecular weight of the functionalized polyimide allows for higher loadings that achieve improved mechanical properties in the cured thermoset, such as toughness, impact strength, and modulus. Functionalized polyimide powders with a maximum particle size of less than 1,000 micrometers can further improve processing for thermosetting compositions. The disclosed method also provides functionalized polyimides with lower amounts of unreacted monomers, such as para-aminophenol and meta-phenylenediamine, which improve the stability of the curable composition and reduce viscosity increase during processing and potential health hazards during handling.

[0011] Thus, one aspect of the present disclosure is a substituted or unsubstituted C 4-40 Bis-anhydrides and substituted or unsubstituted C 1-40 A polyimide composition comprising a functionalized polyimide prepared from an organic diamine and, optionally, an organic compound containing at least two functional groups per molecule. The functionalized polyimide is represented by the formula (C 1-40 Hydrocarbylene)-NH 2 , (C 1-40 hydrocarbylene)-OH, (C 1-40 hydrocarbylene)-SH, (C4-40 The polyimide composition comprises reactive end groups of 0.05 to 1,000 ppm by weight, preferably 0.05 to 500 ppm by weight, more preferably 0.05 to 250 ppm by weight, based on the total weight of the polyimide composition.

[0012] As used herein, the term "carboxylic acid" includes carboxylates. The corresponding cations can be organic or inorganic cations. Exemplary cations include, for example, ammonium, phosphonium, sodium, potassium, lithium, or the like.

[0013] The functionalized polyimide 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, where G is an anhydride group, a carboxylic acid, a carboxylic acid ester, or combinations thereof. In some embodiments, the functionalized polyimide comprises a reactive end group of the formula (C 1-40 Hydrocarbylene)-NH 2 , (C 1-40 hydrocarbylene)-SH, (C 4-40 In yet another embodiment, the functionalized polyimide comprises a reactive end group of the formula (C 1-40 Hydrocarbylene)-NH 2 , (C 4-40 The copolymer comprises reactive end groups of hydrocarbylene)-G or combinations thereof, where G is an anhydride group, a carboxylic acid, a carboxylic acid ester, or combinations thereof.

[0014] Exemplary C 1-40 Hydrocarbylene may include substituted or unsubstituted C 1-40 Alkylene or substituted or unsubstituted C 6-40 Arylene is preferably C 1-40 The hydrocarbylene may be a substituted or unsubstituted C 1-10 Alkylene or substituted or unsubstituted C 6-40 It is arylene.

[0015] The total reactive end group concentration is from 50 to 1,500 microequivalents per gram (μeq / g) of the functionalized polyimide, preferably from 50 to 1,000 μeq / g, and more preferably from 50 to 750 μeq / g.

[0016] As used herein, a reactive end group is a group that can interact with another polymer or prepolymer to promote the formation of a crosslinked network through chemical or physical bonds during cure and / or promote the formation of phase-separated polyimide domains having a morphology that contributes to imparting toughness to the cured thermoset polymer. The reactive end group is attached to an atom of the polyimide chain as a chain end group.

[0017] The concentration of end groups can be analyzed by various titration and spectroscopy methods well known in the art. Spectroscopic methods include infrared, nuclear magnetic resonance, Raman spectroscopy and fluorescence. An example of an infrared method is described in JA Kreuz, et al., and J.Poly.Sci.Part A-1, vol.4, pp.2067-2616 (1966). An example of a titration method is described in YJ Kim, et al., Macromolecules, vol.26, pp.1344-1358 (1993). It may be advantageous to prepare derivatives of the polymer end groups to improve the sensitivity of the measurement, for example, using a variant of the method described in KP Chan et al., Macromolecules, vol.27, p.6731 (1994) and JS Chao, Polymer Bull., vol.17, p.397 (1987). In some embodiments, the reactive end group concentration is determined by nuclear magnetic resonance spectroscopy.

[0018] The functionalized polyimide has the formula (1): [ka] where each V is the same or different and is a substituted or unsubstituted tetravalent C 4-40 Hydrocarbon groups, such as substituted or unsubstituted C 6-20 Aromatic hydrocarbon groups, substituted or unsubstituted C 5-20 Heterocyclic aromatic groups, substituted or unsubstituted, linear or branched, saturated or unsaturated C 4-20 Aliphatic group or substituted or unsubstituted C 4-8 Alicyclic groups, especially substituted or unsubstituted C 6-20 C of aromatic hydrocarbon group 4-40 It can be prepared from the bis-anhydride. 4-40 The hydrocarbon group can optionally contain 1 to 3 heteroatoms. Exemplary aromatic hydrocarbon groups include those of the formula [ka] (Wherein, W is a single bond, -O-, -S-, -C(O)-, -SO 2 C, which can be -, -SO-, cyclic, acyclic, aromatic or non-aromatic 1-18 Hydrocarbylene group, -P(R a )(=O)-(wherein, R a is C 1-8 Alkyl or C 6-12 aryl) or -C y H 2y - (where y is an integer from 1 to 5) or its halogenated derivatives (including perfluoroalkylene groups) or groups of the formula -OZO- described below for formula (5a). The functionalized polyimides can be prepared from a single bis-anhydride or a combination of two or more different bis-anhydrides.

[0019] C 4-40Illustrative examples of bisanhydrides include 3,3-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl ether dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)benzophenone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride, 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride, 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl ether dianhydride, 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(2,3-dicarboxyphenoxy)phenyl Examples of such compounds include 4,4'-bis(2,3-dicarboxyphenoxy)benzophenone dianhydride, 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl sulfone dianhydride, 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl-2,2-propane dianhydride, 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl ether dianhydride, 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)benzophenone dianhydride and 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride.

[0020] C 1-40 The organic diamine is represented by the formula (2): H 2 NR-NH 2 (2) (Wherein, R is C 6-20 Aromatic hydrocarbon radicals or their halogenated derivatives, C 2-20 Substituted or unsubstituted straight or branched chain C, such as an alkylene group 1-40 Alkylene group or substituted or unsubstituted C 3-8 Substituted or unsubstituted divalent C, such as a cycloalkylene group 1-40 or C 1-20is an organic group, or in particular of formula (2a) [ka] (In the formula, Q 1 -O-, -S-, -C(O)-, -SO 2 -, -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 a halogenated derivative thereof (including a perfluoroalkylene group) or -(C 6 H 10 ) z -, where z is an integer from 1 to 4. In some embodiments, R is m-phenylene, p-phenylene, o-phenylene; diarylylene sulfone, particularly bis(4,4'-phenylene) sulfone, bis(3,4'-phenylene) sulfone, or bis(3,3'-phenylene) sulfone; or diarylylene ether, particularly bis(4,4'-phenylene) ether, bis(3,4'-phenylene) ether, or bis(3,3'-phenylene) ether. The functionalized polyimides can be prepared from a single organic diamine or a combination of two or more different organic diamines.

[0021] Exemplary C 1-40Organic diamines include ethylenediamine, propylenediamine, hexamethylenediamine, polymethylated 1,6-n-hexanediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 1,12-dodecanediamine, 1,18-octadecanediamine, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 4-methylnonamethylenediamine, 5-methylnonamethylenediamine, 2,5-dimethylhexamethylene Diamine, 2,5-dimethylheptamethylenediamine, 2,2-dimethylpropylenediamine, N-methyl-bis(3-aminopropyl)amine, 3-methoxyhexamethylenediamine, 1,2-bis(3-aminopropoxy)ethane, bis(3-aminopropyl)sulfide, 1,4-cyclohexanediamine, bis(4-aminocyclohexyl)methane, m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene , m-xylylenediamine, p-xylylenediamine, 2-methyl-4,6-diethyl-1,3-phenylenediamine, 5-methyl-4,6-diethyl-1,3-phenylenediamine, benzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 1,5-diaminonaphthalene, bis(4-aminophenyl)methane, bis(2-chloro-4-amino-3,5-diethylphenyl)methane, bis(4-aminophenyl)propane, 2,4-bis(p-amino-t-butyl)toluene These include ene, bis(p-amino-t-butylphenyl)ether, bis(p-methyl-o-aminophenyl)benzene, bis(p-methyl-o-aminopentyl)benzene, 1,3-diamino-4-isopropylbenzene, oxydianiline, bis((aminophenoxy)phenyl)sulfone, bis(4-aminophenyl)sulfide, bis(4-aminophenyl)sulfone (also known as 4,4'-diaminodiphenylsulfone (DDS)) and bis(4-aminophenyl)ether. 1-40The organic diamine can be m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenyl sulfone, 4,4'-oxydianiline, bis(4-(4-aminophenoxy)phenyl)sulfone, or a combination thereof.

[0022] The optional organic compound includes at least two functional groups per molecule. A first functional group is reactive to anhydrides, amines, or a combination thereof, and the first functional group is different from the second functional group. For example, the organic compound can be represented by the formula (3): R c -L n -Q 2 -L n -R d (3) (In the formula, R c and R d are different and each independently represents -OH, -NH 2 In formula (3), each L may be the same or different and each independently may be a substituted or unsubstituted C 1-10 Alkylene or substituted or unsubstituted C 6-20 Arylene, Q 2 -O-, -S-, -S(O)-, -SO 2 -, -C(O)- or C 1-20 an organic bridging group, preferably substituted or unsubstituted C 1-10 Alkylene or substituted or unsubstituted C 6-20 arylene, and each n is independently 0 or 1. It should be understood that formula (3) is limited to chemically feasible organic compounds, as would be understood by those skilled in the art. For example, the organic compound cannot be HO-O-OH, and therefore, in formula (3), when Q is -O-, n is 1.

[0023] Exemplary organic compounds include para-aminophenol, meta-aminophenol, ortho-aminophenol, 4-hydroxy-4'-aminodiphenylpropane, 4-hydroxy-4'-aminodiphenylmethane, 4-amino-4'-hydroxydiphenylsulfone, 4-hydroxy-4'-aminodiphenylether, 2-hydroxy-4-aminotoluene, 4-aminothiophenol, 3-aminothiophenol, 2-aminothiophenol, 4-hydroxyphthalic anhydride, 3-hydroxyphthalic anhydride, 6-amino-2-naphthol, 5-amino-2-naphthol, 8-amino-2-naphthol and 3-amino-2-naphthol or the like. More than one organic compound can be used. When prepared, the functionalized polyimide contains more than one, for example 10 to 1000 or 10 to 500, of the formula (4): [ka] wherein each V is the same or different and is as defined in formulas (1) and (2). Further, in formula (4), each R is the same or different and is as defined above. In some embodiments, at least 10 mole percent or at least 50 mole percent of the R groups comprise a sulfone group, and in other embodiments, the R groups do not comprise a sulfone group.

[0024] In certain embodiments, the functionalized polyimide has the formula (1a): [ka] C 4-40 Bis anhydride and C 1-40 A functionalized polyetherimide prepared from an organic diamine and, optionally, an organic compound, wherein T is a single bond, -O-, -S-, -S(O)-, -S(O) 2 -, -C(O)- or C 1-18 An organic bridging group or a group of the formula -OZO-, where -O-, -S-, -S(O)-, -C(O)-, -S(O) 2 -, C 1-18The divalent bonds of the organic bridging groups or -OZO- groups can be at the 3,3', 3,4', 4,3' or 4,4' positions, and Z is as defined below in formula (5a), which can be a functionalized polyetherimide.

[0025] The polyetherimide may comprise more than one, for example from 10 to 1000 or from 10 to 500, units of formula (5) or (5a) [ka] wherein each R is the same or different and is as defined in formula (2).

[0026] The Z group in -OZO- of formula (5a) is a substituted or unsubstituted divalent organic group having 1 to 6 C 1-8 Aromatic C optionally substituted with an alkyl group, 1 to 8 halogen atoms, or a combination thereof 6-24 It may be a monocyclic or polycyclic moiety, provided that the valency of Z does not exceed 1. Exemplary Z groups include those of formula (6): [ka] (In the formula, R a and R b may be the same or different and are halogen atoms or monovalent C 1-6 For example, p and q are each independently an integer of 0 to 4, c is an integer of 0 to 4, and X a is a bridging group connecting the hydroxy-substituted aromatic groups, and the bridging group and each C 6 Hydroxy substituents of the arylene group are C relative to each other. 6 The bridging group X includes groups derived from dihydroxy compounds that are ortho, meta or para (especially para) disposed to the arylene group. a is a single bond, -O-, -S-, -S(O)-, -S(O) 2 -, -C(O)- or C 1-18 It may be an organic bridging group. 1-18The organic bridging group may be cyclic or acyclic, aromatic or non-aromatic, and may further contain heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorus. 1-18 The organic group has a C bonded to it. 6 Arylene groups are common to the alkylidene carbon or C 1-18 Specific examples of Z groups include those represented by formula (6a): [ka] (In the formula, Q is -O-, -S-, -C(O)-, -SO 2 -, -SO- or -C y H 2y -, where y is an integer from 1 to 5, or a halogenated derivative thereof (including a perfluoroalkylene group). In certain embodiments, Z is derived from bisphenol A, such that Q in formula (6a) is 2,2-isopropylidene.

[0027] In some embodiments, in formula (5a), R is m-phenylene, o-phenylene, or p-phenylene, and Z is a divalent radical of formula (6a). Alternatively, R is m-phenylene, o-phenylene, or p-phenylene, Z is a divalent radical of formula (6a), and Q is 2,2-isopropylidene.

[0028] In some embodiments, the polyetherimide is a copolymer, e.g., a copolymer of formula (5a), where at least 50 mole percent of the R groups are of formula (2a), where Q 1 -SO 2 -, wherein the remaining R groups are independently p-phenylene, m-phenylene or combinations thereof, and Z is 2,2'-(4-phenylene)isopropylidene.

[0029] Alternatively, the polyetherimide copolymer may contain additional structural imide units, such as those represented by formula (4), where R and V are as described in formulas (1) and (2), e.g., V is [ka] (Wherein, W is a single bond, -O-, -S-, -C(O)-, -SO 2 C, which can be -, -SO-, cyclic, acyclic, aromatic or non-aromatic 1-18 Hydrocarbon moiety, -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 a halogenated derivative thereof (including perfluoroalkylene groups). The additional structural imide units preferably comprise less than 20 mol %, preferably 0 to 10 mol % or 0 to 5 mol %, of the total number of units. In some embodiments, no additional imide units are present in the polyetherimide.

[0030] The functionalized polyimide comprises a polyimide unit of formula (4) or (5), preferably formula (5a), and a polyimide unit of formula (7) [ka] wherein E has an average value of 2 to 100, 2 to 31, 5 to 75, 5 to 60, 5 to 15, or 15 to 40; and each R' is independently C 1-13 and a siloxane block of R′, which is a monovalent hydrocarbyl group. For example, each R′ can independently be an optionally halogenated, C 1-13 Alkyl, C 1-13 Alkoxy, C 2-13 Alkenyl, C 2-13 Alkenyloxy, C 3-6 Cycloalkyl, C 3-6 Cycloalkoxy, C 6-14 Aryl, C 6-10 Aryloxy, C 7-13 Aryl alkyl, C 7-13 Arylalkoxy, C 7-13 Alkylaryl or C 7-13It may be an alkylaryloxy group. In some embodiments, no bromine or chlorine is present, and in other embodiments, no halogen is present. Combinations of the aforementioned R groups may be used in the same copolymer. In some embodiments, the polysiloxane block includes an R' group with a minimal hydrocarbon content, such as a methyl group.

[0031] Poly(siloxane-imides) can be prepared from bis-anhydrides (1) and organic diamines (2) or from organic diamines and the formula (8): [ka] (In the formula, R′ and E are as defined in formula (7), and R 4 are each independently C 2 -C 20 Hydrocarbons, especially C 2 -C 20 In one embodiment, R is an arylene, alkylene, or arylene alkylene group. 4 is C 2 -C 20 and E has an average value of 5 to 100, 5 to 60, or 15 to 40. The diamine component can include 10 to 90 mol %, or 20 to 50 mol %, or 25 to 40 mol % of polysiloxane diamine (8) and 10 to 90 mol %, or 50 to 80 mol %, or 60 to 75 mol % of organic diamine (2), as described, for example, in U.S. Pat. No. 4,404,350. The poly(siloxane-imide) copolymer can be a block, random, or graft copolymer.

[0032] Examples of specific poly(siloxane-imides) are described in U.S. Patent Nos. 4,404,350, 4,808,686, and 4,690,997. In one embodiment, the poly(siloxane-imide) is a poly(siloxane-ether imide) and has the formula (9): [ka] (wherein R′ and E of the siloxane are as in formula (7), R and Z of the imide are as in formulas (1) and (2), and R 4 is R as in equation (8). 4 and n is an integer from 5 to 100. In a particular embodiment, R of the etherimide is phenylene, Z is a residue of bisphenol A, and R 4 is n-propylene, E is 2 to 50, 5 to 30, or 10 to 40, n is 5 to 100, and each R' is methyl.

[0033] The relative amounts of polysiloxane units and imide units in the poly(siloxane-imide) depend on the desired properties and are selected using the guidelines set forth herein, in certain embodiments, the poly(siloxane-imide) contains 10-50 wt%, 10-40 wt%, or 20-35 wt% polysiloxane units based on the total weight of the poly(siloxane-imide).

[0034] In some embodiments, the functionalized polyimide is not a poly(siloxane-imide) copolymer, e.g., the functionalized polyimide does not include a poly(siloxane-imide copolymer).

[0035] The functionalized polyimides may be prepared by reacting substituted or unsubstituted C under reaction conditions effective to provide the functionalized polyimides. 4-40 Bis-anhydrides and substituted or unsubstituted C 1-40 They can be prepared by reacting an organic diamine and, optionally, an organic compound. For example, functionalized polyimides can be prepared by polycondensation of bis-anhydrides and organic diamines.

[0036] The bis-anhydride and organic diamine can be reacted in substantially equimolar amounts or with a molar excess of the amine or bis-anhydride. The term "substantially equimolar amounts" refers to a molar ratio of the bis-anhydride to the organic diamine of 0.9 to 1.1, preferably 0.95 to 1.05, more preferably 0.98 to 1.02. Exemplary molar excesses are represented by molar ratios of the bis-anhydride to the organic diamine of 26 or less, preferably 20 or less, more preferably 15 or less, or 2 to 26, preferably 5 to 26, more preferably 10 to 26.

[0037] Conditions effective to give polyimides can include a temperature of 170-380°C and a solids content of 1-50 wt%, preferably 20-40 wt%, more preferably 25-35 wt%. The polymerization can be carried out for 2-24 hours (hr), preferably 3-16 hr. The polymerization can be carried out at reduced, atmospheric or elevated pressure.

[0038] In certain embodiments, the reaction can be carried out in a first solvent to provide a mixture of the functionalized polyimide and the first solvent, or a functionalized polyimide-solvent mixture. In some embodiments, the reaction in the first solvent provides a solution of the functionalized polyimide in the first solvent, for example a homogeneous solution of the functionalized polyimide in the first solvent.

[0039] The first solvent is an inert non-polar organic solvent or an inert polar solvent that does not adversely affect the reaction. The first solvent can be any solvent in which the functionalized polyimide is chemically stable and has a solubility of greater than 5 grams per liter (g / L). Exemplary first solvents include veratrole, ortho-dichlorobenzene (ODCB), para-dichlorobenzene (PDCB), meta-dichlorobenzene (MDCB), N-methylpyrrolidone (NMP), chloroform, anisole, dichlorotoluene, trichlorobenzene, tetrachlorobenzene, tetrahydrofuran (THF), dimethylformamide (DMF), dichloromethane (DCM), dimethylacetamide (DMAc), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), ethylene carbonate (EC), dimethyl sulfoxide (DMSO), dimethyl sulfone, diphenyl sulfone, sulfolane, diphenyl ether, phenetole, hexafluoro-2-propanol (HFIP), trichloroethane (TCHE), tetrachloroethane, trifluoroacetic acid (TFA), Examples of suitable solvents include phenol (e.g., 4-chloro-3-methylphenol, 4-chloro-2-methylphenol, 2,4-dichloro-6-methylphenol, 2,4-dichlorophenol, 2,6-dichlorophenol, 4-chlorophenol, 2-chlorophenol, 4-methoxyphenol), cresol (e.g., ortho-cresol, meta-cresol, para-cresol), benzoquinone, xylenol (e.g., 2,3-xylenol, 2,6-xylenol), dihydroxybenzene (e.g., catechol, resorcinol), n-ethyl-2-pyrrolidone (NEP), 1-ethenyl-2-pyrrolidone (NVP), 2-pyrrolidone (2-Py), 1,3-dimethyl-2-imidazolidinone (DMI), benzonitrile, dipropylene glycol dimethyl ether (DPGME), or combinations thereof. The first solvent can include one or more solvents, provided that the solvents are miscible.

[0040] The functionalized polyimide-solvent mixture, e.g., a solution of the functionalized polyimide in a first solvent, can be contacted with a second solvent, also known as an organic antisolvent, under conditions effective to isolate the functionalized polyimide by precipitation. In certain embodiments, the polyimide-solvent mixture is not a slurry as described in U.S. Patent Application Publication No. 2006 / 0270825. For example, the functionalized polyimide-solvent mixture can have a polyimide concentration of up to 50% by weight, preferably up to 40% by weight, and more preferably up to 30% by weight, based on the total weight of the mixture. The second solvent can be contacted such that the resulting weight ratio of the second solvent to the functionalized polyimide-solvent mixture is 20:1 to 1:1, preferably 15:1 to 1:1, and more preferably 10:1 to 1:1. The contacting step can be performed using agitation to disperse and mix the functionalized polyimide-solvent mixture and the second solvent. The contacting step can be at a temperature between −78° C. and 150° C., and at ambient or reduced pressure, preferably within the range of 1.3 to 100 kilopascals (kPa), preferably 26.7 to 100 kPa, more preferably 66.7 to 100 kPa.

[0041] The second solvent is a material that induces precipitation of the functionalized polyimide when the second solvent and the functionalized polyimide-solvent mixture are combined. In other words, the functionalized polyimide is insoluble in the second solvent and has a solubility in the second solvent of less than 2 grams per liter (g / L) at the operating temperature of the dispersion medium, particularly 1 g / L or less, or 0.5 g / L or less, or 0.1 g / L or less. Examples of second solvents include C 1-6 Alkyl alcohol, C 3-6 Alkyl ketones, C 5-6 Cycloalkyl ketones, C 3-6 Alkyl ester, C 5-8 Alkane, C 5-7 Cycloalkane, C 2-6 Aliphatic nitrile, C 2-6 Acyclic ethers, C 4-7In certain embodiments, the second solvent can be methanol, isopropanol, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, acetone, acetonitrile, tetrahydrofuran, or a combination thereof. Preferably, the second solvent is miscible with the first solvent.

[0042] The functionalized polyimide-solvent mixture can alternatively be treated under other conditions effective to isolate the functionalized polyimide. Exemplary treatments include volatilizing the first solvent to form a thin film of the functionalized polyimide-solvent mixture under conditions effective to substantially completely remove the first solvent and, optionally, to remove residual water (if present) from the polymerization reaction, such as at a temperature of 200-450°C and a pressure of 0.13 kPa to 102 kPa. For example, after evaporating the first solvent, the resulting functionalized polyimide can be heated above its glass transition temperature, such as at 250-400°C, preferably 300-350°C, and more preferably 350-400°C.

[0043] In another embodiment, the reaction is carried out under conditions effective to provide a polyimide oligomer, which is a substituted or unsubstituted C 4-40 Bis-anhydrides and substituted or unsubstituted C 1-40 The process includes polymerizing an organic diamine with a polyimide oligomer and melt mixing the polyimide oligomer with an organic compound under conditions effective to provide a functionalized polyimide. For example, the melt mixing can be carried out at ambient or reduced pressure in a large volume processing device capable of handling viscosities of greater than 100,000 centipoise (cP), such as in a wiped film evaporator or in an extruder, or a combination thereof. The melt mixing can be at a temperature of 150 to 450°C, preferably 200 to 400°C, more preferably 250 to 375°C. The melt mixing can be carried out in an extruder operated at 50 to 500 revolutions per minute (rpm), or 50 to 400 rpm, or 50 to 350 rpm. The melt mixing can be carried out for less than 15 minutes, preferably 1 to 10 minutes, more preferably 1 to 5 minutes. The resulting functionalized polyimide can be prepared by the process described above. 6 - 36Substantially free of alkylimide and aliphatic amine endblocking functional groups.

[0044] The reaction can be carried out with substituted or unsubstituted C 4-40 Bis-anhydrides and substituted or unsubstituted C 1-40 The method may include melt polymerizing an organic diamine and, optionally, an organic compound to provide a functionalized polyimide. g The melt polymerization can be carried out at a temperature 50-200°C, preferably 100-150°C, higher than 1.3 to 100 kilopascals (kPa), more preferably 26.7 to 100 kPa, and even more preferably 66.7 to 100 kPa. The melt polymerization can be carried out using a batch mixer, kneader reactor, stirred thin film evaporator, or other large volume processing equipment capable of handling viscosities of greater than 100,000 centipoise (cP). The melt polymerization can be carried out for 5 minutes to 24 hours, preferably 30 minutes to 12 hours, and more preferably 1 to 6 hours.

[0045] Endblocking agents, particularly monofunctional compounds capable of reacting with amines or anhydrides, may be present in the reaction. Exemplary compounds include monofunctional aromatic anhydrides such as phthalic anhydride, aliphatic monoanhydrides such as maleic anhydride, or monofunctional aldehydes, ketones, esters, isocyanates, aromatic monoamines such as anilines, or C 1 -C 18 Linear or cyclic aliphatic monoamines are included. The amount of endblocking agent that can be added depends on the desired amount of chain terminator and can be, for example, 0-10 mol%, or 0.1-10 mol%, or 0.1-6 mol%, based on the moles of endblocking agent and diamine or bis-anhydride reactant. In some embodiments, no additional endblocking agent is used to prepare the functionalized polyimide.

[0046] In some embodiments, the functionalized polyimide has greater than 0.05 ppm by weight, preferably greater than 100 ppm by weight, more preferably greater than 500 ppm by weight, and even more preferably greater than 1,000 ppm by weight of non-reactive end groups based on the total weight of the functionalized polyimide.

[0047] A catalyst may be present during the reaction. Exemplary catalysts include sodium arylphosphinate, guanidinium salts, pyridinium salts, imidazolium salts, tetra(C 7-24 arylalkylene)ammonium salts, dialkylheteroalicyclic ammonium salts, bis-alkyl quaternary ammonium salts, (C 7-24 Aryl alkylene) (C 1-16 alkyl)phosphonium salts, (C 6-24 Aryl)(C 1-16 Examples of the anionic component of the salt include alkyl)phosphonium salts, phosphazenium salts, and combinations thereof. The anionic component of the salt is not particularly limited and can be, for example, chloride, bromide, iodide, sulfate, phosphate, acetate, maculate, tosylate, and the like. Combinations of different anions can be used. The catalytic activity amount of the catalyst can be determined by one of skill in the art without undue experimentation and can be, for example, greater than 0 to 5 mol%, or 0.01 to 2 mol%, or 0.1 to 1.5 mol%, or 0.2 to 1.0 mol%, based on the moles of the organic diamine.

[0048] In one embodiment, the functionalized polyimide is a substituted or unsubstituted C-type polyimide having a molecular weight of 50-90 wt%, preferably 60-90 wt%, more preferably 70-90 wt%, based on the total weight of the bis-anhydride, organic diamine, and organic compound. 4-40 Bis-anhydride and 5 to 50 wt%, preferably 15 to 50 wt%, more preferably 15 to 35 wt% of substituted or unsubstituted C 1-40 It is prepared from a reaction mixture containing an organic diamine and 0 to 45 wt %, preferably 0 to 35 wt %, and more preferably 0 to 25 wt % of an organic compound.

[0049] In another embodiment, the functionalized polyimide is a polyimide having 50-90 wt %, preferably 60-90 wt %, more preferably 70-90 wt % substituted or unsubstituted C based on the total weight of the bis-anhydride, organic diamine and organic compound. 4-40 Bis-anhydride and 5 to 50 wt%, preferably 15 to 50 wt%, more preferably 15 to 35 wt% of substituted or unsubstituted C 1-40 It is prepared from a reaction mixture containing an organic diamine and 1 to 45 wt %, preferably 3 to 45 wt %, and more preferably 5 to 45 wt % of an organic compound.

[0050] The functionalized polyimide has a weight average molecular weight (M) of 5,000 to 45,000 grams / mole (g / mol), preferably 10,000 to 45,000 g / mol, and more preferably 15,000 to 35,000 g / mol, as determined by gel permeation chromatography (GPC) using polystyrene standards. w The polydispersity (PDI) may be less than 4.5, preferably less than 4.0, more preferably less than 3.0, and even more preferably less than 2.80.

[0051] The functionalized polyimide can have a maximum absolute particle size of less than 1,000 micrometers (μm), preferably less than 500 μm, more preferably less than 100 μm, and even more preferably less than 75 μm. The maximum absolute particle size is defined by the pore size of the sieve used to isolate the functionalized polyimide particles and does not represent an average particle size.

[0052] The functionalized polyimides may have an average reactive end group functionality greater than 0.75, preferably greater than 0.9, more preferably greater than 1.1, and even more preferably greater than 1.5. The average reactive end group functionality is defined as the average number of hydroxyl, amino, and carboxylic acid end groups per polyimide chain.

[0053] The functionalized polyimides have a glass transition temperature (T g ) can be used. For example, T gThe temperature may be 155 to 280° C., preferably 175 to 280° C., and more preferably 190 to 280° C., as determined by differential scanning calorimetry (DSC) according to ASTM D3418.

[0054] The functionalized polyimide can have an amide-acid concentration, as determined by nuclear magnetic resonance spectroscopy, of 0.5 to 5000 microequivalents per gram (μeq / g), preferably 0.5 to 1000 μeq / g, and more preferably 0.5 to 500 μeq / g of the functionalized polyimide. For example, the functionalized polyimide can have an amide-acid end group concentration, as determined by nuclear magnetic resonance spectroscopy, of 0.5 to 5000 μeq / g, preferably 0.5 to 1000 μeq / g, and more preferably 0.5 to 500 μeq / g of the functionalized polyimide.

[0055] The polyimide composition has a residual organic diamine of 0.05 to 1,000 ppm, preferably 0.05 to 500 ppm, and more preferably 0.05 to 250 ppm by weight, based on the total weight of the polyimide composition, as determined by ultra-performance liquid chromatography (UPLC).

[0056] The polyimide composition can contain 0.05 to 5,000 ppm by weight, preferably 0.05 to 1000 ppm by weight, more preferably 0.05 to 500 ppm by weight, and even more preferably 0.05 to 250 ppm by weight of residual solvent, based on the total weight of the polyimide composition, as determined by gas chromatography.

[0057] The polyimide composition may contain residual bis-anhydrides and residual organic compounds in an amount of 0.05 to 1,000 ppm by weight, preferably 0.05 to 750 ppm by weight, and more preferably 0.05 to 500 ppm by weight, each based on the total weight of the polyimide composition, as determined by UPLC.

[0058] As used herein, "residual bis-anhydride" refers to the substituted or unsubstituted C anhydride remaining from the preparation of the functionalized polyimide. 4-40As used herein, "residual organic compounds" refers to the organic compounds, if any, remaining from the preparation of a functionalized polyimide. As used herein, "residual diamines" refers to the substituted or unsubstituted C2H3O4-containing amines remaining from the preparation of a functionalized polyimide. 1-40 It means an organic diamine.

[0059] The polyimide composition may have a total content of residual bis-anhydrides, residual diamines and residual organic compounds of 0.05 to 3,000 ppm by weight, preferably 0.05 to 2,000 ppm by weight, more preferably 0.05 to 1,000 ppm by weight, and even more preferably 0.05 to 500 ppm by weight, based on the total weight of the polyimide composition.

[0060] The polyimide composition may contain 0.1 to 100 ppm by weight, 0.1 to 75 ppm by weight, and 0.1 to 25 ppm by weight of Na, K, Ca, Zn, Al, Cu, Ni, P, Ti, Mg, Mn, Si, Cr, Mo, Co, and Fe, respectively, based on the total weight of the polyimide composition, as determined by inductively coupled plasma spectroscopy.

[0061] The polyimide composition may have a total content of Na, K, Ca, Zn, Al, Cu, Ni, P, Ti, Mg, Mn, Si, Cr, Mo, Co, and Fe of 0.1 to 200 ppm by weight, 0.1 to 100 ppm by weight, 0.1 to 50 ppm by weight, or 0.1 to 25 ppm by weight based on the total weight of the polyimide composition, as determined by inductively coupled plasma spectroscopy.

[0062] The polyimide composition may contain 0.3 to 500 ppm by weight, 0.3 to 250 ppm by weight, respectively, of phosphate ions, nitrate ions, nitrite ions, sulfate ions, bromide ions, fluoride ions, and chloride ions, based on the total weight of the polyimide composition, as determined by total ion chromatography combustion.

[0063] The functionalized polyimide can have greater than 0.05 ppm by weight, preferably greater than 100 ppm by weight, more preferably greater than 500 ppm by weight, and even more preferably greater than 1,000 ppm by weight of non-reactive end groups based on the total weight of the functionalized polyimide, as determined by nuclear magnetic resonance spectroscopy.

[0064] The polyimide composition may further comprise additives generally known in the art for polyimide compositions, provided that the additive(s) are selected so as not to significantly adversely affect the desired properties of the composition, particularly the formation of the poly(imide). Such additives include particulate fillers, fibrous fillers, antioxidants, heat stabilizers, light stabilizers, ultraviolet light stabilizers, ultraviolet light absorbing compounds, near infrared light absorbing compounds, infrared light absorbing compounds, plasticizers, lubricants, mold release agents, antistatic agents, storage stabilizers, antiozonants, optical stabilizers, thickeners, conductivity affecting agents, radiation interfering agents, nucleating agents, antifog agents, antimicrobial agents, metal deactivators, colorants, surface effect additives, radiation stabilizers, flame retardants, anti-drip agents, fragrances, adhesion promoters, flow improvers, coating additives, one or more epoxy resins and different polymers, or combinations thereof. The total amount of the additive composition can be from 0.001 to 20 wt %, or from 0.01 to 10 wt %, based on the total weight of the polyimide composition.

[0065] The functionalized polyimide can be further processed to obtain a powder having a specified maximum particle size. Processing includes grinding, milling, cryogenic grinding, sieving, and combinations thereof. Because the processing does not affect the weight average molecular weight, PDI, and reactive end group content, the treated polyimide powder has these properties consistent with the functionalized polyimide. The treated powder can be sieved to obtain a desired maximum particle size. In one embodiment, the maximum diameter is 1,000 μm. In another embodiment, the maximum absolute particle size is 1 to 1,000 micrometers, preferably 1 to 500 micrometers, more preferably 1 to 100 micrometers, and even more preferably 1 to 75 micrometers, as determined by the pore size of the sieve used to isolate the functionalized polyimide.

[0066] The functionalized polyimide can also be blended with other polymers to produce polymer blends. Polymers that can be used include polyacetals, poly(meth)acrylates, poly(meth)acrylonitriles, polyamides, polycarbonates, polydienes, polyesters, polyethers, polyetheretherketones, polyetherimides, polyethersulfones, polyfluorocarbons, polyfluorochlorocarbons, polyimides, poly(phenylene ethers), polyketones, polyolefins, polyoxazoles, polyphosphazenes, polysiloxanes, polystyrenes, polysulfones, polyurethanes, polyvinyl acetates, polyvinyl chlorides, polyvinylidene chlorides, polyvinyl esters, polyvinyl ethers, polyvinyl ketones, polyvinyl pyridines, polyvinyl pyrrolidones, and copolymers thereof, such as polyetherimide siloxanes, ethylene vinyl acetates, acrylonitrile butadiene styrene, or combinations thereof. Preferably, the functionalized polyimide may be combined with another polymer such as polyarylates, polyamides, polyimides, polyetherimides, poly(amideimides), poly(aryl ethers), phenoxy resins, poly(arylsulfones), poly(ethersulfones), poly(phenylenesulfones), poly(etherketones), poly(etheretherketones), poly(etherketoneketones), poly(arylketones), poly(phenylene ethers), polycarbonates, carboxyl-terminated butadiene-acrylonitrile (CTBN), amine-terminated butadiene-acrylonitrile (ATBN), epoxy-terminated butadiene-acrylonitrile (ETBN), core-shell rubber particles, or combinations thereof.

[0067] A functionalized polyimide can also be incorporated into the curable composition. The curable composition includes a functionalized polyimide (or polyimide composition) and a thermosetting component. In an embodiment, the curable composition includes a functionalized polyimide, another polymer different from the functionalized polyimide, and a thermosetting component. The thermosetting component can include an epoxy component, a phenol / formaldehyde component, a bismaleimide component, a cyanoacrylate component, a polyurethane prepolymer, and combinations thereof. More specifically, the thermosetting component can include an epoxy component, a bismaleimide component, a cyanoacrylate component, or combinations thereof. The epoxy component can be selected from epoxy compounds having a wide range of structures and molecular weights, so long as it contains at least two glycidyl groups per molecule. Exemplary epoxy components include aliphatic, cycloaliphatic, and aromatic epoxy compounds, as well as combinations of the foregoing.

[0068] Exemplary cycloaliphatic epoxy compounds include vinylcyclohexane dioxide, 4(1,2 epoxyethyl)1,2 epoxycyclohexane, 3,4 epoxycyclohexylmethyl(3,4 epoxy)cyclohexanecarboxylate, and 2-(3,4 epoxy)cyclohexyl-5,5 spiro(3,4-epoxy)-cyclohexane-m-dioxane. Exemplary aromatic epoxy compounds include resorcinol diglycidyl ether (or 1,3-bis(2,3-epoxypropoxy)benzene); diglycidyl ether of bisphenol A (or 2,2-bis(4-(2,2-bis(4-(2,3-epoxypropoxy)3-bromophenyl)propane); diglycidyl ether of bisphenol F; triglycidyl p-aminophenol (or 4-(2,3-epoxypropoxy)-N,N-bis(2,3-epoxypropyl)aniline); diglycidyl ether of bromobisphenol A (or 2,2-bis(4-(2,2-bis(4-(2,3-epoxypropoxy)3-bromophenyl)propane); diglycidyl ether of bisphenol F triglycidyl ether of meta-aminophenol (or 3-(2,3-epoxypropoxy)-N,-N-bis12,3-epoxypropyl)aniline); tetraglycidylmethylenediaminodiphenylmethane; N,N,N',N'-tetraglycidyl-4,4'-bisbenzeneamine; low viscosity epoxy cresol resins and low viscosity epoxy novolac resins. The curable composition may further comprise a curing agent. Exemplary curing agents include phenolic resins, acid anhydrides, amines and imidazoles. The curable composition is typically heated to cure, resulting in a thermoset composite.

[0069] Also provided is an article comprising the functionalized polyimide. The article may include a composite, an adhesive, a film, a layer, a coating, an encapsulant, a sealant, a part, a prepreg, a laminate, a casing, a molded part, or a combination thereof.

[0070] The present disclosure is further illustrated by the following non-limiting examples. EXAMPLES

[0071] Using the ingredients in Table 1, Examples 1-4, or comparative examples, were prepared. [Table 1]

[0072] In the following example, M w and M. n is determined by GPC using polystyrene standards unless otherwise indicated.

[0073] Comparative Example 1 The procedure used to prepare the amine-terminated PEI oligomers was described in Example 1 of US Patent Application Publication No. 2006 / 0270825 with the following modifications: 50.05 grams (g) of BPA-DA (94.6 mmol), 14.6 g of mPD (134.5 mmol) and 200 g of oDCB were used. When the reaction was heated to 175° C., a clear homogenous solution (rather than a homogenous slurry) was produced throughout the temperature gradient. Once the target molecular weight was achieved, the mixture was allowed to slowly cool to room temperature. This cooling of the reaction mixture resulted in a more viscous solution that could not be filtered by vacuum filtration to isolate the desired product in powder form. Attempts at filtration were unsuccessful and resulted in clogging of the filter paper.

[0074] Example 1 Synthesis of amine-terminated PEI oligomers To an oven-dried 500 mL three-neck round-bottom flask equipped with a mechanical stirrer, nitrogen adapter, and Dean-Stark condenser was added 50.06 grams (g) of BPA-DA (94.6 mmol), 14.6 g of mPD (134.5 mmol), and 200 g of oDCB. The oil bath temperature was increased to 180° C., and the reaction was refluxed at this temperature for 3-4 hours. A small sample was removed for molecular weight determination. The target M w The reaction was stoichiometrically corrected with DA or amine to obtain M wOnce this was achieved, the reaction mixture was allowed to slowly cool to room temperature (approximately 25 °C), then 150 g of dichloromethane (alternatively, a similar amount of oDCB can be used) was added to it, and the contents were vigorously stirred to obtain an oligomer solution. The oligomer solution was slowly added under high shear mixing conditions to a 2 L beaker containing 800-850 mL of MeOH, resulting in the formation of a precipitate. The resulting fine off-white powder was filtered and washed with MeOH (2 × 50 mL). The isolated solid was dried in a vacuum oven at 130-135 °C for 12 h to give an M of 5,766 g / mol. w The amine-terminated PEI oligomer was obtained as a powder with a polydispersity index (PDI) of 2.37.

[0075] Example 2 Synthesis of amine-terminated PEI oligomers Following the same procedure as in Example 1, 50 g of BPA-DA (94.17 mmol), 12.40 g of mPD (114.67 mmol) and 200 g of oDCB gave a M w and gave an amine-terminated PEI oligomer powder with a PDI of 2.12.

[0076] Example 3 Synthesis of hydroxy-terminated PEI oligomers Following the same procedure as in Example 1, 56.10 g of BPA-DA (107.74 mmol), 7.80 g of mPD (72.13 mmol), 8.01 g of PAP (73.31 mmol) and 200 g of oDCB gave a 4,598 g / mol M w and gave a hydroxy-terminated PEI oligomer powder with a PDI of 2.32.

[0077] Example 4 Synthesis of hydroxy-terminated PEI oligomers Following the same procedure as in Example 1, 52.20 g of BPA-DA (97.47 mmol), 8.97 g of mPD (82.95 mmol), 3.50 g of PAP (32.07 mmol) and 200 g of oDCB gave a 1:1 ratio of 9,214 g / mol M wand gave a hydroxy-terminated PEI oligomer powder with a PDI of 2.42.

[0078] Example 5 Synthesis of amine-terminated PEI oligomers Following the same procedure as in Example 1, 65 g of BPA-DA (121.56 mmol), 14.83 g of mPD (137.14 mmol) and 230 g of oDCB gave a 17,819 g / mol M w and gave an amine-terminated PEI oligomer powder with a PDI of 2.42.

[0079] Example 6 Synthesis of amine-terminated PEI oligomers Following the same procedure as in Example 1, 65 g of BPA-DA (121.37 mmol), 14.12 g of mPD (130.57 mmol) and 230 g of oDCB gave a 26,180 g / mol M w and gave an amine-terminated PEI oligomer powder with a PDI of 2.36.

[0080] Example 7 Synthesis of amine-terminated PEI oligomers Following the same procedure as in Example 1, 64.8 g of BPA-DA (121.00 mmol), 13.84 g of mPD (127.99 mmol) and 230 g of oDCB gave a 32,968 g / mol M w and gave an amine-terminated PEI oligomer powder with a PDI of 2.35.

[0081] Example 8 Synthesis of amine-terminated PEI oligomers A vessel equipped with a mechanical stirrer, condenser, and hot oil jacket, maintained under a nitrogen atmosphere, was charged with 1 equivalent of BPA-DA, 1.16 equivalents of mPD, and oDCB with percent solids kept between 25-50%. The reaction mixture was heated to 180-190°C and the reaction was heated at this temperature for 3-4 hours to allow for imidization and for some of the water of solvent to condense overhead. A small sample of the reaction mixture was removed for molecular weight determination. The target M wTo obtain the desired stoichiometry, the reaction was stoichiometrically corrected with DA or diamine. w Once stoichiometry was achieved, the mixture was then liquefied at 180-350 °C under vacuum. The resulting polymer mass was ground into a fine powder using an appropriate mill grinding device. The isolated functionalized PEI oligomer had a molecular weight of 10,692 g / mol, a PDI of 2.86, a residual oDCB of 560 ppm, a residual mPD of 144.24 ppm, and an amine end group concentration of 525.7 μeq / g of functionalized polyimide.

[0082] Example 9 Synthesis of amine-terminated PEI oligomers A vessel equipped with a mechanical stirrer, condenser, and hot oil jacket, maintained under a nitrogen atmosphere, was charged with 1 equivalent of BPA-DA, 1.16 equivalents of mPD, and oDCB with percent solids kept between 25-50%. The reaction mixture was heated to 180-190°C and the reaction was heated at this temperature for 3-4 hours to allow for imidization and for some of the water of solvent to condense overhead. A small sample of the reaction mixture was removed for molecular weight determination. The target M w The reaction was stoichiometrically corrected with DA or diamine to obtain the desired stoichiometry. w Once stoichiometry was achieved, the mixture was then liquefied at 180-350 °C under vacuum. The resulting polymer mass was ground into a fine powder using an appropriate mill grinding device. The isolated functionalized PEI oligomer had a molecular weight of 10,323 g / mol, a PDI of 2.93, a residual oDCB of 570 ppm, a residual mPD of 133.59 ppm, and an amine end group concentration of 540.12 μeq / g of functionalized polyimide.

[0083] Example 10 Synthesis of amine-terminated PEI oligomers A vessel equipped with a mechanical stirrer, condenser, and hot oil jacket, maintained under a nitrogen atmosphere, was charged with 1 equivalent of BPA-DA, 1.16 equivalents of mPD, and oDCB with percent solids kept between 25-50%. The reaction mixture was heated to 180-190°C and the reaction was heated at this temperature for 3-4 hours to allow for imidization and for some of the water of solvent to condense overhead. A small sample of the reaction mixture was removed for molecular weight determination. The target M w The reaction was stoichiometrically corrected with DA or diamine to obtain the desired stoichiometry. w Once the desired stoichiometry was achieved, the mixture was then liquefied at 180-350 °C under vacuum. The resulting polymer mass was ground into a fine powder using an appropriate mill grinding device. The isolated functionalized PEI oligomer had a molecular weight of 10,414 g / mol, a PDI of 2.84, 1170 ppm residual oDCB, and 270.73 ppm residual mPD.

[0084] Example 11 Synthesis of amine-terminated PEI oligomers A vessel equipped with a mechanical stirrer, condenser, and hot oil jacket, maintained under a nitrogen atmosphere, was charged with 1 equivalent of BPA-DA, 1.11 equivalents of mPD, and oDCB with percent solids kept between 25-50%. The reaction mixture was heated to 180-190°C and the reaction was heated at this temperature for 3-4 hours to allow for imidization and for some of the solvent water to condense overhead. A small sample of the reaction mixture was removed for molecular weight determination. The target M w The reaction was stoichiometrically corrected with DA or diamine to obtain the desired stoichiometry. w Once the desired stoichiometry was achieved, the mixture was then liquefied at 180-350 °C under vacuum. The resulting polymer mass was ground into a fine powder using an appropriate mill grinding device. The isolated functionalized PEI oligomer had a molecular weight of 22,797 g / mol, a PDI of 2.52, and an amine end group concentration of 248.91 μeq / g of functionalized polyimide.

[0085] Example 12 Synthesis of amine-terminated PEI oligomers A vessel equipped with a mechanical stirrer, condenser, and hot oil jacket, maintained under a nitrogen atmosphere, was charged with 1 equivalent of BPA-DA, 1.06 equivalents of mPD, and oDCB with percent solids kept between 25-50%. The reaction mixture was heated to 180-190°C and the reaction was heated at this temperature for 3-4 hours to allow for imidization and for some of the solvent water to condense overhead. A small sample of the reaction mixture was removed for molecular weight determination. The target M w The reaction was stoichiometrically corrected with DA or diamine to obtain the desired stoichiometry. w Once the desired stoichiometry was achieved, the mixture was then liquefied at 180-350 °C under vacuum. The resulting polymer mass was ground into a fine powder using an appropriate mill grinding device. The isolated functionalized PEI oligomer had a molecular weight of 30,986 g / mol, a PDI of 2.36, a residual oDCB of 4574 ppm, and an amine end group concentration of 165.8 μeq / g of functionalized polyimide.

[0086] analysis The functionalized oligomers of Examples 1-4 were characterized. The results are shown in Tables 2-5. The weight average molecular weight (M w ) and number average molecular weight (M n The glass transition temperature (T) was determined by differential scanning calorimetry (DSC) using a second heating cycle from 40 to 300 °C (heating rate of 20 °C / min) according to ASTM D3418. g ) was determined. Thermal stability was determined by thermogravimetric analysis (TGA) from 40 to 800 °C (heating rate of 20 °C / min) under nitrogen and air. Thermal stability is reported as the onset temperature of decomposition at 5%, 10% and 50% weight loss. Hydroxyl and amine end groups were identified and quantified by derivatizing the oligomers with a phosphorus reagent (o-phenylene phosphorochloridite) and analyzing by phosphorus-31 nuclear magnetic resonance spectroscopy ( 31 Quantification was performed by 1 P NMR.

[0087] All residual levels of metals (sodium, potassium, calcium, zinc, aluminum, nickel, copper, phosphorus, titanium, magnesium, manganese, silicon, chromium, molybdenum and iron) in the following examples are determined by the Inductively Coupled Plasma-Digestion (ICP-Dig) method using an ICP spectrometer equipped with axial and / or radial viewing, a Gem Cone and / or ultrasonic nebulizer, and a microwave digestion system with appropriate sample digestion vessel set. Samples are prepared using concentrated nitric acid, hydrochloric acid, sulfuric acid and / or hydrofluoric acid - ultrapure grade.

[0088] Residual levels of anions (sulfate, chloride, bromide, fluoride, phosphate, nitrate, nitrite) present in polyimide oligomer samples were measured by extraction-ion chromatography (IC-Extract). Polyimide oligomer samples were dissolved in methylene chloride. The solution was then extracted with deionized water, and the aqueous extract was then analyzed by total ion chromatography combustion (IC-Total).

[0089] Table 2 shows the molecular weights of the PEI oligomers before and after precipitation using an antisolvent (MeOH). [Table 2]

[0090] The results in Table 2 showed an increase in molecular weight upon precipitation for the amino-terminated PEI oligomers of Examples 1 and 2, and a decrease in molecular weight for the hydroxyl-terminated PEI oligomers of Examples 3 and 4. Further analysis of the filtrate containing a blend of oDCB, DCM, and MeOH showed that lower molecular weight species and unreacted monomers were removed during the precipitation and product isolation. Amine analysis by UPLC showed less than 1 ppm residual amines present in the anti-solvent from the precipitated oligomer product.

[0091] Table 3 shows the glass transition temperatures of the PEI oligomers and comparative oligomers. [Table 3]

[0092] Examples 2 and 4 revealed comparable glass transition temperatures (Tg) for amino-terminated and hydroxyl-terminated PEI oligomers. A similar trend was not observed in Examples 1 and 3, where the lower molecular weight amine-terminated PEI oligomers had Tg nearly 20° C. lower than the lower molecular weight hydroxyl-terminated PEI oligomers. Furthermore, as the molecular weight of the amino-terminated PEI oligomers increased, the glass transition temperature (T g ) was observed. The Tg of the comparative PEI polymer and polyethersulfone (PESU) oligomer were higher than those of Examples 1-7 due to their higher molecular weight.

[0093] Table 4 shows the thermal stability of PEI oligomers and comparative oligomers. [Table 4]

[0094] Thermogravimetric analysis was used to determine the onset temperatures at which 5%, 10% and 50% weight loss occurred. The onset temperatures for 5% and 10% weight loss with the PEI oligomers of Examples 1-4 were lower than those for the comparative PEI and PESU oligomers. Surprisingly, the lower molecular weight hydroxyl-terminated PEI oligomer (Example 3) had a higher onset temperature for 5% and 10% weight loss, respectively, compared to the higher molecular weight hydroxyl-terminated PEI oligomer (Example 4). The opposite trend was observed for the amino-terminated PEI oligomers, with Example 1 having a lower onset temperature for 5% and 10% weight loss, respectively, compared to Example 2. In summary, Examples 1-4 were found to have good thermal stability at high temperatures (>350°C).

[0095] Table 5 shows the reactive end group analysis of the PEI oligomers of Examples 1 to 4 (in the table, "ND" stands for not detected). [Table 5]

[0096] Phosphorus functionalization of the reactive end groups of the PEI oligomers was utilized to convert the end groups of the PEI oligomers of Examples 1 to 4 into 31 The molecular weights of the PEI oligomers were quantified by P NMR spectroscopy. The amine-terminated oligomers of Examples 1 and 2 exhibited two distinct peaks in the NMR spectrum, corresponding to aromatic amines and carboxylic acids. The hydroxyl-terminated oligomers of Examples 3 and 4 exhibited three distinct peaks, corresponding to aromatic amines, carboxylic acids, and phenols (hydroxyl groups). As the molecular weight increased, the amount of aromatic amino end groups decreased for the amino-terminated PEI oligomers of Examples 1 and 2. Similarly, as the molecular weight increased, the amount of hydroxyl end groups decreased for the hydroxyl-terminated PEI oligomers of Examples 3 and 4.

[0097] The present disclosure further includes the following non-limiting aspects.

[0098] Aspect 1. Substituted or unsubstituted C 4-40 Bis-anhydrides and substituted or unsubstituted C 1-40 1. A polyimide composition comprising a functionalized polyimide prepared from an organic diamine and, optionally, an organic compound comprising at least two functional groups per molecule, wherein a first functional group is reactive to an anhydride group, an amine group, or a combination thereof, and the first functional group is different from a second functional group, the functionalized polyimide having a structure represented by the formula (C 1-40 Hydrocarbylene)-NH 2 , (C 1-40 hydrocarbylene)-OH, (C 1-40 hydrocarbylene)-SH, (C 4-40and wherein G is an anhydride group, a carboxylic acid, a carboxylic acid ester, or a combination thereof; the functionalized polyimide has a total reactive end group concentration of 50 to 1,500 microequivalents / gram of the functionalized polyimide, preferably 50 to 1,000 microequivalents / gram, and more preferably 50 to 750 microequivalents / gram; the polyimide composition has a residual organic diamine of 0.05 to 1,000 ppm by weight, preferably 0.05 to 500 ppm by weight, and more preferably 0.05 to 250 ppm by weight, based on the total weight of the polyimide composition; and the functionalized polyimide is obtained by precipitation or devolatilization from solution using an organic antisolvent.

[0099] Aspect 2. The polyimide composition according to aspect 1, further comprising: a residual solvent of 0.05 to 1,000 ppm by weight, preferably 0.05 to 500 ppm by weight, and more preferably 0.05 to 250 ppm by weight, based on the total weight of the polyimide composition; a residual bis-anhydride and a residual organic compound of 0.05 to 1,000 ppm by weight, preferably 0.05 to 750 ppm by weight, and more preferably 0.05 to 500 ppm by weight, based on the total weight of the polyimide composition; a total content of a residual bis-anhydride, a residual organic diamine, and a residual organic compound of 0.05 to 3,000 ppm by weight, preferably 0.05 to 2,000 ppm by weight, more preferably 0.05 to 1,000 ppm by weight, and even more preferably 0.05 to 500 ppm by weight, based on the total weight of the polyimide composition; ppm, 0.1 to 75 ppm by weight, 0.1 to 25 ppm by weight of sodium, potassium, calcium, zinc, aluminum, nickel, copper, phosphorus, titanium, magnesium, manganese, silicon, chromium, cobalt and iron; a total content of sodium, potassium, calcium, zinc, aluminum, nickel, copper, phosphorus, titanium, magnesium, manganese, silicon, chromium, cobalt and iron of 0.1 to 200 ppm by weight, 0.1 to 100 ppm by weight, 0.1 to 50 ppm by weight, 0.1 to 25 ppm by weight based on the total weight of the polyimide composition; or a polyimide composition containing one or more of phosphate ions, nitrate ions, nitrite ions, sulfate ions, bromide ions, fluoride ions and chloride ions of 0.3 to 50 ppm by weight, preferably 0.3 to 25 ppm by weight, respectively, based on the total weight of the polyimide composition.

[0100] Aspect 3. Substituted or unsubstituted C 4-40 Bis-anhydrides and substituted or unsubstituted C 1-40 A functionalized polyimide prepared from an organic diamine and, optionally, an organic compound, the organic compound comprising at least two functional groups per molecule, a first functional group being reactive towards an anhydride group, an amine group or a combination thereof, the first functional group being different from the second functional group, the functionalized polyimide being represented by the formula (C 1-40 Hydrocarbylene)-NH 2 , (C1-40 hydrocarbylene)-OH, (C 1-40 hydrocarbylene)-SH, (C 4-40 wherein G is an anhydride group, a carboxylic acid, a carboxylic acid ester, or a combination thereof, said functionalized polyimide having a total reactive end group concentration of 50 to 1,500 microequivalents per gram of functionalized polyimide, preferably 50 to 1,000 microequivalents per gram, and more preferably 50 to 750 microequivalents per gram, and said polyimide composition has a residual organic diamine of 0.05 to 1,000 ppm by weight, preferably 0.05 to 500 ppm by weight, and more preferably 0.05 to 250 ppm by weight, based on the total weight of the polyimide composition.

[0101] Aspect 4. The functionalized polyimide of aspect 3, comprising: a weight average molecular weight, as determined by GPC, of ​​5,000 to 45,000 grams / mole, preferably 10,000 to 45,000 g / mol, more preferably 15,000 to 35,000 g / mol; a maximum absolute particle size, as determined by the pore size of the sieve used to isolate the functionalized polyimide, of less than 1,000 μm, preferably less than 500 μm, more preferably less than 100 μm, and even more preferably less than 75 micrometers; an average reactive end group functionality, defined as the average number of hydroxyl, amino, and carboxylic acid end groups per polyimide chain, of greater than 0.75, preferably greater than 0.9, more preferably greater than 1.1, and even more preferably greater than 1.5; and an ASTM a glass transition temperature of 155-280°C, preferably 175-280°C, more preferably 190-280°C, as determined by differential scanning calorimetry in accordance with D3418; an amide-acid concentration of 0.5-5000 microequivalents per gram of the functionalized polyimide, preferably 0.5-1000 μeq / g, more preferably 0.5-500 μeq / g; a polydispersity of less than 4.5, preferably less than 4.0, more preferably less than 3.0, even more preferably less than 2.80, as determined by gel permeation chromatography using polystyrene standards, or a non-reactive end group of more than 0.05 ppm by weight, preferably more than 100 ppm by weight, more preferably more than 500 ppm by weight, even more preferably more than 1,000 ppm by weight, based on the total weight of the functionalized polyimide.

[0102] Embodiment 5. The functionalized polyimide of any one of embodiments 1 to 4, comprising units of formula (4) as described herein.

[0103] Embodiment 6. The functionalized polyimide of embodiment 5, wherein each R is independently a divalent radical of formula (2a) described herein and each V is independently a divalent radical of formula [ka] in which W is as described herein or is a group of formula -OZO-; Z is [ka] (In the formula, R a and R b is a tetravalent group of a functionalized polyimide,

[0104] Embodiment 7. The functionalized polyimide according to any one of embodiments 1 to 6, wherein the functionalized polyimide is a polyetherimide comprising units of formula (5a), where R and Z are as defined in embodiment 6.

[0105] Embodiment 8. A method for producing a functionalized polyimide according to any one of embodiments 1 to 7, comprising reacting a substituted or unsubstituted C under reaction conditions effective to provide the functionalized polyimide. 4-40 Bis-anhydrides and substituted or unsubstituted C 1-40 A method comprising reacting an organic diamine and, optionally, an organic compound.

[0106] Embodiment 9. The method of embodiment 8, wherein the reacting step is carried out in a first solvent to provide a mixture of the functionalized polyimide and the first solvent, and further comprising treating the mixture under conditions effective to isolate the functionalized polyimide, or contacting the mixture with a second solvent under conditions effective to isolate the functionalized polyimide by precipitation.

[0107] Aspect 10. The method of aspect 9, wherein the first solvent is dichlorobenzene, N-methylpyrrolidone, dimethylacetamide, dimethylformamide, chlorobenzene, anisole, veratrole, dichlorotoluene, trichlorobenzene, diphenyl sulfone, diphenyl ether, phenetole, dimethyl sulfoxide, dimethyl sulfone, sulfolane, cresol, benzonitrile, or a combination thereof, preferably the first solvent is ortho-dichlorobenzene.

[0108] Aspect 11. The method of aspect 9 or aspect 10, wherein the second solvent is C 1-6 Alkyl alcohol, C 3-6Alkyl ketones, C 5-6 Cycloalkyl ketones, C 3-6 Alkyl ester, C 5-8 Alkane, C 5-7 Cycloalkane, C 2-6 Aliphatic nitrile, C 2-6 Acyclic ethers, C 4-7 A process wherein the second solvent is a cyclic ether, water or a combination thereof, preferably wherein the second solvent is methanol, isopropanol, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, acetone, acetonitrile, tetrahydrofuran or a combination thereof.

[0109] Embodiment 12. The method of embodiment 8, wherein the reacting step comprises reacting a substituted or unsubstituted C under conditions effective to provide a polyimide oligomer. 4-40 Bis-anhydrides and substituted or unsubstituted C 1-40 and melt mixing the polyimide oligomer with an organic compound under conditions effective to provide a functionalized polyimide.

[0110] Embodiment 13. The method of embodiment 8, wherein the reacting step comprises reacting a substituted or unsubstituted C 4-40 Bis-anhydrides and substituted or unsubstituted C 1-40 A method comprising melt polymerizing an organic diamine and, optionally, an organic compound to provide a functionalized polyimide.

[0111] Embodiment 14. The method of any one of embodiments 8 to 13, wherein the organic compound is of 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 an anhydride group, a carboxylic acid or a carboxylic acid ester, and each L is the same or different and each independently is a substituted or unsubstituted C 1-10 Alkylene or substituted or unsubstituted C 6-20 Arylene, Q2 -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 C 6-20 and each n is independently 0 or 1), more preferably wherein the organic compound is para-aminophenol, meta-aminophenol, ortho-aminophenol, 4-hydroxy-4'-aminodiphenylpropane, 4-hydroxy-4'-aminodiphenylmethane, 4-amino-4'-hydroxydiphenylsulfone, 4-hydroxy-4'-aminodiphenylether, 2-hydroxy-4-aminotoluene, 4-aminothiophenol, 3-aminothiophenol, 2-aminothiophenol, 4-hydroxyphthalic anhydride, 3-hydroxyphthalic anhydride, 6-amino-2-naphthol, 5-amino-2-naphthol, 8-amino-2-naphthol, 3-amino-2-naphthol, or a combination thereof.

[0112] Example 15. A curable composition comprising the functionalized polyimide of any one of Examples 1 to 7 and a thermosetting component.

[0113] The compositions, methods and articles can alternatively comprise, consist of, or consist essentially of any suitable components or steps disclosed herein. The compositions, methods and articles can additionally or alternatively be constructed to be free of, or substantially free of, any steps, components, materials, ingredients, adjuvants or species that are not otherwise necessary to the function or accomplishment of the purpose of the compositions, methods and articles.

[0114] The singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. "Or" means "and / or" unless the context clearly dictates otherwise. Terms such as "first," "second," and the like do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. References throughout this specification to "an embodiment" mean that a particular element described in connection with this embodiment is included in at least one embodiment described herein and may or may not be present in other embodiments. The described elements can be combined in any suitable manner in the various embodiments. "Combinations" include blends, mixtures, alloys, reaction products, and the like. As used herein, "combinations thereof" is open-ended and refers to combinations including one or more of the listed items, optionally with one or more similar items not listed.

[0115] All ranges disclosed herein are inclusive, and the endpoints are independently combinable with each other. The endpoints of all ranges directed to the same component or property are inclusive and independently combinable. The disclosure of a narrower range or more specific group in addition to a broader range does not disclaim the broader range or larger group.

[0116] Unless otherwise defined, technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this application belongs. All cited patents, patent applications and other references are incorporated by reference in their entirety into this application. However, if the terms of this application contradict or conflict with the terms of the incorporated references, the terms of this application shall take precedence over the conflicting terms of the incorporated references.

[0117] As used herein, the term "hydrocarbyl" includes groups containing carbon, hydrogen, and optionally one or more heteroatoms (e.g., 1, 2, 3, or 4 atoms such as halogen, O, N, S, P, or Si). "Alkyl" means a branched or straight-chain saturated monovalent hydrocarbon group, such as methyl, ethyl, i-propyl, and n-butyl. "Alkylene" means a straight-chain or branched saturated divalent hydrocarbon group, such as methylene (-CH 2 -) or propylene (-(CH 2 ) 3 "Alkenyl" and "alkenylene" refer to a monovalent or divalent, respectively, straight or branched chain hydrocarbon radical having at least one carbon-carbon double bond, such as ethenyl (-HC=CH 2 ) or propenylene (-HC(CH 3 )=CH 2 "Alkynyl" means a straight or branched chain monovalent hydrocarbon radical having at least one carbon-carbon triple bond, such as ethynyl. "Alkoxy" means an alkyl radical attached through an oxygen (i.e., alkyl-O-), such as methoxy, ethoxy, and sec-butyloxy. "Cycloalkyl" and "cycloalkylene" refer to groups of the formula -C n H 2n-x and -C n H 2n-2x- (where x is the number of cyclizations), respectively. "Aryl" means a monovalent monocyclic or polycyclic aromatic group (e.g., phenyl or naphthyl). "Arylene" means a divalent monocyclic or polycyclic aromatic group (e.g., phenylene or naphthylene). "Arylene" means a divalent aryl group. "Alkylaryl" means an aryl group substituted with an alkyl group. "Arylalkyl" means an alkyl group substituted with an aryl group (e.g., benzyl). The prefix "halo" means a group or compound containing one or more halogen (F, Cl, Br or I) substituents, which may be the same or different. The prefix "hetero" means a group or compound containing at least one ring member that is a heteroatom (e.g., 1, 2 or 3 heteroatoms), where each heteroatom is independently N, O, S or P.

[0118] Unless a substituent is specifically indicated otherwise, each of the foregoing groups may be unsubstituted or substituted, provided that the substitution does not significantly adversely affect the synthesis, stability, or use of the compound. "Substituted" means that the compound, group, or atom is substituted in place of hydrogen with at least one (e.g., 1, 2, 3, or 4) substituent, where each substituent is independently selected from the group consisting of nitro (-NO 2 ), cyano (-CN), hydroxy (-OH), halogen, thiol (-SH), thiocyano (-SCN), C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 1-6 Haloalkyl, C 1-9 Alkoxy, C 1-6 Haloalkoxy, C 3-12 Cycloalkyl, C 5-18 Cycloalkenyl, C 6-12 Aryl, C 7-13 Arylalkyl (e.g., benzyl), C 7-12 Alkylaryl (e.g., toluyl), C 4-12 Heterocycloalkyl, C 3-12 Heteroaryl, C 1-6Alkylsulfonyl (-S(=O) 2 -alkyl), C 6-12 Arylsulfonyl (-S(=O) 2 -aryl) or tosyl (CH 3 C 6 H 4 SO 2 -), but the normal valence of the substituted atom is not exceeded, and the substitution does not significantly adversely affect the preparation, stability, or desired properties of the compound. The number of carbon atoms shown in the group is exclusive of all substituents. For example, -CH 2 CH 2 CN is a nitrile-substituted C 2 It is an alkyl group.

[0119] While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are not presently foreseen or that cannot be presently foreseen will occur to the applicant or those skilled in the art. Accordingly, the appended claims, as filed and as they may be amended, are intended to cover all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

1. Substituted or unsubstituted C ４－４０ Bis anhydride, Substituted or unsubstituted C １－４０ An organic diamine, an organic compound comprising at least two functional groups per molecule, optionally wherein a first functional group is reactive to an anhydride group, an amine group, or a combination thereof, said first functional group being different from a second functional group; 1. A polyimide composition comprising a functionalized polyimide prepared from The functionalized polyimide 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 polyimide has a total reactive end group concentration of 50 to 1,500 microequivalents per gram of the functionalized polyimide, preferably 50 to 1,000 microequivalents per gram, and more preferably 50 to 750 microequivalents per gram, as determined by nuclear magnetic resonance spectroscopy; the polyimide composition having 0.05 to 1,000 ppm by weight, preferably 0.05 to 500 ppm by weight, and more preferably 0.05 to 250 ppm by weight, of residual organic diamine based on the total weight of the polyimide composition, as determined by ultra-performance liquid chromatography; A polyimide composition, wherein the functionalized polyimide is obtained by precipitation or devolatilization from a solution using an organic antisolvent.

2. 2. The polyimide composition according to claim 1, 0.05 to 5,000 ppm by weight, preferably 0.05 to 1000 ppm by weight, more preferably 0.05 to 500 ppm by weight, and even more preferably 0.05 to 250 ppm by weight of residual solvent based on the total weight of the polyimide composition, as determined by gas chromatography; 0.05 to 1,000 ppm by weight of residual bis-anhydrides and residual organic compounds, each of which is determined by ultra-performance liquid chromatography, based on the total weight of said polyimide composition, preferably 0.05 to 750 ppm by weight, and more preferably 0.05 to 500 ppm by weight; a total content of residual bis-anhydrides, residual organic diamines and residual organic compounds of 0.05 to 3,000 ppm by weight, preferably 0.05 to 2,000 ppm by weight, more preferably 0.05 to 1,000 ppm by weight, and even more preferably 0.05 to 500 ppm by weight, based on the total weight of the polyimide composition, as determined by ultra-performance liquid chromatography; 0.1 to 100 ppm by weight, 0.1 to 75 ppm by weight, and 0.1 to 25 ppm by weight of sodium, potassium, chromium, magnesium, manganese, cobalt, titanium, silicon, molybdenum, calcium, zinc, aluminum, nickel, copper, phosphorus, and iron, respectively, based on the total weight of the polyimide composition, as determined by inductively coupled plasma spectroscopy; a total content of sodium, potassium, chromium, magnesium, manganese, cobalt, titanium, silicon, molybdenum, calcium, zinc, aluminum, nickel, copper, phosphorus, and iron of 0.1 to 200 ppm by weight, 0.1 to 100 ppm by weight, 0.1 to 50 ppm, or 0.1 to 25 ppm by weight based on the total weight of the polyimide composition, as determined by inductively coupled plasma spectroscopy; or 0.3 to 500 ppm by weight, 0.3 to 250 ppm by weight, respectively, of phosphate ions, nitrite ions, sulfate ions, bromide ions, fluoride ions, and chloride ions, based on the total weight of the polyimide composition, as determined by total ion chromatography combustion. A polyimide composition comprising one or more of the following:

3. Substituted or unsubstituted C ４－４０ Bis-anhydrides and substituted or unsubstituted C １－４０ A functionalized polyimide prepared from an organic diamine and, optionally, an organic compound, the organic compound comprises at least two functional groups per molecule, a first functional group being reactive towards an anhydride group, an amine group or a combination thereof, the first functional group being different from the second functional group; The functionalized polyimide 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 polyimide has a total reactive end group concentration of 50 to 1,500 microequivalents per gram of the functionalized polyimide, preferably 50 to 1,000 microequivalents per gram, and more preferably 50 to 750 microequivalents per gram, as determined by nuclear magnetic resonance spectroscopy; 1. A functionalized polyimide composition characterized in that the polyimide composition has a residual organic diamine content of 0.05 to 1,000 ppm by weight, preferably 0.05 to 500 ppm by weight, and more preferably 0.05 to 250 ppm by weight, based on the total weight of the polyimide composition, as determined by ultra performance liquid chromatography.

4. 4. The functionalized polyimide of claim 3, A weight average molecular weight, as determined by gel permeation chromatography using polystyrene standards, of from 5,000 to 45,000 grams / mole, preferably from 10,000 to 45,000 grams / mole, more preferably from 15,000 to 35,000 grams / mole; a maximum absolute particle size of from 1 to 1,000 micrometers, preferably from 1 to 500 micrometers, more preferably from 1 to 100 micrometers, and even more preferably from 1 to 75 micrometers, as determined by the pore size of the sieve used to isolate said functionalized polyimide; an average reactive end group functionality, defined as the average number of hydroxyl, amino and carboxylic acid end groups per polyimide chain, greater than 0.75, preferably greater than 0.9, more preferably greater than 1.1, and even more preferably greater than 1.5; a glass transition temperature of 155-280°C, preferably 175-280°C, more preferably 190-280°C, as determined by differential scanning calorimetry according to ASTM D3418; an amide-acid concentration of said functionalized polyimide, as determined by nuclear magnetic resonance spectroscopy, of 0.5 to 5000 microequivalents / gram, preferably 0.5 to 1000 microequivalents / gram, more preferably 0.5 to 500 microequivalents / gram; Polydispersity less than 4.5, preferably less than 4.0, more preferably less than 3.0, even more preferably less than 2.80 or 1. A functionalized polyimide having greater than 0.05 ppm by weight of non-reactive end groups, based on the total weight of said functionalized polyimide, as determined by nuclear magnetic resonance spectroscopy, preferably greater than 100 ppm by weight, more preferably greater than 500 ppm by weight, and even more preferably greater than 1,000 ppm by weight.

5. 5. The functionalized polyimide of claim 1, wherein the functionalized polyimide has the formula 【Chemistry 1】 (In the formula, Each R is the same or different and independently represents a substituted or unsubstituted divalent C １－２０ an organic group, preferably a substituted or unsubstituted divalent C ６－２０ Aromatic hydrocarbon group, substituted or unsubstituted C ２－２０ Alkylene group or substituted or unsubstituted C ３－８ is a cycloalkylene group, Each V is the same or different and independently represents a substituted or unsubstituted tetravalent C ４－４０ Hydrocarbon group, preferably substituted or unsubstituted C ６－２０ Aromatic hydrocarbon group, substituted or unsubstituted C ５－２０ Heteroaromatic groups, substituted or unsubstituted C ４－２０ an aliphatic group or a substituted or unsubstituted C ４－８ It is an alicyclic group. A functionalized polyimide comprising the units:

6. 6. The functionalized polyimide of claim 5, Each R independently represents the formula 【Chemistry 2】 (In the formula, Q １ is -O-, -S-, -C(O)-, -SO ２ -, -SO-, -P(R ’ )(=O)-(wherein, R ’ is C １－８ Alkyl or C ６－１２ aryl), -C ｙ H ２ｙ - (wherein y is an integer from 1 to 5) or a halogenated derivative thereof or -(C ６ H １０ ) ｚ -, where z is an integer from 1 to 4; Each V independently represents the formula 【Chemistry 3】 (In the formula, W is a single bond, —O—, —S—, —C(O)—, or —SO ２ -, -SO-, C １－１８ Hydrocarbylene group, -P(R ’ )(=O)-(wherein, R ’ 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 a halogenated derivative thereof or a group of formula -O-Z-O-, 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 is an alkyl group, 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)- or C １－１８ is a tetravalent group of an organic bridging group, Preferably, each R is independently meta-phenylene, ortho-phenylene, para-phenylene, bis(4,4'-phenylene)sulfonyl, bis(3,4'-phenylene)sulfonyl, bis(3,3'-phenylene)sulfonyl, bis(4,4'-phenylene)oxy, bis(3,4'-phenylene)oxy, bis(3,3'-phenylene)oxy or combinations thereof, and each Z is 2,2'-(4-phenylene)isopropylidene.

7. 7. The functionalized polyimide of claim 1, having the formula 【Chemistry 5】 (wherein R and Z are as defined in claim 6).

1. A functionalized polyimide, characterized in that it is a polyetherimide comprising units of:

8. A method for producing a functionalized polyimide according to any one of claims 1 to 7, comprising the steps of: The substituted or unsubstituted C under reaction conditions effective to provide a functionalized polyimide. ４－４０ A bis-anhydride and the substituted or unsubstituted C １－４０ 13. A method comprising reacting an organic diamine with, optionally, said organic compound.

9. 10. The method of claim 8, wherein the reacting step is carried out in a first solvent to provide a mixture of the functionalized polyimide and the first solvent; treating the mixture under conditions effective to isolate the functionalized polyimide; or contacting the mixture with a second solvent under conditions effective to isolate the functionalized polyimide by precipitation. The method further comprising:

10. 10. The method of claim 9, wherein the first solvent is dichlorobenzene, N-methylpyrrolidone, dimethylacetamide, dimethylformamide, chlorobenzene, anisole, veratrole, dichlorotoluene, trichlorobenzene, diphenylsulfone, diphenyl ether, phenetole, dimethylsulfoxide, dimethylsulfone, sulfolane, cresol, benzonitrile or a combination thereof, preferably the first solvent is ortho-dichlorobenzene.

11. 11. The method of claim 9 or 10, wherein the second solvent is １－６ Alkyl alcohol, C ３－６ Alkyl ketones, C ５－６ Cycloalkyl ketones, C ３－６ Alkyl esters, C ５－８ Alkane, C ５－７ Cycloalkane, C ２－６ Aliphatic nitriles, C ２－６ Acyclic ethers, C ４－７ cyclic ethers or combinations thereof; Preferably, the second solvent is methanol, isopropanol, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, acetone, acetonitrile, tetrahydrofuran or a combination thereof.

12. 9. The method of claim 8, wherein the step of reacting comprises: said substituted or unsubstituted C under conditions effective to provide a polyimide oligomer. ４－４０ A bis-anhydride and the substituted or unsubstituted C １－４０ and polymerizing an organic diamine. melt mixing said polyimide oligomer with said organic compound under conditions effective to provide said functionalized polyimide; The method according to claim 1, further comprising:

13. 9. The method of claim 8, wherein the step of reacting comprises the step of: ４－４０ A bis-anhydride and the substituted or unsubstituted C １－４０ a step of melt polymerizing an organic diamine and, optionally, said organic compound to provide said functionalized polyimide.

14. 14. The method according to any one of claims 8 to 13, wherein the organic compound is represented by the formula R ｃ -L ｎ -Q ２ -L ｎ -R ｄ (In the formula, R ｃ and R ｄ are different and each independently represents -OH, -NH ２ , -SH or an anhydride group, 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 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 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'-hydroxydiphenylsulfone, 4-hydroxy-4'-aminodiphenylether, 2-hydroxy-4-aminotoluene, 4-aminothiophenol, 3-aminothiophenol, 2-aminothiophenol, 4-hydroxyphthalic anhydride, 3-hydroxyphthalic anhydride, 6-amino-2-naphthol, 5-amino-2-naphthol, 8-amino-2-naphthol, 3-amino-2-naphthol or a combination thereof.

15. A curable composition comprising the functionalized polyimide of any one of claims 1 to 7 and a thermosetting component.

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