3, 3 '-aromatic bis (etherimide), polyetherimide thereof and preparation method of 3, 3'-aromatic bis (etherimide)

Abstract

A process for the preparation of a 3-nitro-N-(C1-C13 alkyl) phthalimide composition comprising reacting 3-nitrophthalic acid, optionally in the presence of a solvent, to provide 3-nitro-phthalic anhydride, and reacting 3-nitro-N-(C1-C13 alkyl) phthalimide, optionally in the presence of a solvent, to provide 3-nitro-phthalic anhydride, optionally in the presence of a solvent, to provide 3-nitro-N-(C1-C13 alkyl) phthalimide. A 3-nitro-phthalic anhydride is reacted with a C1-13 alkyl amine to provide a 3-nitro-N-(C1-13 alkyl) phthalimide composition comprising a 3-nitro-N-(C1-13 alkyl) phthalimide and, optionally, a 4-nitro-N-(C1-13 alkyl) phthalimide. The 3-nitro-N-(C1-13 alkyl) phthalimide composition is characterized in that the 3-nitro-N-(C1-13 alkyl) phthalimide composition is obtained by reacting the 3-nitro-N-(C1-13 alkyl) phthalimide with a C1-13 alkyl amine. The 3-nitro-N-(C1-C13 alkyl) phthalimide composition may have an undetectable level of 4-nitro-N-(C1-C13 alkyl) phthalimide, and thus, the polyetherimides, which are ultimately derived from the 3-nitro-N-(C1-C13 alkyl) phthalimide composition, may be enriched in 3, 3 'bonds and / or exclude 3, 4' and 4 '4 bonds. The disclosed polyetherimides can have improved flowability and a reduced yellowness index.

Description

Technical Field

[0001] The present disclosure relates to aromatic bis(etherimides), and in particular to 3,3'-aromatic bis(etherimides), polyetherimides thereof, preparation methods and uses thereof. Background Art

[0002] Polyetherimides are a class of high-performance polymers that can be processed to prepare molded articles, fibers, films, foams, and the like. Polyetherimides further have high strength, toughness, heat resistance, modulus, and a wide range of chemical resistance and are therefore widely used in a variety of industries, such as automotive, telecommunications, aerospace, electrical / electronics, transportation, and healthcare. Polyetherimides have shown versatility in a variety of manufacturing methods, demonstrating suitability for techniques including injection molding, extrusion, and thermoforming to prepare articles.

[0003] Polyetherimides can be prepared from aromatic bis(etherimide) monomers. Conventional methods for preparing aromatic bis(etherimide) monomers often result in isomeric mixtures, including 3,3'-aromatic bis(etherimide), 3,4'-aromatic bis(etherimide), and 4,4'-aromatic bis(etherimide). The flow properties of polyetherimides derived from a mixture of aromatic bis(etherimide) isomers are related to the ratio of 3,3'-aromatic bis(etherimide) to 3,4'-aromatic bis(etherimide) and 4,4'-aromatic bis(etherimide). Polyetherimides derived from aromatic bis(etherimide) isomer mixtures rich in 3,4'-bis(etherimide) and 4,4'-aromatic bis(etherimide) generally have lower flow rates than polyetherimides having smaller amounts of 3,4'-aromatic bis(etherimide) and 4,4'-aromatic bis(etherimide) in the aromatic bis(etherimide) isomer mixture. Thus, in applications where specific flow properties are desired, there is a need for polyetherimides obtained from monomer mixtures rich in 3,3'-aromatic bis(etherimide). Thus, there remains a need in the art for methods of preparing polyetherimides in which the presence of 3,4'-aromatic bis(etherimide) and 4,4'-aromatic bis(etherimide) in the monomer mixture can be minimized, controlled to a predetermined level, or eliminated. Summary of the invention

[0004] By a method for preparing 3-nitro-N-(C 1-13 The above and other shortcomings of the art are met by a method for preparing a phthalimide composition comprising reacting 3-nitrophthalic acid, optionally in the presence of a solvent, under conditions effective to provide a reaction mixture comprising 3-nitrophthalic anhydride and water, and wherein during the reaction, water is removed from the reaction mixture, and optionally in the presence of a solvent, under conditions effective to provide a reaction mixture comprising 3-nitro-N-(C 1-13alkyl)phthalimide and optionally 4-nitro-N-(C 1-13 3-nitro-N-(C-alkyl)phthalimide 1-13 Under the conditions of the alkyl) phthalimide composition, 3-nitro-phthalic anhydride and C 1-13 Alkylamine combinations.

[0005] 3-Nitro-N-(C 1-13 The composition comprises 3-nitro-N-(C 1-13 alkyl)phthalimide and optionally 4-nitro-N-(C 1-13 Alkyl)phthalimide, of which 3-nitro-N-(C 1-13 The composition comprises less than 20,000 ppm, less than 10,000 ppm, less than 5000 ppm, less than 2500 ppm, or less than 1000 ppm of 4-nitro-N-(C 1-13 Alkyl)phthalimide.

[0006] A method for preparing N-(C 1-13 A method for preparing a composition of an aromatic bis(etherimide) having an N-(C 1-13 Alkyl)-3,3'-aromatic bis(etherimide) composition (comprising N-(C 1-13 alkyl)-3,3-aromatic bis(etherimide)) and optionally, N-(C 1-13 Alkyl)-3,4'-aromatic bis(ether imide), N-(C 1-13 alkyl)-4,4'-aromatic bis(etherimide), or a combination thereof, wherein when present, N-(C 1-13 Alkyl)-3,4'-aromatic bis(ether imide), N-(C 1-13 alkyl)-4,4'-aromatic bis(etherimide), or a combination thereof.

[0007] The 3,3'-aromatic bis(etherimide) composition comprises 3,3'-aromatic bis(etherimide) and optionally 3,4'-aromatic bis(etherimide), 4,4'-aromatic bis(etherimide), or a combination thereof, wherein the 3,3'-aromatic bis(etherimide) composition comprises less than 20,000 ppm, less than 10,000 ppm, less than 5000 ppm, less than 2500 ppm, or less than 1000 ppm of 3,4'-aromatic bis(etherimide), 4,4'-aromatic bis(etherimide), or a combination thereof.

[0008] A method for making a polyetherimide comprises contacting a 3,3'-aromatic bis(ether phthalic anhydride) composition prepared by the method described above with phthalic anhydride in the presence of a catalyst and under conditions effective to provide a 3,3'-aromatic bis(ether phthalic anhydride) composition comprising 3,3'-aromatic bis(ether phthalic anhydride) of formula (Va) and, optionally, 3,4'-aromatic bis(ether phthalic anhydride) of formula (Vb), 4,4'-aromatic bis(ether phthalic anhydride) of formula (Vc), or a combination thereof.

[0009]

[0010] Where Z is optionally replaced by 1-6 C 1-8 Alkyl groups, 1-8 halogen atoms, or a combination thereof substituted aromatic C 6-24 Monocyclic or polycyclic moiety; N-(C 1-13 The composition is contacted with an organic diamine of formula (H2N-R-NH2), wherein R is C 6-20 Aromatic hydrocarbon groups or their halogenated derivatives, straight chain or branched C 2-20 Alkylene group or its halogenated derivative, C 3-8 A cycloalkylene group or a halogenated derivative thereof, or a combination thereof.

[0011] Another method for making a polyetherimide comprises hydrolyzing a 3,3′-aromatic bis(etherimide) composition prepared by the above method under conditions effective to provide a corresponding aromatic bis(ether tetraacid) composition comprising an aromatic bis(ether tetraacid) of formula (VII-a) and optionally an aromatic bis(ether tetraacid) of formula (VII-b), an aromatic bis(ether tetraacid) of formula (VII-c), or a combination thereof.

[0012]

[0013] condensing the aromatic bis(ether tetraacid) composition under conditions effective to provide an aromatic bis(ether phthalic anhydride) composition comprising 3,3'-aromatic bis(ether phthalic anhydride) and, optionally, 3,4'-aromatic bis(ether phthalic anhydride), 4,4'-aromatic bis(ether phthalic anhydride), or a combination thereof,

[0014]

[0015] Among them, Z is composed of 1-6 C 1-8 Alkyl or 1-8 halogen atoms optionally substituted aromatic C 6-24monocyclic or polycyclic moiety; and contacting the 3,3'-aromatic bis(ether phthalic anhydride) composition with an organic diamine of formula (H2N-R-NH2), wherein R is C 6-20 Aromatic hydrocarbon groups or their halogenated derivatives, straight chain or branched C 2-20 An alkylene group or a halogenated derivative thereof, or a C 3-8 A cycloalkylene group or a halogenated derivative thereof.

[0016] The polyetherimide comprises a repeating unit of formula (VIII-a) and optionally a repeating unit of formula (VIII-b), a repeating unit of formula (VIII-c), or a combination thereof

[0017]

[0018]

[0019] Where Z is optionally replaced by 1-6 C 1-8 Alkyl groups, 1-8 halogen atoms, or a combination thereof substituted aromatic C 6-24 Monocyclic or polycyclic moiety, R is C 6-20 Aromatic hydrocarbon groups or their halogenated derivatives, straight-chain or branched C 2-20 An alkylene group or a halogenated derivative thereof, or a C 3-8 cycloalkylene groups or halogenated derivatives thereof, and wherein the polyetherimide comprises less than 20,000 ppm, less than 10,000 ppm, less than 5000 ppm, less than 2500 ppm, or less than 1000 ppm of repeating units of formula (VIII-b), repeating units of formula (VIII-c), or combinations thereof.

[0020] The article comprises the polyetherimide described above.

[0021] The invention discloses a method for manufacturing the product.

[0022] The above described and other features are exemplified by the following detailed description, examples, and claims. DETAILED DESCRIPTION

[0023] Conventional methods for preparing aromatic bis(etherimide) monomers often result in isomeric mixtures of 3,3'-aromatic bis(etherimide), 3,4'-aromatic bis(etherimide), and 4,4'-aromatic bis(etherimide). For example, conventional methods for preparing aromatic bis(etherimides) use chlorophthalic anhydride, which is a mixture of 4-chlorophthalic anhydride and 3-chlorophthalic anhydride in a ratio of about 95:5 obtained from a supplier. Although the isomers are separable by distillation, the boiling points are very close (i.e., 290° C. for 4-chlorophthalic anhydride and 295° C. for 3-chlorophthalic anhydride, each at atmospheric pressure), so a certain amount of 4-chlorophthalic anhydride is present in the 3-chlorophthalic anhydride distillate and a certain amount of 3-chlorophthalic anhydride is present in the 4-chlorophthalic anhydride distillate. Thus, there is some loss of 3-chlorophthalic anhydride to the 4-chlorophthalic anhydride distillate, and 4-chlorophthalic anhydride is often carried through the synthesis co-distilled with the 3-chlorophthalic anhydride, ultimately producing a mixture of aromatic bis(etherimide) isomers including 3,3'-aromatic bis(etherimide), 3,4'-aromatic bis(etherimide), and 4-4'-aromatic bis(etherimide) (shown below as derived from bisphenol A for illustrative purposes only).

[0024]

[0025] The present inventors have discovered a process for preparing 3,3'-aromatic bis(etherimides) from 3-nitrophthalic acid that can minimize or eliminate the formation of 3,4'-aromatic bis(etherimides) and 4,4'-aromatic bis(etherimides). Thus, polyetherimides derived from aromatic 3,3'-bis(etherimides) compositions include very low levels or no repeating units derived from 3,4'-aromatic bis(etherimides) and 4,4'-aromatic bis(etherimides). As previously discussed, polyetherimides derived from monomer mixtures enriched in 3,3'-aromatic bis(etherimides) have improved flow, which is desirable for applications where higher flow is advantageous. As an additional advantage, the 3,3'-aromatic bis(etherimide)-rich monomer mixtures and polyetherimides derived therefrom can have a lower yellowness index (YI) than aromatic bis(etherimides) and polyetherimides prepared using conventional methods.

[0026] The disclosed process is also an improvement over other conventional processes using nitric acid to introduce nitro substituents onto the aromatic ring of N-alkylphthalimide, which produces a mixture of 3-nitro-N-alkylphthalimide, 4-nitro-N-alkylphthalimide and 4-hydroxy-3,5-dinitro-N-alkylphthalimide, with 4-nitro-N-alkylphthalimide being the major product.

[0027]

[0028] As shown above, a mixture of 3-nitro-N-alkylphthalimide and 4-nitro-N-alkylphthalimide is obtained during nitration, and any polyetherimide ultimately derived from such a mixture may have higher levels of repeat units derived from 3,4'-aromatic bis(etherimide) and 4,4'-aromatic bis(etherimide), resulting in lower flow and higher YI. In addition, this conventional process, in which N-alkylphthalimide is nitrated, results in the formation of 3,5-dinitro-4-hydroxyphthalimide, which reduces the overall yield of the desired product and must be removed. Therefore, the disclosed process is an improvement over this conventional process because 3-nitro-N-alkylphthalimide can be prepared as the main product without being contaminated by significant amounts of 4-nitro-N-alkylphthalimide, and 4-nitro-N-alkylphthalimide can be excluded. The disclosed process also avoids the formation of 3,5-dinitro-4-hydroxyphthalimide.

[0029] As an additional advantage, the disclosed method avoids the use of halogenated synthetic intermediates, making it possible to prepare monomers and polyetherimides with reduced halogen content. In some respects, monomers and polyetherimides can be substantially halogen-free and have improved mobility and YI. As used herein, the phrase "substantially halogen-free" is defined by IEC 61249-2-21 or UL 746H. According to the International Electrochemical Commission, halogen restrictions are used (IEC 61249-2-21), and the composition should include each of 900ppm (ppm) of chlorine and bromine, and also include total bromine, chlorine and fluorine content below 1500ppm. According to UL746H, the composition should include each of 900ppm or less chlorine, bromine and fluorine and 1500ppm or less total chlorine, bromine and fluorine content. Bromine, chlorine and fluorine content (in ppm) can be calculated by the composition or measured by elemental analysis technology.

[0030] Therefore, another aspect of the present disclosure is a method for producing an N-alkylphthalimide composition. The method includes first reacting 3-nitrophthalic anhydride to form a 3-nitrophthalic anhydride composition. The 3-nitrophthalic acid is substantially free of 4-nitrophthalic acid, producing 3-nitrophthalic anhydride substantially free of 4-nitrophthalic anhydride, 3-nitrophthalic anhydride substantially free of 4-nitrophthalic anhydride, 3-nitro-N-alkylphthalimide compositions substantially free of 4-nitrophthalic anhydride, 3,3'-aromatic bis(etherimide) compositions substantially free of 3,4'-aromatic bis(etherimide) or 4,4'-aromatic bis(etherimide), and polyetherimide substantially free of 3,4' or 4,4' bonds in the chain. As used herein, the term "substantially free" means that the presence of the component is undetectable by analytical methods (such as NMR, LC-MC, HPLC, GC-MS, etc.).

[0031] In some respects, 3-nitrophthalic acid can include very low levels of 4-nitrophthalic acid. In fact, the isomer purity of 3-nitro-phthalic acid starting material is related to the isomer purity of downstream synthetic intermediates and polyetherimide. It will be appreciated by those of ordinary skill in the art that the purity of 3-nitrophthalic acid can be different according to suppliers and can include very low levels of 4-nitrophthalic acid (i.e., ppm levels), and this low level of 4-nitrophthalic acid can ultimately provide polyetherimide with desired flow properties, even if polyetherimide includes a limited amount of 3,4'-and 4,4'-keys in the polymer chain.

[0032] The cyclization of 3-nitrophthalic acid can be completed by heating, optionally in the presence of a solvent. The conversion of 3-nitrophthalic acid to 3-nitrophthalic anhydride can be carried out by heating 3-nitrophthalic acid in the absence of a solvent, so that the 3-nitrophthalic acid begins to melt. The 3-nitrophthalic acid can be partially melted or completely melted. When the anhydride is formed, water is produced by the reaction mixture, and as the reaction proceeds, water is removed from the reaction mixture. When the reaction is completed or close to completion, water production slows down or stops.

[0033] In preferred aspects, 3-nitrophthalic anhydride is prepared in the absence of solvent. Advantageously, under solvent-free conditions, the conversion of 3-nitrophthalic anhydride to 3-nitrophthalic anhydride is completed after about 1 hour. This is a much shorter reaction time than the conversion of 4-chlorophthalic anhydride to 4-chlorophthalic anhydride, and when effectively removing water from the reactor, the reaction time range is 6-10h. If a solvent is used, the solvent can be removed, or the reaction mixture comprising 3-nitrophthalic anhydride and a solvent can be carried out to the next step without separating 3-nitrophthalic anhydride. The solvent-free method is preferred because it avoids the use of a solvent, which is an increased expense and the reaction is carried out at a lower temperature, thus reducing the energy use of this step.

[0034] For the preparation of 3-nitro-N-(C 1-13 The method of preparing a phthalimide composition comprises reacting 3-nitrophthalic anhydride with C 1-13 The reaction can be carried out under heating and optionally in the presence of a solvent. 1-13 The conversion of 3-nitrophthalic acid to 3-(C-alkyl)phthalimide can be carried out by heating 3-nitrophthalic acid in the absence of a solvent so that the 3-nitrophthalic acid begins to melt. The 3-nitrophthalic acid can be partially melted or completely melted. Similar to the previous step, when 3-nitro-N-(C-alkyl)phthalimide is formed, 1-13 When 3-nitro-N-(C-(alkyl)phthalimide) is added, water is produced by the reaction mixture, and as the reaction proceeds, water is removed from the reaction mixture. When the reaction is complete, water production stops. Preferably, 3-nitro-N-(C-(alkyl)phthalimide) is added. 1-13 The phthalimide is substantially free of 4-nitro-N-(C 1-13 As used herein, “substantially free of 4-nitro-N-(C 1-13 The term "4-nitro-N-(C-alkyl)phthalimide" means that no 4-nitro-N-(C-alkyl)phthalimide can be detected in the 3-nitro-N-alkylphthalimide composition by analytical methods (e.g., LC-MS, HPLC, GC-MS). 1-13 Suitable HPLC conditions can be found in U.S. Pat. No. 4,902,809.

[0035] Depending on the purity of 3-phthalic acid, 3-nitro-N-(C 1-13 The phthalimide composition may include a low amount of 3-nitro-N-(C 1-13alkyl)phthalimide, such as, for example, less than 20,000 ppm, less than 10,000 ppm, less than 5000 ppm, less than 2500 ppm, less than 1000 ppm, less than 500 ppm, or less than 100 ppm of 4-nitro-N-(C 1-13 In some aspects, the presence of 4-nitro-N-alkylphthalimide cannot be detected in the 3-nitro-N-alkylphthalimide composition by analytical methods (e.g., LC-MS, HPLC, GC-MS). Suitable HPLC conditions can be found in U.S. Pat. No. 4,902,809. When no 4-nitro-N-(C 1-13 In the presence of alkyl)phthalimide, N-(C 1-13 The phthalimide is substantially free of 4-nitro-N-(C 1-13 Alkyl)phthalimide.

[0036] The anhydride formation and phthalimide formation can be conducted at a temperature less than or equal to 250° C., such as about 150-250° C., or 150-225° C. Temperatures outside of the above ranges can also be used; however, lower temperatures may result in reaction rates that are too slow to be cost effective.

[0037] The pressure range under which the nitration process is carried out can vary from vacuum to above atmospheric pressure. However, these conditions depend on the type of reactor or reactors used. Otherwise, the process is generally carried out at atmospheric pressure.

[0038] From 3-nitrophthalic acid to 3-nitro-N-(C 1-13 The yield of the conversion of the alkyl)phthalimide composition can be improved. Based on the weight % of 3-nitrophthalic acid, the yield % can be at least 60%, or 65%, or 70%, or 75%, or 80%.

[0039] Thus, another aspect of the present disclosure is a method for producing an aromatic bis(etherimide) monomer. The method comprises reacting a dialkali metal salt of a dihydroxy aromatic compound with a nitro-N-alkylphthalimide composition under conditions effective to form a product mixture comprising the aromatic bis(etherimide) monomer.

[0040] The specific conditions for reacting the dialkali metal salt of a dihydroxy aromatic compound with a 3-nitro-N-alkylphthalimide composition to provide an aromatic bis(etherimide) will depend on the specific dihydroxy aromatic compound, the specific components of the nitro-N-alkylphthalimide composition, the solvent, the presence or absence of a phase transfer catalyst, and similar considerations. For example, the reaction can be at a temperature of about 25-250° C., e.g., 100-250° C., or 115-200° C., or 100-125° C., or 115-125° C. The reaction can be at atmospheric pressure, superatmospheric pressure, or subatmospheric pressure. For example, the reaction can be at a pressure of 0-70 kPa, or 30-70 kPa, or 50-70 kPa, or 10-30 kPa, or 10-40 kPa, or 10-50 kPa, or 10-60 kPa, or 20-40 kPa, or 20-50 kPa, or 20-60 kPa, or 30-50 kPa, or 30-60 kPa, or 40-60 kPa.

[0041] The reaction mixture can have 1-90wt%, or 10-90wt%, or 10-80wt%, or 10-70wt%, or 10-60wt%, or 40-90wt%, or 50-90wt%, or 60-90wt%, or 10-50wt%, or 20-50wt%, or 30-50wt%, or 10-40wt%, or 10-30wt%, or 20-40wt% solid content, each based on the gross weight of the reaction mixture, depending on the property of the N- alkyl group. In some aspects, the reaction mixture can have a solid content of 20-30wt% or 22-26wt% based on the gross weight of the reaction mixture. As used herein, "solid content" refers to the weight of non-solvent components (whether dissolved or in solid form) divided by the gross weight of the reaction mixture.

[0042] One molar equivalent of the dialkali metal salt and two molar equivalents of the nitro-N-alkylphthalimide composition can be used, while higher or lower amounts of either do not substantially interfere with the formation of the desired aromatic bis(etherimide). However, in some aspects, two moles of the nitro-N-alkylphthalimide composition per mole of the dialkali metal salt are preferred. In some aspects, the molar ratio of the dialkali metal salt to the nitro-N-alkylphthalimide composition can be from 1:1.5 to 1:2.5, or from 1:1.7 to 1:2.3, or from 1:1.8 to 1:2.2, or from 1:1.9 to 1:2.1.

[0043] In some aspects, the reaction of preparing aromatic bis(ether imide) is carried out in the presence of a solvent. Any organic solvent that does not react with the reactant during the formation of aromatic bis(ether imide) can be used in the reaction. In some aspects, the solvent includes a non-polar organic solvent. Suitable non-polar organic solvents include but are not limited to toluene, benzene, chlorobenzene, bromobenzene, dichlorobenzene (e.g., o-dichlorobenzene, m-dichlorobenzene or p-dichlorobenzene), trichlorobenzene (e.g., 1,2,4-trichlorobenzene), xylene (including m-xylene, o-xylene, p-xylene and including at least one combination of the foregoing), anisole, ethylbenzene, propylbenzene, mesitylene, etc., or a combination thereof. In some aspects, the solvent can be a combination of toluene, benzene, chlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, xylene, etc., or a non-polar organic solvent thereof. In some aspects, the solvent preferably includes toluene.

[0044] The solvent can include a kind of dipole aprotic solvent. Suitable dipole aprotic solvent can include but is not limited to dimethyl sulfoxide, dimethylacetamide, N-methyl pyrrolidone, 1-cyclohexyl-2-pyrrolidone, N-isopropyl-pyrrolidone, tetramethyl urea, dimethylformamide, cyclopentane, N-methyl caprolactam and the like or a combination thereof. In some aspects, the solvent can be a combination of a non-polar organic solvent and a dipole aprotic solvent. For example, a non-polar organic solvent and a dipole aprotic solvent can be present in a weight ratio of 1: 99 to 99: 1, or 5: 95 to 95: 5, or 10: 90 to 90: 10, or 20: 80 to 80: 20, or 30: 70 to 70: 30, or 40: 60 to 60: 40.

[0045] The solids content of the product mixture comprising the aromatic bis(etherimide) can be 5-90 wt%, or 10-90 wt%, or 10-80 wt%, or 10-70 wt%, or 10-60 wt%, or 10-50 wt%, or 10-40 wt%, or 10-30 wt%, or 10-20 wt%, or 5-80 wt%, or 5-70 wt%, or 5-60 wt%, or 5-50 wt%, or 5-40 wt%, or 5-30 wt%. 0wt% or 5-20wt%; or 10-90wt%, or 10-80wt%, or 10-70wt%, or 10-60wt%, or 10-50wt%, or 10-40wt%, or 10-30wt%, or 10-20wt%; or 20-90wt%, or 20-80wt%, or 20-70wt%, or 20-60wt%, or 20-50wt%, or 20-40wt%, or 20-30wt%.

[0046] In some aspects, the reaction can be carried out in the presence of a phase transfer catalyst. A variety of phase transfer catalysts can be used, for example, various phosphonium salts, ammonium salts, guanidinium salts and pyridinium salts can be used. The phase transfer catalyst can be hexa(C 1-12 Alkyl)guanidinium salt, tetra(C 1-12 Alkyl) ammonium salt, tetra(C 1-12 alkyl)phosphonium salt, or tetra(C 6-20 The phase transfer catalyst may be tetraethylammonium bromide, tetraethylammonium acetate, tetrabutylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium fluoride, tetrabutylammonium acetate, tetrahexylammonium chloride, tetraheptylammonium chloride, Aliquat 336 phase transfer catalyst, tetrabutylphosphonium bromide, tetraphenylphosphonium bromide, tetrabutylphosphonium chloride, hexaethylguanidinium chloride, etc. Pyridinium salts may also be used, such as di-aminopyridinium salts.

[0047] The phase transfer catalyst can be a quaternary salt or a diquaternary salt. The quaternary salt that can be used is of the formula (R 3 )4Q + X catalyst, where each R 3 Same or different, and C 1-10 alkyl; Q is a nitrogen or phosphorus atom; and X is a halogen atom or C 1-8 Alkoxy or C 6-18 Aryloxy. Exemplary phase transfer catalysts include ((CH3(CH2)3)4NX, (CH3(CH2)3)4PX, (CH3(CH2)5)4NX, (CH3(CH2)6)4NX, (CH3(CH2)4)4NX, CH3(CH3(CH2)3)3NX, and CH3(CH3(CH2)2)3NX, where X is Cl - Br - , C 1-8 Alkoxy or C 6-18 Aryloxy.

[0048] The bis-quaternary salts which can be used are those having the formula (R 4 ) k Q + (R 3 ) m + Q(R 4 ) k (X 2 )2, where each R 3 Independently divalent C 1-60 Hydrocarbon, all R 3 Total contains 4-54 carbon atoms, each R 4 Independently C 1-12 Hydrocarbyl, Q is nitrogen or phosphorus, preferably nitrogen, X 2is an organic or inorganic anionic atom or group, k is an integer from 1 to 3, and m is 4 to k, wherein R attached to each Q atom 3 and R 4 At least three of the groups are aliphatic or alicyclic. In particular, each R 3 Can be divalent C 1-18 Alkylene, C 3-8 Cycloalkylene, or C 6-18 Aryl, such as ethylene, propylene, trimethylene, tetramethylene, hexamethylene, octamethylene, decamethylene, dodecamethylene, cyclohexylene, phenylene, tolylene, or naphthylene, or C 2- or C3-6 ... 3-12 In some aspects, each R 3 It is C 1-12 Alkylene, specifically C 3-8 Preferably, there is only one R 3 A group (ie, m is 1 and each k is 3) and which contains 5 to 10, specifically 6, carbon atoms. Illustrative R 4 The radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-hexyl, n-heptyl, cyclopentyl, cyclohexyl, methylcyclohexyl, phenyl, tolyl, 2-(1,4-dioxanyl) and 2-furanyl. Preferably, these R 4 The groups are all alkyl groups, such as C 1-4 n-Alkyl. X 2 R may be any anion that is stable under the conditions used; suitable anions include chloride, bromide, sulfate, p-toluenesulfonate, and methanesulfonate, preferably bromide. The integer k may have a value of 1-3, and m may have a value of 4-k. In some aspects, each k is 3 and m is 1. In some aspects, all R 3 and R 4 The group is aliphatic. Illustrative di-quaternary salts of this type include those wherein R 3 is a polymethylene chain from trimethylene to dodecamethylene, each R 4 is n-butyl or n-hexyl, Q is nitrogen, X 2 is bromine, each k is 2 and m is 2; wherein R 3 Each is ethylene, R 4 is n-butyl, Q is nitrogen, X 2 is bromine, k is each 1 and m is 3; and R 3 For hexamethylene, each R 4 is n-butyl, Q is phosphorus, X 2 is a compound wherein each k is 3 and m is 1.

[0049] Quaternary ammonium salts that can be used as phase transfer catalysts include quaternary ammonium salts of dihydroxy aromatic compounds, such as those described in U.S. Pat. No. 5,756,843 to Webb et al. For example, the quaternary salt of a dihydroxy aromatic compound may have the formula A + (OZO)2H3, wherein A is a monocationic carbon and nitrogen or phosphorus-containing group (i.e., a group having a single positive charge including carbon and nitrogen or carbon and phosphorus). Group A includes 1-6 C 2-12 In some aspects, A preferably includes nitrogen. In some aspects, A can be tetra(C 2-12 alkyl)ammonium or tetra(C 2-12 In some aspects, A is preferably a hexa(C2-12 alkyl)guanidinium group, such as hexaethylguanidinium, hexa-n-butylguanidinium, or tetraethyldi-n-butylguanidinium. Z is optionally substituted by 1-6 C 1-8 Alkyl groups, 1-8 halogen atoms, or a combination thereof substituted aromatic C 6-24 Monocyclic or polycyclic moiety. In some aspects, Z has the chemical formula (IIa) as described below. Z is 2,2-(4-phenylene) isopropylidene (i.e., the dihydroxy aromatic compound from which Z is obtained is 2,2-bis-(4-hydroxyphenyl) propane or bisphenol A). For example, the quaternary salt of the dihydroxy aromatic compound can be prepared by the reaction of the dihydroxy aromatic compound of formula HO-Z-OH with an alkali metal hydroxide and a quaternary salt of formula A+X. The group X can be as described above, and is a halide, or a bromide or a chloride, most preferably a chloride. The typical reaction temperature is about 1-125°C, preferably about 10-50°C, and preferably in an inert atmosphere such as nitrogen or argon.

[0050] In some aspects, the phase transfer catalyst is preferably hexa(C 1-12 alkyl)guanidinium salts, for example hexaethylguanidinium chloride.

[0051] Based on the total moles of the dialkali metal salt of the dihydroxy aromatic compound, the phase transfer catalyst may be present in an amount of 0.1-10 mole percent (mol%), 0.5-10 mol%, 0.5-5.0 mol%. In some aspects, the phase transfer catalyst may be present in an amount of 0.1-2.5 mol%, or 0.5-2.5 mol%. It has been found that in the disclosed method, the amount of catalyst required can be less than that of conventional methods, wherein 4-hydroxy-3,5-dinitro-N-(C 1-13 Alkyl)phthalimide (DNPI) is formed as a by-product.

[0052] Aromatic bis(ether imide) can be recovered from the product mixture and purified by a variety of procedures. One procedure includes dissolving the aromatic bis(ether imide) in an organic solvent such as toluene, and then washing or extracting with an alkaline solution containing 0.1wt%-10wt%, or 1wt%-5wt% of an alkali to remove by-products, such as monoimides, etc., phase transfer catalysts, and unreacted starting materials. In some aspects, during washing or extraction, the volume ratio of the alkaline solution to the organic phase (e.g., aromatic bis(ether imide) in an organic solvent) can be 1:5 to 1:15, or 1:5 to 1:10, or 1:6 to 1:9, or 1:6 to 1:8.

[0053] The aromatic bis(etherimide) prepared according to the above method can be obtained in a yield of greater than 75%, greater than 80%, greater than 85%, or greater than 90%.

[0054] After recovery, the aromatic bis(etherimide) can have a high or low color, as shown by the yellow index (YI). The YI is a value calculated from spectrophotometer data that describes the color of the test sample as transparent or white (low YI) versus more yellow (high YI). Sample handling and preparation can affect the test results. The YI of the aromatic bis(etherimide) can be measured according to ASTM D1925 by dissolving 0.5 g of the aromatic bis(etherimide) in 10 milliliters of dichloromethane and measuring the YI of the resulting solution, such as on a Xrite 7000 Color Eye device (Xrite, Incorporated). In some aspects, the YI of the aromatic bis(etherimide) can be 15 or less, or 10 or less, such as 1-15 or 1-10. In preferred aspects, the YI of the aromatic bis(etherimide) can be 5 or less, measured at a thickness of 3.2 mm according to ASTM D-1925. For example, the aromatic bis(etherimide) can have a YI of 1-15, or 1-10, 5-15, or 5-10, or 1-9, or 1-8, or 1-7, or 1-6, or 1-5, or 1-4, or 1-3, or 2-9, or 2-8, or 2-7, or 2-6, or 2-5, or 2-4, or 3-9, or 3-8, or 3-7, or 3-6, or 3-5, or 4-9, or 4-8, or 4-7, or 4-6, or 5-9, or 5-8, or 5-7, or 6-9, or 6-8, or 7-9.

[0055] In one aspect, the process for producing an aromatic bis(etherimide) preferably comprises reacting a dialkali metal salt of a dihydroxy aromatic compound with a nitro-N-alkylphthalimide composition in the presence of a hexaethylguanidinium chloride phase transfer catalyst and under conditions effective to form a product mixture comprising the aromatic bis(etherimide), wherein the nitro-N-alkylphthalimide composition comprises 3-nitro-N-(C 1-13 alkyl)phthalimide and optionally 4-nitro-N-(C 1-13 The aromatic bis(ether imide) may be an alkyl)phthalimide, and the aromatic bis(ether imide) may have a YI of less than 15, or less than 10, or less than 5 as determined according to ASTM D-1925.

[0056] In some aspects, the aromatic bis(etherimide) composition can be substantially free of 4-hydroxy-3,5-dinitro-N-(C 1-13 alkyl)phthalimide, which means 4-hydroxy-3,5-dinitro-N-(C 1-13 The presence of alkyl)phthalimide is not detectable, for example, by high performance liquid chromatography (HPLC) methods after recovery. Suitable HPLC conditions can be found in U.S. Pat. No. 4,902,809.

[0057] The dialkali metal salt of a dihydroxy aromatic compound has the formula (I):

[0058] M +- OZO -+ M(I)

[0059] wherein M is an alkali metal, and Z is optionally replaced by 1-6 C 1-8 Alkyl groups, 1-8 halogen atoms, or a combination thereof substituted aromatic C 6-24 Monocyclic or polycyclic moieties. The alkali metal M can be, for example, lithium, sodium, potassium, or a combination thereof. In some aspects, M is sodium. Exemplary groups Z include groups derived from aromatic dihydroxy compounds of formula (II):

[0060]

[0061] Among them, R a and R b may be the same or different and are, for example, halogen atoms or monovalent C 1-6 alkyl group; p and q are each independently an integer of 0-4; 0-4; and X ais a bridging group connecting hydroxy-substituted aromatic groups, wherein the bridging group and the hydroxy substituent of each C6 arylene group are arranged ortho, meta, or para (especially para) to each other on the C6 arylene group. a It can be a single bond, -O-, -S-, -S(O)-, -S(O)2-, -C(O)-, or C 1-18 Organic bridging group. 1-18 The organic bridging group may be cyclic or acyclic, aromatic or non-aromatic, and may further contain heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorus. 1-18 The organic group is such that the C6 arylene groups attached thereto are each attached to a common alkylidene carbon or to a C 1-18 Different carbon atoms of the organic bridging group. Specific examples of the group Z are divalent groups of formula (II-a):

[0062]

[0063] Wherein, Q is -O-, -S-, -C(O)-, -SO2-, -SO-, or -C y H 2y -, wherein y is an integer from 1 to 5 or a halogenated derivative thereof. Exemplary dihydroxy aromatic compounds from which Z can be derived include, but are not limited to, 2,2-bis(2-hydroxyphenyl)propane, 2,4'-dihydroxydiphenylmethane, bis(2-hydroxyphenyl)methane, 2,2-bis-(4-hydroxyphenyl)propane ("bisphenol A' or "BPA"), 1,1-bis-(4-hydroxyphenyl)ethane, 1,1-bis-(4-hydroxyphenyl)propane, 2,2-bis-(4-hydroxyphenyl)pentane, 3,3'-bis-(4-hydroxyphenyl)pentane, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxy-3,3,5,5'-tetramethylbiphenyl, 2,4 In some aspects, Z is 2,2-(4-phenylene)isopropylidene (i.e., the dihydroxy aromatic compound from which the dialkali metal salt is derived is 2,2-bis-(4-hydroxyphenyl)propane or bisphenol A, so that Q in formula (IIa) is 2,2-isopropylidene).

[0064] The nitro-N-alkylphthalimide composition comprises a 3-nitro-N-(C 1-13 alkyl)phthalimide and optionally 4-nitro-N-(C 1-13 Alkyl)phthalimide:

[0065]

[0066] Among them, R 1 It is a one-price C 1-13 Alkyl, preferably C 1-4 An alkyl group, such as a methyl group.

[0067] The 3,3'-aromatic bis(etherimide) composition comprises a 3,3'-aromatic bis(etherimide) of formula (IV-a) and optionally a 3,4'-aromatic bis(etherimide) of formula (IV-b), a 4,4'-aromatic bis(etherimide) of formula (IV-c)

[0068]

[0069] Among them, R 1 It is C 1-13 Alkyl, or C 1-4 Alkyl, preferably methyl, and Z is as described in formula (I). In some aspects, Z is a divalent group of formula (IIa) as described above, preferably 2,2-(4-phenylene)isopropylidene (i.e., the dihydroxy aromatic compound from which the dialkali metal salt is derived is 2,2-bis-(4-hydroxyphenyl)propane or bisphenol A).

[0070] In some aspects, the aromatic bis(etherimide) comprises 3,3′-bisphenol-A-bis-N-methylphthalimide and optionally 3,4′-bisphenol-A-bis-N-methylphthalimide, 4,4′-bisphenol-A-bis-N-methylphthalimide, or a combination thereof.

[0071] Also disclosed is a method for preparing polyetherimide. Advantageously, the disclosed method can provide N-(C 1-13 alkyl)-3,3'-aromatic bis(etherimide), which is the major product rather than a minor product as in the case of conventional processes. This allows control of the 1-13 Alkyl)-3,3'-aromatic bis(etherimide) repeating units, derived from N-(C 1-13 Alkyl)-3,4'-aromatic bis(etherimide) repeating units, and N-(C 1-13 The ratio of repeating units of N-(C-alkyl)-4,4'-aromatic bis(etherimide) can be controlled. Thus, by controlling the ratio of repeating units incorporated into the polyetherimide, the flow properties can be adjusted. In some aspects, it can be desirable for the polyetherimide to be substantially free of (i.e., undetectable by analytical methods) N-(C-alkyl)-4,4'-aromatic bis(etherimide)-4,4'-aromatic bis(etherimide)-4,4'-aromatic bis(etherimide)-4,4'-alkyl ... 1-13 Alkyl)-3,4'-aromatic bis(ether imide) and N-(C 1-13As an additional advantage, compared with polyetherimides prepared according to conventional methods, the N-(C-(4-(4-alkyl)-4,4'-aromatic)-bis(etherimide) derived from the disclosed method can be 1-13 In some aspects, the polyetherimide derived from N-(C-alkyl)-3,3-aromatic bis(etherimide) prepared according to the disclosed method can have a lower halogen content, as defined in IEC 61249-2-21 or UL 746H. 1-13 The polyetherimide of the (alkyl)-3,3-aromatic bis(etherimide) is substantially free of halogen.

[0072] In other aspects, it may be desirable for the polyetherimide to contain a predetermined amount of N-(C 1-13 Thus, in addition to the N-(C-(alkyl)-3,3'-aromatic bis(etherimide) prepared using the disclosed method, 1-13 In addition to the aromatic bis(ether imide)-3,3'-alkyl)-3,3'-aromatic bis(ether imide), N-(C 1-13 Alkyl)-3,3'-aromatic bis(ether imide), N-(C 1-13 Alkyl)-3,4'-aromatic bis(etherimide), and N-(C 1-13 A mixture of alkyl)-4,4'-aromatic bis(etherimides) is prepared to achieve a predetermined ratio of the monomers.

[0073] The method for preparing polyetherimide may include reacting N-(C 1-13 The aromatic bis(ether phthalic anhydride) composition (IV) is contacted with phthalic anhydride to provide an aromatic bis(ether phthalic anhydride) composition comprising a 3,3'-aromatic bis(ether phthalic anhydride) of formula (Va) and, optionally, a 3,4'-aromatic bis(ether phthalic anhydride) of formula (Vb) and a 4,4'-aromatic bis(ether phthalic anhydride) of formula (Vc)

[0074]

[0075] Where Z is composed of 1 to 6 C 1-8 an alkyl group, 1 to 8 halogen atoms, or a combination thereof, an optionally substituted aromatic C 6-24Monocyclic or polycyclic moieties are as described above. In some aspects, Z is 2,2(4-phenylene)isopropylidene. Illustrative examples of aromatic bis(ether phthalic anhydrides) 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) 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, and various combinations thereof.

[0076] The catalyst may be a tertiary amine. Among the tertiary amines that may be used as catalysts are aliphatic tertiary amines such as triethylamine and tributylamine, alicyclic tertiary amines such as N,N-diethyl-cyclohexylamine, and aromatic tertiary amines such as N,N-dimethylaniline. In some aspects, the catalyst comprises C 1-20 A trialkylamine, such as triethylamine, tributylamine, or the like, or a combination thereof. In one aspect, the catalyst is triethylamine. In some aspects, the contacting can occur in the presence of 0.5-15 mole percent of the catalyst relative to the anhydride.

[0077] 3,3'-aromatic bis(ether imide) compositions and phthalic anhydride are contacted under conditions generally known to effectively provide 3,3'-aromatic bis(ether phthalic anhydride) compositions comprising 3,3'-aromatic bis(ether phthalic anhydride) and optional 3,4'-aromatic bis(ether phthalic anhydride) and 4,4'-aromatic bis(ether phthalic anhydride). For example, phthalic anhydride may be present in molar excess, such as 3-8 molar excess of phthalic anhydride relative to aromatic bis(ether imide). Contact may be further carried out in the presence of a solvent, such as an aromatic solvent, including but not limited to benzene, toluene, xylene, chlorobenzene and o-dichlorobenzene, preferably toluene. In some aspects, the solvent may include a solvent mixture, such as water and toluene. The contacting can be at a temperature of 100-300° C., or 100-280° C., or 100-250° C., or 110-240° C., or 120-230° C., or 130-220° C., or 150-210° C., or 150-250° C., or 170-260° C. The contacting can be at superatmospheric pressure, such as 200-700 pounds per square inch (psi), or 200-400 psi, or 200-600 psi, or 300-500 psi, or 300-600 psi, or 300-700 psi, or 400-600 psi, or 500-700 psi. The contacting of the aromatic bis(etherimide) and phthalic anhydride can be carried out for 0.5 to 3 hours, preferably with agitation (e.g., stirring).

[0078] The method for making the polyetherimide further comprises contacting a 3,3'-aromatic bis(ether phthalic anhydride) composition of formula (V) with an organic diamine of formula (VI):

[0079] H2N-R-NH2(VI)

[0080] The polyetherimide is provided. In formula (VI), R is a substituted or unsubstituted divalent organic group, such as a substituted or unsubstituted C 6-20 Aromatic hydrocarbon, substituted or unsubstituted straight chain or branched C 4-20 Alkylene, substituted or unsubstituted C 3-8 Cycloalkylene, especially a halogenated derivative of any of the foregoing. Specifically, in particular, is a divalent radical of one or more of the following formulae:

[0081]

[0082] Among them, Q 1 Is -O-, -S-, -C(O)-, -SO2-, -SO-, -P(R a )(=O)-, where R a It is C 1-8 Alkyl or C6-12 Aryl, -C y H 2y -, wherein y is an integer from 1 to 5 or a halogenated derivative thereof (which contains a perfluoroalkylene group), or -(C6H 10 ) z -, wherein z is an integer from 1 to 4. In one aspect, R is m-phenylene, p-phenylene, or arylene sulfone, particularly bis(4,4'-phenylene)sulfone.

[0083] Examples of the organic diamines include 1,4-diaminobutane, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 1,18-octadecanediamine, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 4-methylnonamethylenediamine, 5-methylnonamethylenediamine, 2,5-diaminobutane, 1,5-diaminobutane, 1,6-hexanediamine, 1,7-heptamethylenediamine, 1,8-octadecanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 1,18-octadecanediamine, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 4-methylnonamethylenediamine, 5-methylnonamethylenediamine, 2,5-diaminobutane ... Methylhexamethylenediamine, 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, 2,4-diaminotoluene, 2,6-diaminoformyl Benzene, m-xylylenediamine, p-xylylenediamine, 2-methyl-4,6-diethyl-1,3-phenylenediamine, 5-methyl-4,6-diethyl-1,3-phenylene-diamine, 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-amino 1,3-diamino-4-isopropylbenzene, bis(4-aminophenyl)sulfide, bis-(4-aminophenyl)sulfone (also known as 4,4′-diaminodiphenylsulfone (DDS)), and bis(4-aminophenyl)ether. Any of the aforementioned C 1-4 Alkylated or poly(C 1-4 ) alkylated derivatives, such as a polymethylated 1,6-hexanediamine. Regioisomers of any of the above may also be used. Combinations of these compounds may also be used. In some aspects, the organic diamine is m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodiphenyl sulfone, 3,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, or a combination thereof.

[0084] The contacting of the 3,3'-aromatic bis(ether phthalic anhydride) composition with the organic diamine can be in the presence of a solvent, for example, N-methylpyrrolidone, dimethylacetamide, dimethylformamide, cresol, veratrole, phenetole, dimethyl sulfoxide, chloroform, acetone, methanol, ethanol, toluene, benzene, chlorobenzene, bromobenzene, dichlorobenzene, trichlorobenzene (e.g., 1,2,4-trichlorobenzene), xylene (including m-xylene, o-xylene, p-xylene, and a combination comprising at least one of the foregoing), anisole, ethylbenzene, propylbenzene, mesitylene, etc., or a combination thereof. Sufficient solvent is typically used to provide a solids content of 1-90%, or 10-90%, or 30-90%, or 50-90%, or 70-90%, or 1-10%, or 10-30%, or 10-50%, or 10-70%, or 10-80%, or 20-40%, or 20-60%, or 20-80%, or 30-50%, or 30-70%, or 30-80%, or 40-60%, or 40-80%, or 50-80%. In some aspects, the solids content can be 15%-60%.

[0085] In some aspects, the contacting can be carried out in the presence of an end-capping agent. The end-capping agent limits the molecular weight growth rate, and therefore can be used to control the molecular weight in the polyetherimide. Exemplary end-capping agents include certain monoamines (e.g., aniline), monoanhydrides (e.g., phthalic anhydride), etc. In one aspect, the end-capping agent is phthalic anhydride, so that the obtained polyetherimide includes phthalimide as the end-capping of the polymer chain. However, it should be understood that the polyetherimide disclosed herein with any end-capping with any desired weight-average molecular weight (Mw) can be produced.

[0086] The contact of the 3,3'-aromatic bis(ether phthalic anhydride) composition with the organic diamine may be carried out at a temperature of 100-250°C, or 120-230°C, or 150-210°C, or 150-250°C, and may preferably be accompanied by stirring (e.g., stirring) for 0.5-10 hours. In order to avoid harmful oxidation reactions, the contact of the aromatic bis(ether phthalic anhydride) with the organic diamine may be covered under an inert gas. Examples of such gases are dry nitrogen, helium, argon, and the like. Dry nitrogen may be preferred. The reaction may be carried out at atmospheric pressure to superatmospheric pressure.

[0087] Alternatively, a method for making a polyetherimide comprises hydrolyzing an aromatic bis(etherimide) composition of formula (IV) prepared by the above method under conditions effective to provide a corresponding aromatic tetraacid composition comprising an aromatic tetraacid of formula (VII-a), and optionally, an aromatic tetraacid of formula (VII-b), an aromatic tetraacid of formula (VII-c), or a combination thereof,

[0088]

[0089] wherein Z is as defined above. In some aspects, Z is 2,2-(4-phenylene)isopropylidene.

[0090] Hydrolysis of the 3,3'-aromatic bis(etherimide) composition to provide the corresponding tetraacid can be under conditions effective to provide an aromatic tetraacid composition, for example, as described in U.S. Pat. No. 3,879,428. For example, the aromatic bis(etherimide) can be hydrolyzed in an alkaline aqueous solution, for example containing an alkali metal hydroxide, preferably sodium hydroxide. The reaction time can vary from 1 to 24 hours or more, depending on the reactants, degree of agitation, temperature, pressure, etc. The organic amine byproduct can be removed by standard procedures such as steam distillation, decantation (when using butyl-derived materials), etc. In addition, the hydrolysis rate is accelerated by conducting the reaction at a temperature above atmospheric pressure and at 100°C-220°C. For example, the hydrolysis can be at a temperature of 120-220° C., or 140-220° C., or 160-220° C., or 180-220° C., or 200-220° C., or 100-210° C., or 100-190° C., or 100-170° C., or 100-150° C., or 100-130° C. The hydrolysis can be at a pressure of 0 MPa-2 MPa. The hydrolyzed bis(etherimide) can be acidified with an acidic aqueous solution, for example containing an inorganic acid, such as sulfuric acid, hydrochloric acid, etc., to provide a tetraacid.

[0091] The aromatic tetraacid composition can be condensed (i.e., dehydrated) under conditions that effectively provide an aromatic bis(ether phthalic anhydride) composition of formula (V). Condensing the aromatic tetraacid composition to provide the corresponding aromatic aromatic bis(ether phthalic anhydride) composition can be under conditions that effectively provide an aromatic bis(ether phthalic anhydride) composition. For example, the aromatic tetraacid can be condensed by refluxing in the presence of a dehydrating agent (e.g., acetic anhydride). In some aspects, a temperature of 100° C.-225° C. and a pressure of 0 MPa-1 MPa can be used. The aromatic bis(ether phthalic anhydride) composition can optionally use any commonly known separation technique, for example, filtration separation. Alternatively, the aromatic bis(ether phthalic anhydride) composition can be directly used to prepare a polyetherimide without further purification or separation.

[0092] The method for manufacturing polyetherimide by aromatic tetraacid composition (VII) can also include contacting aromatic bis(ether phthalic anhydride) composition (V) (obtained by dehydrating aromatic tetraacid composition as described above) with organic diamine of formula (VI) to provide polyetherimide. The contact can be carried out in the presence of solvent or end-capping agent as described above. Alternatively, in some aspects, polyetherimide can be prepared by directly contacting aromatic tetraacid composition (VII) with organic diamine (VI) to provide polyetherimide (that is, dehydration of tetraacid is not required to provide corresponding aromatic bis(ether phthalic anhydride)).

[0093] The polyetherimide prepared according to any of the above methods for preparing polyetherimide can have a YI of less than 120, or less than 110, or less than 100, or less than 90, or less than 80, or less than 70, or less than 60, or less than 50. For example, the polyetherimide can have a YI of 40-120, or 40-110, or 40-100, or 40-90, or 40-80, or 40-70, or 40-60, or 40-50. In some aspects, the polyetherimide can have a YI of 45-120, or 45-100, or 45-90, or 45-80, or 45-70, or 45-60, or 45-55. In other aspects, the polyetherimide can have a YI of 50-120, or 50-100, or 50-90, or 50-80, or 50-70, or 50-60. In other aspects, the polyetherimide can have a YI of 60-120, or 60-100, or 60-90, or 60-80, or 60-70; or 70-120, or 70-100, or 70-90 or 70-80; or 80-120, or 80-100. In any of the foregoing aspects, the YI of the polyetherimide can be determined according to ASTM D1925 at a thickness of 3.2 millimeters.

[0094] The polyetherimide prepared according to any one of the above methods for preparing polyetherimide may have a melt volume flow rate of 1 to 50 cubic centimeters per 10 minutes (cc / 10 min), preferably 2 to 30 cc / 10 min, measured at 337° C. / 6.6 kgf or 367° C. / 6.6 kgf determined according to ASTM D1238.

[0095] The polyetherimide comprises a repeating unit of formula (VIII-a), and optionally, a repeating unit of formula (VIII-b), a repeating unit of formula (VIII-c), or a combination thereof,

[0096]

[0097] Where Z is optionally replaced by 1-6 C 1-8Alkyl groups, 1-8 halogen atoms, or a combination thereof substituted aromatic C 6-24 Monocyclic or polycyclic moiety, R is C 6-20 Aromatic hydrocarbon groups or their halogenated derivatives, straight-chain or branched C 2-20 An alkylene group or a halogenated derivative thereof, or a C 3-8 A cycloalkylene group or a halogenated derivative thereof, and wherein the polyetherimide comprises less than 20,000 ppm, less than 10,000 ppm, less than 5000 ppm, less than 2500 ppm, or less than 1000 ppm of a repeating unit of formula (VIII-b), a repeating unit of formula (VIII-c), or a combination thereof. The presence of the repeating unit of formula (VIII-b) and the repeating unit of formula (VIII-c) in ppm can be measured by NMR.

[0098] The polyetherimide prepared according to the above method comprises repeating units of formula (VIII-a) and optionally, formula (VIII-b), formula (VIII-c), or a combination thereof, wherein Z is as defined in formula (I) and each R is the same or different and is as defined in formula (VI). In one aspect, in formula (VIII), R is m-phenylene, p-phenylene, 4,4′-diaminodiphenyl sulfone, 3,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, or a combination thereof, and Z is a divalent group of formula (II-a), wherein Q is 2,2-isopropylidene.

[0099] Also disclosed are articles comprising the polyetherimide prepared as described above. Also disclosed are articles comprising the polyetherimide prepared as described above. Articles comprising polyetherimide can be prepared by any number of methods, including forming, foaming, extruding, thermoforming, rotating, or molding. Articles can be in the form of, for example, fibers, hollow fibers, hollow tubes, sheets, films, multilayer sheets, multilayer films, molded parts, extruded profiles, coated parts, foams, filaments, or powders. In some embodiments, the article is a fiber, film, sheet, foam, filament, molded article, extruded article, or powder.

[0100] Articles comprising polyetherimide can be prepared by any number of methods, including forming, foaming, extruding, thermoforming, spinning, or molding. Articles can be in the form of, for example, fibers, hollow fibers, hollow tubes, sheets, films, multilayer sheets, multilayer films, molded parts, extruded profiles, coated parts, foams, filaments, or powders. In some aspects, the article is a fiber, film, sheet, foam, filament, molded article, extruded article, or powder.

[0101] The present disclosure is further illustrated by the following examples, which are non-limiting.

[0102] Example

[0103] Example 1

[0104] 3-Nitro-N-methylphthalimide (3-NPI) is synthesized from 3-nitrophthalic acid. The reaction is carried out on a scale of 5g and 25g. 3-nitrophthalic acid (3-NP acid) is heated at 210°C. As 3-NP acid begins to melt, anhydride rings begin to form and produce water. After 1h, the conversion of 3-NP acid to 3-NP-anhydride is complete, and the temperature is reduced to 165°C under stirring. Monomethylamine gas (MMA) is introduced into the reaction vessel. MMA reacts with anhydride in a ring-opening reaction, and the ring-opening intermediate undergoes a closed loop in situ, thereby producing water. When the reaction no longer produces water, it indicates that it is completely converted into 3-NPI. The reaction mixture is cooled to provide a solid substance. The solid mass is tableted to provide tableted 3-NPI. The crude product is characterized by LC-MS and used in the next step without further purification. Suitable HPLC conditions can be found in U.S. Patent No. 4,902,809.

[0105] Table 1

[0106]

[0107] 3-NPI acid (3-nitrophthalic acid), MMA (monomethylamine), 3-NPI (3-nitrophthalimide)

[0108] Synthesis of 3,3'-bisphenol A bis(imide ether) (3,3-BPABI). The crude product obtained in the above table was forwarded in two batches. 3-NPI was dissolved in toluene at 75-85°C. Once 3-NPI was completely dissolved, the solution was washed with a 2% sodium bicarbonate (aqueous solution) solution, followed by water washing, and then the organic layer containing 3-NPI in toluene was dried with 1 mol% hexaethylguanidine chloride (HEG-Cl) until the water content was less than 200 ppm. The pre-dried 3-NPI (45.5 g, 0.217 mol) in toluene (275 mL) was combined with a solution of 1 mol% HEG-Cl and a pre-dried salt of BPA (BPANa2, 25 g, 0.1096 mol) in toluene (275 mL) under stirring. The pre-dried salt of BPA was prepared as described in U.S. Pat. No. 7,902,407 and U.S. Pat. No. 395,786. The reaction was carried out to completion within 1 hour. Aliquots were taken for LC-MS analysis. The results of the first batch were labeled 1-RM and the results of the second batch were labeled 1-2-RM. The reaction mixture was washed with water and then with 2% NaHCO3 (aq.) to remove unreacted bisphenol, 3-NPI and other impurities. Toluene was removed and the isolated solid was characterized. The LC-MS results of the first batch were labeled 1-P and the results of the second batch were labeled 2-P.

[0109] In Table 2, the abbreviations are as follows: 3-NPI (3-nitrophthalimide), BPA (bisphenol A), MI (monoimide), 3,3'-BI (3,3'-bis(etherimide)), 3,4-BI (3,4-bis(etherimide)), and 4,4'-BI (4,4'-bis(etherimide)). The amount of each component was measured using LC-MS.

[0110] Table 2

[0111]

[0112] Comparative Example 1

[0113] Five batches of aromatic bis(etherimide) ("BI") were prepared using 3-chlorophthalimide as the starting material. The abbreviations used in Table 3 are defined as follows: 3-ClPI (3-chlorophthalimide), BPA (bisphenol A), MI (monoimide), 3,3'-BI (3,3'-bis(etherimide)), 3,4-BI (3,4-bis(etherimide)), and 4,4'-BI (4,4'-bis(etherimide)). The amount of each component was measured using LC-MS.

[0114] Table 3

[0115]

[0116] The conversion of 3-chlorophthalic anhydride to 3-chlorophthalimide (3-ClPI) can be accomplished using two methods.

[0117] 3-Chlorophthalic anhydride is dissolved in o-dichlorobenzene. To this solution is added an aqueous solution of monomethylamine under stirring. The reaction mixture is stirred at less than 70°C while removing most of the water. Once most of the water (145°C) is removed, drying is continued to remove the water produced by the closed loop, and the solvent is removed by distillation with heating (180°C) to provide 3ClPI.

[0118] Alternatively, 3-chlorophthalic anhydride is melted and MMA gas is passed through the melt to provide the ring-opened amide intermediate. In situ ring closure provides 3ClPI.

[0119] Preparation of 3,3-BPABI from 3ClPI. 3ClPI (410 kg) was dissolved in toluene (3800 L). The solution was dried with 4-6 mol% HEG-Cl to reduce the moisture content to less than 200 ppm. A solution of BPA salt in toluene (1400 kg) was added in batches to the dried solution. The reaction was carried out for 6-10 hours to ensure maximum conversion. The reaction mixture was washed with 2% NaHCO (aqueous) to remove unreacted starting materials and impurities.

[0120] In reaction batches C1-C5, although 3-ClPI was almost completely consumed or completely consumed, the reaction resulted in significantly higher levels of 3,4-BI and 4,4-BI than the process of Example 1 due to the presence of 4-chlorophthalic anhydride in the starting material.

[0121] Starting with 400 kg 3-NPI (1.89 kmol) and 55 kg MMA (1.77 kmol), the above process was repeated on a commercial scale. After the reaction was complete, the reaction mixture was washed twice with 2% NaHCO (aqueous). The resulting product 3-NPI (367 kg) was characterized by LC-MS and was carried to the next step without further purification.

[0122] The analysis of the products is summarized in Table 4. "ND" means not detected. The abbreviations used in Table 4 are defined as follows: 3-NPA (3-nitrophthalimide), 3-NPI (3-nitrophthalimide), PI (phthalimide), DNPI (4-hydroxy-3,5-dinitro-N-methylphthalimide), MI (monoimide), 3,3'-BI (3,3'-bis(etherimide)), 3,4'-BI (3,4'-bis(etherimide)) and 4,4'-BI (4,4'-bis(etherimide)). The amount of each component was measured using LC-MS.

[0123] Table 4

[0124] 3NPA DNPI PI 3-NPI 4NPI Maximum Unimp. Water content <2.0％ <0.3％ <0.5％ >95％ <1％ <2％ <0.5％ 0.01 ND ND 98.0 ND 0.84 0.12

[0125] As shown in the above table, 3-NPI was almost completely consumed and the by-products 4-hydroxy-3,5-dinitro-N-methylphthalimide, 4-nitrophthalimide and phthalimide were not detected.

[0126] 3-NPI (367kg, 1.78kmol) was dissolved in toluene (3.1kL). The temperature of the solution was raised to 75-85°C to completely dissolve 3-NPI. The heated solution was washed with 20kg of 2% NaHCO3 and then with 1.5L of water. HEG-Cl (2mol%) was added to the resulting organic layer to dry the material. BPANa2 (total volume 3.1L) was added in two portions in toluene. After the reaction was complete, the reaction mixture was washed with water and then with 1% NaOH (aqueous). The solvent was removed and the product was characterized by LC-MS. N-methyl-3,3-aromatic bis(etherimide) was obtained with a yield of 99.98%. N-methyl-3,4'-aromatic bis(etherimide) and N-methyl-4,4'-aromatic bis(etherimide) were present at 700ppm and 500ppm, respectively.

[0127] The present invention further encompasses the following aspects.

[0128] Aspect 1a. A method for preparing 3-nitro-N-(C 1-13 A method for preparing a phthalimide composition comprising reacting 3-nitrophthalic acid under conditions effective to provide 3-nitrophthalic anhydride and water, optionally in the presence of a solvent, and wherein water is removed from the reaction mixture during the reaction, and optionally in the presence of a solvent, under conditions effective to provide 3-nitro-N-(C 1-13 alkyl)phthalimide and optionally 4-nitro-N-(C 1-13 3-nitro-N-(C-alkyl)phthalimide 1-13 alkyl) phthalimide composition, 3-nitro-phthalic anhydride and C 1-13 Alkylamine contact.

[0129] Aspect 1b. A method according to aspect 1, wherein 3-nitro-N-(C 1-13 The phthalimide composition comprises less than 20,000 ppm, less than 10,000 ppm, less than 5000 ppm, less than 2500 ppm, or less than 1000 ppm of 4-nitro-N-(C 1-13 Alkyl)phthalimide.

[0130] Aspect 2. The method according to aspect 1a or 1b, wherein based on the weight of 3-nitrophthalic acid, 3-nitro-N-(C 1-13 The percent yield of the alkyl)phthalimide composition is at least 60%, 65%, 70%, 75%, or 80%.

[0131] Aspect 2a. A method according to aspect 1a or 1b, wherein based on 25 g or less of 3-nitrophthalic acid, or based on 25 g of 3-nitrophthalic acid, 3-nitro-N-(C 1-13 The percent yield of the alkyl)phthalimide composition is at least 60%, 65%, or 70%.

[0132] Aspect 2b. A method according to aspect 1a or 1b, wherein based on 5 g or less of 3-nitrophthalic acid, or based on 5 g of 3-nitrophthalic acid, 3-nitro-N-(C 1-13 The percent yield of the alkyl)phthalimide composition is at least 70%, 75%, or 80%.

[0133] Aspect 3a. A method for preparing N-(C 1-13 A method for preparing a 3,3'-aromatic bis(etherimide) composition, the method comprising reacting a dialkali metal salt of a dihydroxy aromatic compound with a 3-nitro-N-(C 1-13 The phthalimide composition is effective to form a 1-13 The N-(C 1-13 The composition comprises N-(C 1-13 alkyl)-3,3'-aromatic bis(etherimide) and optionally, N-(C 1-13 Alkyl)-3,4'-aromatic bis(ether imide), N-(C 1-13 alkyl)-4,4'-aromatic bis(etherimide), or a combination thereof.

[0134] Aspect 3b. A method according to aspect 3a, wherein the N-(C 1-13 Alkyl)-3,4'-aromatic bis(ether imide), the N-(C 1-13 alkyl)-4,4'-aromatic bis(ether imide), or a combination thereof containing less than 20,000 ppm, less than 10,000 ppm, less than 5000 ppm, less than 2500 ppm, or less than 1000 ppm of the N-(C 1-13 Alkyl)-3,3'-aromatic bis(etherimide) compositions.

[0135] Aspect 4. A method according to any one of the above aspects, wherein the reaction of 3-nitrophthalic anhydride is carried out under heating in the absence of a solvent to provide 3-nitrophthalic anhydride, and the reaction of 3-nitrophthalic anhydride with C 1-13 The alkylamines react to provide 3-nitro-N-(C1-13 alkyl)phthalimide composition, or a combination thereof.

[0136] Aspect 5. The method according to any one of aspects 1 to 4, wherein 3-nitrophthalic anhydride is reacted to provide 3-nitrophthalic anhydride and 3-nitrophthalic anhydride and C 1-13 The alkylamines react to provide 3-nitro-N-(C 1-13 The alkyl)phthalimide composition is a continuous process.

[0137] Aspect 6. The method according to any one of aspects 3a, 3b, 4 or 5, wherein the dialkali metal salt of the dihydroxy aromatic compound is of the formula:

[0138] M +- OZO -+ M;

[0139] 3-Nitro-N-(C 1-13 Alkyl)phthalimide has the formula (III-a), and 4-nitro-N-(C 1-13 Alkyl)phthalimide has the formula (III-b):

[0140]

[0141] N-(C 1-13 Alkyl)-3,3'-aromatic bis(ether imide) has the formula (IV-a), N-(C 1-13 Alkyl)-3,4'-aromatic bis(etherimide) has the formula (IV-b), and N-(C 1-13 Alkyl)-4,4'-aromatic bis(etherimide) having formula (IV-c)

[0142]

[0143] Wherein, in the above formula, M is an alkali metal; Z is optionally substituted by 1-6 C 1-8 Alkyl groups, 1-8 halogen atoms, or a combination thereof substituted aromatic C 6-24 a monocyclic or polycyclic moiety; and R 1 It is a one-price C 1-13 Alkyl group, preferably methyl group.

[0144] Aspect 7. The method according to aspect 5 or 6, wherein Z is a divalent group of the formula:

[0145]

[0146] Wherein, Q is -O-, -S-, -C(O)-, -SO2-, -SO-, or -C y H 2y-, wherein y is an integer from 1 to 5 or a halogenated derivative thereof, preferably wherein Z is 2,2-(4-phenylene)isopropylidene.

[0147] Aspect 8. The method according to any of aspects 3a, 3b, 4, 5, 6 or 7, further comprising isolating the 3,3-aromatic bis(etherimide) composition, wherein the isolated aromatic bis(etherimide) has a yellowness index of less than 10 measured at 3.2 mm thickness according to ASTM D-1925.

[0148] Aspect 9a. 3-nitro-N-(C 1-13 Alkyl)phthalimide) composition.

[0149] Aspect 9b. A 3-nitro-N-(C 1-13 Alkyl) phthalimide composition, comprising 3-nitro-N-(C 1-13 alkyl)phthalimide and optionally 4-nitro-N-(C 1-13 Alkyl)phthalimide, of which 3-nitro-N-(C 1-13 The phthalimide composition comprises less than 20,000 ppm, less than 10,000 ppm, less than 5000 ppm, less than 2500 ppm, or less than 1000 ppm of 4-nitro-N-(C 1-13 Alkyl)phthalimide.

[0150] Aspect 10a. A 3,3'-aromatic bis(etherimide) composition comprising a 3,3'-aromatic bis(etherimide) and optionally a 3,4'-aromatic bis(etherimide), a 4,4'-aromatic bis(etherimide), or a combination thereof, wherein the 3,3'-aromatic bis(etherimide) composition comprises less than 20,000 ppm, less than 10,000 ppm, less than 5000 ppm, less than 2500 ppm, or less than 1000 ppm of 3,4'-aromatic bis(etherimide) or 4,4'-aromatic bis(etherimide).

[0151] Aspect 10b. A 3,3′-aromatic bis(etherimide) composition prepared according to the method of any one of aspects 3-8.

[0152] Aspect 11. A method for making a polyetherimide, the method comprising contacting a 3,3'-aromatic bis(etherimide) composition prepared by the method of any one of aspects 3-8 with phthalic anhydride in the presence of a catalyst and under conditions effective to provide a 3,3'-bis(ether phthalic anhydride) composition, the 3,3'-bis(ether phthalic anhydride) composition comprising 3,3'-aromatic bis(ether phthalic anhydride) of formula (Va) and optionally 3,4'-aromatic bis(ether phthalic anhydride) of formula (Vb), 4,4'-aromatic bis(ether phthalic anhydride) of formula (Vc), or a combination thereof.

[0153]

[0154] Where Z is optionally replaced by 1-6 C 1-8 Alkyl groups, 1-8 halogen atoms, or a combination thereof substituted aromatic C 6-24 Monocyclic or polycyclic moiety; 1-13 The composition is contacted with an organic diamine of the formula:

[0155] H2N-R-NH2

[0156] Where R is C 6-20 Aromatic hydrocarbon groups or their halogenated derivatives, straight chain or branched C 2-20 Alkylene group or its halogenated derivative, C 3-8 A cycloalkylene group or a halogenated derivative thereof.

[0157] Aspect 12. A method for making a polyetherimide, the method comprising hydrolyzing an aromatic bis(etherimide) prepared by the method of any one of Aspects 3-8 under conditions effective to provide a corresponding aromatic bis(ether tetraacid) composition, the aromatic bis(ether tetraacid) composition comprising an aromatic bis(ether tetraacid) of formula (VII-a) and optionally an aromatic bis(ether tetraacid) of formula (VII-b), an aromatic bis(ether tetraacid) of formula (VII-c), or a combination thereof,

[0158]

[0159] condensing the aromatic bis(ether tetraacid) composition under conditions effective to provide a 3,3'-aromatic bis(ether phthalic anhydride) composition comprising 3,3'-aromatic bis(ether phthalic anhydride) and, optionally, 3,4'-aromatic bis(ether phthalic anhydride), 4,4'-aromatic bis(ether phthalic anhydride), or a combination thereof,

[0160]

[0161] Where Z is optionally replaced by 1-6 C 1-8 Alkyl groups, or 1-8 halogen atoms, or a combination thereof substituted aromatic C 6-24 monocyclic or polycyclic moiety; and contacting the 3,3'-bis(ether phthalic anhydride) composition with an organic diamine of formula (H2N-R-NH2), wherein R is C 6-20 Aromatic hydrocarbon groups or their halogenated derivatives, straight chain or branched C 2-20 An alkylene group or a halogenated derivative thereof, or a C 3-8 A cycloalkylene group or a halogenated derivative thereof.

[0162] Aspect 13a. A polyetherimide comprising repeating units of formula (VIII-a) and optionally repeating units of formula (VIII-b), repeating units of formula (VIII-c), or a combination thereof,

[0163]

[0164] Where Z is optionally replaced by 1-6 C 1-8 Alkyl groups, 1-8 halogen atoms, or a combination thereof substituted aromatic C 6-24 Monocyclic or polycyclic moiety, R is C 6-20 Aromatic hydrocarbon groups or their halogenated derivatives, straight-chain or branched C 2-20 An alkylene group or a halogenated derivative thereof, or a C 3-8 cycloalkylene groups or halogenated derivatives thereof, and wherein the polyetherimide comprises less than 20,000 ppm, less than 10,000 ppm, less than 5000 ppm, less than 2500 ppm, or less than 1000 ppm of repeating units of formula (VIII-b), repeating units of formula (VIII-c), or combinations thereof.

[0165] Aspect 13b. A polyetherimide prepared according to the method of aspect 11 or 12.

[0166] Aspect 14. An article comprising the polyetherimide of aspect 13a or 13b, wherein the article is in the form of a fiber, a film, a sheet, a foam, a filament, a molded article, an extruded article, or a powder.

[0167] Aspect 15. A method of making the article of aspect 14, comprising molding, casting or extruding the composition to provide the article.

[0168] Alternatively, the compositions, methods and articles may comprise, consist of or consist essentially of any suitable material, step or component disclosed herein. The compositions, methods and articles may additionally or alternatively be formulated so as to be free of or essentially free of any material (or species), step, or component that is otherwise not necessary for achieving the function or purpose of the compositions, methods and articles.

[0169] All ranges disclosed herein include endpoints, and the endpoints can be combined independently of each other (e.g., "up to 25wt%, or more specifically, 5wt% to 20wt%" includes endpoints and all intermediate values ​​of the "5wt% to 25wt%" range, etc.). "Combination" includes blends, mixtures, alloys, reaction products, etc. The terms "first", "second", etc. do not indicate any order, quantity, or importance, but are used to distinguish one element from another. Unless otherwise indicated herein or clearly contradicted by the context, the terms "one", "a kind of", and "the" do not indicate a limit on quantity, but are interpreted to cover the singular and plural. Unless otherwise explicitly stated, "or" means "and / or". Throughout the specification, "some aspects", "one aspect", etc. refer to specific elements described in conjunction with the aspect, which are included in at least one aspect described herein, and may or may not be present in other aspects. In addition, it should be understood that the described elements can be combined in any suitable manner in various aspects. "Their combination" is open and includes any combination, which contains at least one of the listed components or properties, optionally together with unlisted similar or equivalent components or properties.

[0170] Unless specified to the contrary herein, all test standards are the most current standards in effect as of the filing date of this application, or, if priority is claimed, the filing date of the earliest priority application in which the test standards appear.

[0171] Unless otherwise defined, technical and scientific terms used herein have the same meanings as those generally understood by those of ordinary skill in the art to which this application belongs. All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if a term in this application contradicts or conflicts with a term in a combined reference, the term from this application takes precedence over the conflicting term from the combined reference.

[0172] Compounds are described using standard nomenclature. For example, any position not substituted by any indicator group is understood to have its valency filled by a bond or hydrogen atom as indicated. A dash ("-") not between two letters or symbols is used to indicate the point of attachment of a substituent. For example, -CHO is connected through the carbon of a carbonyl group.

[0173] The term "alkyl" refers to a branched or straight chain, unsaturated aliphatic hydrocarbon group, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, and n-hexyl and sec-hexyl. "Alkenyl" refers to a straight or branched monovalent hydrocarbon group having at least one carbon-carbon double bond (for example, vinyl (-HC=CH2)). "Alkoxy" refers to an alkyl group connected via oxygen (i.e., alkyl-O-), such as methoxy, ethoxy and sec-butoxy. "Alkylene" refers to a straight or branched, saturated, divalent aliphatic hydrocarbon group (for example, methylene (-CH2-) or propylene (-(CH2)3-)). "Cycloalkylene" refers to a divalent cyclic alkylene group, -C n H 2n-x , wherein x is the number of hydrogens replaced by cyclization. "Cycloalkenyl" refers to a monovalent group having one or more rings and one or more carbon-carbon double bonds in the ring, wherein all ring members are carbon (e.g., cyclopentyl and cyclohexyl). "Aryl" refers to an aromatic hydrocarbon group containing a specified number of carbon atoms, such as phenyl, cycloheptatrienone, indanyl, or naphthyl. "Arylene" refers to a divalent aryl group. "Alkylidenearylene" refers to an arylidene group substituted by an alkyl group. "Arylalkylene" refers to an alkylene group substituted by an aryl group (e.g., benzyl). The prefix "halo" refers to a group or compound comprising one or more of fluorine, chlorine, bromine, or iodine substituents. There may be a combination of different halogen groups (e.g., bromine and fluorine) or only chlorine groups. The prefix "hetero" refers to a compound or group comprising at least one ring member of a heteroatom (e.g., 1, 2, or 3 heteroatoms), wherein the heteroatoms are each independently N, O, S, Si, or P. "Substituted" means that the compound or group is substituted with at least one (e.g., 1, 2, 3, or 4) substituents, each of which may be independently C 1-9 Alkoxy, C 1-9 Haloalkoxy, nitro (-NO2), cyano (-CN), C 1-6 Alkylsulfonyl (-S(=O)2-alkyl), C 6-12 Arylsulfonyl (-S(=O)2-aryl)thiol (-SH), thiocyanato (-SCN), tosyl (CH3C6H4SO2-), C 3-12 Cycloalkyl, C 2-12 Alkenyl, C 5-12 Cycloalkenyl, C 6-12 Aryl, C 7-13 Arylalkylene, C 4-12 Heterocycloalkyl, and C 3-12 A heteroaryl group replaces a hydrogen provided that the normal valence of the substituted atom is not exceeded. The number of carbon atoms indicated in the group does not include any substituents. For example, -CH2CH2CN is a C2 alkyl group substituted with a nitrile.

[0174] While certain aspects have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are not presently foreseeable or may not be foreseeable may occur to the applicant or others 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. A method for preparing 3-nitro-N-(C 1-13 A method for preparing a phthalimide composition comprising: reacting 3-nitrophthalic acid, optionally in the presence of a solvent, under conditions effective to provide a reaction mixture comprising 3-nitrophthalic anhydride and water, and wherein water is removed from the reaction mixture during the reaction; Optionally, in the presence of a solvent, 3-nitro-phthalic anhydride is reacted with C 1-13 alkylamine to provide a 3-nitro-N-(C 1-13 alkyl)phthalimide and optionally 4-nitro-N-(C 1-13 3-nitro-N-(C-alkyl)phthalimide 1-13 Alkyl)phthalimide composition.

2. The method according to claim 1, wherein: Based on the weight of 3-nitrophthalic acid, the 3-nitro-N-(C 1-13 The percent yield of the alkyl)phthalimide composition is at least 60%, 65%, 70%, 75%, or 80%.

3. A method for preparing N-(C 1-13 A method for preparing a bis(alkyl)-3,3'-aromatic bis(etherimide) composition, comprising: Preparation of 3-nitro-N-(C 1-13 alkyl)phthalimide composition; and In the effective formation of N-(C 1-13 The product mixture of the dihydroxy aromatic compound and the 3-nitro-N-(C 1-13 The N-(C 1-13 Alkyl)-3,3'-aromatic bis(etherimide) compositions comprising N-(C 1-13 alkyl)-3,3'-aromatic bis(etherimide) and optionally N-(C 1-13 Alkyl)-3,4'-aromatic bis(ether imide), N-(C 1-13 alkyl)-4,4'-aromatic bis(etherimide), or a combination thereof.

4. The method according to claim 3, wherein: Reaction of 3-nitrophthalic acid in the absence of solvent with heating to provide 3-nitro-phthalic anhydride, or In the absence of solvent, 3-nitro-phthalic anhydride and C 1-13 alkylamine to provide the 3-nitro-N-(C 1-13 alkyl)phthalimide composition, or a combination thereof.

5. The method according to any one of claims 1 to 4, wherein: 3-nitrophthalic acid is reacted to provide 3-nitrophthalic anhydride and 3-nitrophthalic anhydride is reacted with C 1-13 alkylamine to provide the 3-nitro-N-(C 1-13 The alkyl)phthalimide composition is a continuous process.

6. The method according to any one of claims 3 to 5, wherein: The dialkali metal salt of a dihydroxy aromatic compound is of the formula: M +- O-Z-O -+ M; 3-Nitro-N-(C 1-13 Alkyl)phthalimide has the formula (III-a), and 4-nitro-N-(C 1-13 Alkyl)phthalimide has the formula (III-b): N-(C 1-13 Alkyl)-3,3'-aromatic bis(ether imide) has the formula (IV-a), N-(C 1-13 Alkyl)-3,4'-aromatic bis(etherimide) has the formula (IV-b), and N-(C 1-13 alkyl 4,4'-aromatic bis(etherimide) having the formula (IV-c) Among them, in the above formula, M is an alkali metal; Z is optionally replaced by 1-6 C 1-8 Alkyl groups, 1-8 halogen atoms, or a combination thereof substituted aromatic C 6-24 a monocyclic or polycyclic moiety; and R 1 It is a one-price C 1-13 Alkyl group, preferably methyl group.

7. The method according to claim 5 or 6, wherein: Z is a divalent group of the formula: Wherein, Q is -O-, -S-, -C(O)-, -SO2-, -SO-, or -C y H 2y -, or halogenated derivatives thereof, wherein y is an integer from 1 to 5, preferably wherein Z is 2,2-(4-phenylene)isopropylidene.

8. The method according to any one of claims 3 to 7, further comprising: The 3,3-aromatic bis(etherimide) composition is isolated, wherein the isolated aromatic bis(etherimide) has a yellowness index of less than 10 measured at a thickness of 3.2 mm according to ASTM D-1925.

9. A 3-nitro-N-(C 1-13 Alkyl) phthalimide composition, comprising 3-nitro-N-(C 1-13 alkyl)phthalimide and optionally 4-nitro-N-(C 1-13 alkyl)phthalimide, wherein the 3-nitro-N-(C 1-13 The phthalimide composition comprises less than 20,000 ppm, less than 10,000 ppm, less than 5000 ppm, less than 2500 ppm, or less than 1000 ppm of 4-nitro-N-(C 1-13 Alkyl)phthalimide.

10. A 3,3'-aromatic bis(etherimide) composition comprising a 3,3'-aromatic bis(etherimide) and optionally a 3,4'-aromatic bis(etherimide), a 4,4'-aromatic bis(etherimide), or a combination thereof, wherein the 3,3'-aromatic bis(etherimide) composition comprises less than 20,000 ppm, less than 10,000 ppm, less than 5000 ppm, less than 2500 ppm, or less than 1000 ppm of 3,4'-aromatic bis(etherimide), 4,4'-aromatic bis(etherimide), or a combination thereof.

11. A method for producing a polyetherimide, the method comprising: Preparation of N-(C) according to any one of claims 3 to 8 1-13 alkyl)-3,3'-aromatic bis(etherimide) compositions; and contacting a 3,3'-aromatic bis(ether imide) composition with phthalic anhydride in the presence of a catalyst and under conditions effective to provide a 3,3'-bis(ether phthalic anhydride) composition comprising 3,3'-aromatic bis(ether phthalic anhydride) of formula (Va) and optionally 3,4'-aromatic bis(ether phthalic anhydride) of formula (Vb), 4,4'-aromatic bis(ether phthalic anhydride) of formula (Vc), or a combination thereof, Where Z is optionally replaced by 1-6 C 1-8 Alkyl groups, 1-8 halogen atoms, or a combination thereof substituted aromatic C 6-24 a monocyclic or polycyclic moiety; The 3,3'-bis(ether phthalic anhydride) composition is contacted with an organic diamine of the formula: H2N-R-NH2 Where R is C 6-20 Aromatic hydrocarbon groups or their halogenated derivatives, straight-chain or branched C 2-20 An alkylene group or a halogenated derivative thereof, or a C 3-8 A cycloalkylene group or a halogenated derivative thereof.

12. A method for producing a polyetherimide, the method comprising: Preparation of N-(C) according to any one of claims 3 to 8 1-13 alkyl)-3,3'-aromatic bis(etherimide) compositions; and hydrolyzing an aromatic bis(ether imide) composition under conditions effective to provide a corresponding aromatic bis(ether tetraacid) composition comprising an aromatic bis(ether tetraacid) of formula (VII-a) and optionally an aromatic bis(ether tetraacid) of formula (VII-b), an aromatic bis(ether tetraacid) of formula (VII-c), or a combination thereof, condensing an aromatic bis(ether tetraacid) composition under conditions effective to provide an aromatic bis(ether phthalic anhydride) composition comprising 3,3'-aromatic bis(ether phthalic anhydride) of formula (Va) and optionally 3,4'-aromatic bis(ether phthalic anhydride) of formula (Vb), 4,4'-aromatic bis(ether phthalic anhydride) of formula (Vc), or a combination thereof, Where Z is optionally replaced by 1-6 C 1-8 Alkyl or 1-8 halogen substituted aromatic C 6-24 Monocyclic or polycyclic moieties; and The 3,3'-bis(ether phthalic anhydride) composition is contacted with an organic diamine of the formula: H2N-R-NH2 Where R is C 6-20 Aromatic hydrocarbon groups or their halogenated derivatives, straight-chain or branched C 2-20 An alkylene group or a halogenated derivative thereof, or a C 3-8 A cycloalkylene group or a halogenated derivative thereof.

13. A polyetherimide comprising a repeating unit of formula (VIII-a) and optionally a repeating unit of formula (VIII-b), a repeating unit of formula (VIII-c), or a combination thereof, in, Z is optionally replaced by 1-6 C 1-8 Alkyl groups, 1-8 halogen atoms, or a combination thereof substituted aromatic C 6-24 a monocyclic or polycyclic moiety, R is for C 6-20 Aromatic hydrocarbon groups or their halogenated derivatives, straight-chain or branched C 2-20 An alkylene group or a halogenated derivative thereof, or a C 3-8 A cycloalkylene group or a halogenated derivative thereof, and wherein, The polyetherimide comprises less than 20,000 ppm, less than 10,000 ppm, less than 5000 ppm, less than 2500 ppm, or less than 1000 ppm of repeating units of formula (VIII-b), repeating units of formula (VIII-c), or combinations thereof.

14. An article comprising the polyetherimide of claim 13, wherein: The article is in the form of a fiber, film, sheet, foam, filament, molded article, extruded article or powder.

15. A method of making an article as claimed in claim 14 comprising moulding, casting or extruding the composition to provide the article.

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