3,3'-Aromatic bis(etherimide), their polyetherimide, and method for making them

Abstract

3-Nitro-N-(C 1~13 A method for the preparation of a 3-nitro-N-(C 1~13 alkyl)phthalimide composition comprises, optionally, reacting 3-nitrophthalic acid in the presence of a solvent to provide 3-nitro-phthalic anhydride, and, optionally, reacting the 3-nitro-phthalic anhydride with a C 1~13 alkylamine to provide a 3-nitro-N-(C 1~13 alkyl)phthalimide, and optionally, a 3-nitro-N-(C 1~13 alkyl)phthalimide composition comprising 4-nitro-N-(C 1~13 alkyl)phthalimide. The 3-nitro-N-(C 1~13 alkyl)phthalimide composition may have undetectable levels of 4-nitro-N-(C 1~13 alkyl)phthalimide and, as a result, ultimately, polyetherimides derived from the 3-nitro-N-(C 1~13 alkyl)phthalimide composition may be rich in 3,3'-linkages and / or may exclude 3,4' and 4,4'-linkages. The disclosed polyetherimides may have improved flow and reduced yellowness.

Description

Technical Field

[0001] The present disclosure relates to aromatic bis(etherimide), specifically 3,3'-aromatic bis(etherimide), their polyetherimides, methods for making them, and their use.

Background Art

[0002] Polyetherimide is a class of high-performance polymers that can be processed to make molded articles, fibers, films, foams, etc. Polyetherimide further has high strength, toughness, heat resistance, modulus, and a wide range of chemical resistance, and thus is widely used in various industries such as automotive, telecommunications, aerospace, electrical / electronic, transportation, and healthcare. Polyetherimide shows versatility in various manufacturing processes and is applicable to techniques including injection molding, extrusion molding, and thermoforming for preparing molded articles.

[0003] Polyetherimides can be prepared from aromatic bis(etherimide) monomers. Conventional methods for the preparation of aromatic bis(etherimide) monomers often result in a mixture of isomers including 3,3'-aromatic bis(etherimide), 3,4'-aromatic bis(etherimide), and 4,4'-aromatic bis(etherimide). The flow properties of polyetherimides derived from mixtures of aromatic bis(etherimide) isomers correlate with the ratio of 3,3'-aromatic bis(etherimide) to 3,4'-aromatic bis(etherimide) and 4,4'-aromatic bis(etherimide). Polyetherimides derived from mixtures of aromatic bis(etherimide) isomers rich in 3,4'-bis(etherimide) and 4,4'-aromatic bis(etherimide) generally have lower flow than polyetherimides having a lesser amount 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 derived from monomer mixtures rich in 3,3'-aromatic bis(etherimide). SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION

[0004] Accordingly, there remains a need in the art for a method for the preparation of 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. MEANS FOR SOLVING THE PROBLEMS

[0005] The above and other deficiencies of the art are 3-nitro-N-(C 1~13A method for the preparation of an (alkyl)phthalimide composition, comprising reacting 3-nitrophthalic acid, optionally in the presence of a solvent, under effective conditions to provide a reaction mixture comprising 3-nitro-phthalic anhydride and water, wherein the water is removed from the reaction mixture during the reaction, and combining the 3-nitro-phthalic anhydride with an C 1~13 alkylamine, optionally in the presence of a solvent, under effective conditions to provide a 3-nitro-N-(C 1~13 alkyl)phthalimide composition comprising, optionally, 4-nitro-N-(C 1~13 alkyl)phthalimide, which is satisfied by a method comprising 1~13 providing a 3-nitro-N-(C

[0006] The 3-nitro-N-(C 1~13 alkyl)phthalimide composition comprises 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 alkyl)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.

[0007] A method for the preparation of an N-(C 1~13 alkyl)-3,3'-aromatic bis(etherimide) composition comprises reacting a dialkali metal salt of a dihydroxy aromatic compound with the 3-nitro-N-(C 1~13 alkyl)phthalimide composition prepared by the above method under effective conditions to provide an N-(C 1~13 alkyl)-3,3-aromatic bis(etherimide) and, optionally, an N-(C 1~13 alkyl)-3,4'-aromatic bis(etherimide), N-(C 1~13 alkyl)-4,4'-aromatic bis(etherimide), or a combination thereof, comprising an N-(C 1~13Forming a product mixture comprising an alkyl)-3,3'-aromatic bis(etherimide) composition.

[0008] 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.

[0009] A method for the production of polyetherimide comprises contacting a 3,3'-aromatic bis(etherimide) composition prepared by the above method with phthalic anhydride in the presence of a catalyst and under effective conditions to provide a 3,3'-aromatic bis(etherphthalic anhydride) composition comprising 3,3'-aromatic bis(etherphthalic anhydride) of formula (V-a), and optionally 3,4'-aromatic bis(etherphthalic anhydride) of formula (V-b), 4,4'-aromatic bis(etherphthalic anhydride) of formula (V-c), or a combination thereof,

Chemical formula

[0010] Another method for the production of polyetherimide is to hydrolyze the 3,3'-aromatic bis(etherimide) composition prepared by the above method under effective conditions to obtain an aromatic bis(ethertetracarboxylic acid) of formula (VII-a), and optionally, a corresponding aromatic bis(ethertetracarboxylic acid) composition containing an aromatic bis(ethertetracarboxylic acid) of formula (VII-b), an aromatic bis(ethertetracarboxylic acid) of formula (VII-c), or a combination thereof,

Chemical formula

Chemical formula

[0011] The polyetherimide includes 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, [Chemical formula] In the formula, Z is an aromatic C 6~24 monocyclic or polycyclic moiety, optionally substituted by 1 to 6 C 1~8 alkyl groups, 1 to 8 halogen atoms, or combinations thereof, and R is a C 6~20 aromatic hydrocarbon group or a halogenated derivative thereof, a linear or branched C 2~20 alkylene group or a halogenated derivative thereof, or a C 3~8 cycloalkylene group or a halogenated derivative thereof, where the polyetherimide contains less than 20,000 ppm, less than 10,000 ppm, less than 5,000 ppm, less than 2,500 ppm, or less than 1,000 ppm of repeating units of formula (VIII-b), repeating units of formula (VIII-c), or combinations thereof.

[0012] The molded article contains the above polyetherimide.

[0013] A method for manufacturing the above molded article is disclosed.

[0014] The above and other features are illustrated by the following detailed description, examples, and claims.

Embodiments for Carrying Out the Invention

[0015] Conventional methods for the preparation of aromatic bis(etherimide) monomers often result in a mixture of isomers 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(etherimide) use chlorophthalic anhydride, which is a mixture of 4-chlorophthalic anhydride and 3-chlorophthalic anhydride in an approximate ratio of 95:5 as obtained from the supplier. The isomers are separable by distillation, but the boiling points are very close (i.e., 290 °C for 4-chlorophthalic anhydride and 295 °C for 3-chlorophthalic anhydride at atmospheric pressure, respectively), so that some amount of 4-chlorophthalic anhydride is present in the 3-chlorophthalic anhydride distillate and some amount of 3-chlorophthalic anhydride is present in the 4-chlorophthalic anhydride distillate. As a result, there is some loss of 3-chlorophthalic anhydride to the 4-chlorophthalic anhydride distillate, and the 4-chlorophthalic anhydride co-distilled with 3-chlorophthalic anhydride typically remains through the synthesis and ultimately results in 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 being derived from bisphenol A for illustrative purposes only). [Chemical formula]

[0016] The inventors have discovered a method for preparing 3,3'-aromatic bis(etherimide) from 3-nitrophthalic acid that can minimize or eliminate the formation of 3,4'-aromatic bis(etherimide) and 4,4'-aromatic bis(etherimide). As a result, polyetherimides derived from aromatic 3,3'-bis(etherimide) compositions do not contain or contain very low levels of repeating units derived from 3,4'-aromatic bis(etherimide) and 4,4'-aromatic bis(etherimide). As discussed previously, polyetherimides derived from monomer mixtures rich in 3,3'-aromatic bis(etherimide) have improved flow, which is desirable for applications where higher flow is advantageous. As an additional advantage, the yellowness index (YI) of monomer mixtures rich in 3,3'-aromatic bis(etherimide) and polyetherimides derived from monomer mixtures rich in 3,3'-aromatic bis(etherimide) can be lower than that of aromatic bis(etherimide) and polyetherimide prepared using conventional methods.

[0017] The disclosed method is also an improvement over other conventional methods that use nitric acid to introduce a nitro substituent onto the aromatic ring of N-alkylphthalimide, which results in a mixture of 3-nitro-N-alkylphthalimide, 4-nitro-N-alkylphthalimide, and 4-hydroxy-3,5-dinitro-N-alkylphthalimide where 4-nitro-N-alkylphthalimide is the major product.

Chemical formula

[0018] As shown above, a mixture of 3-nitro-N-alkylphthalimide and 4-nitro-N-alkylphthalimide is obtained during nitration. Ultimately, any polyetherimide derived from such a mixture will have repeating units derived from higher levels of 3,4'-aromatic bis(etherimide) and 4,4'-aromatic bis(etherimide), and thus may result in lower flow and higher YI. In addition, this conventional method in which N-alkylphthalimide is nitrated results in the formation of 3,5-dinitro-4-hydroxyphthalimide. This lowers the overall yield of the desired product and must be removed. Thus, the disclosed method is an improvement over this conventional method because 3-nitro-N-alkylphthalimide is prepared as the major product uncontaminated with significant amounts of 4-nitro-N-alkylphthalimide and can exclude 4-nitro-N-alkylphthalimide. The disclosed method also avoids the formation of 3,5-dinitro-4-hydroxyphthalimide.

[0019] As an additional advantage, the disclosed method avoids the use of halogenated synthetic intermediates and enables the preparation of monomers and polyetherimides having a reduced halogen content. In some embodiments, the monomers and polyetherimides can not only have improved flow and YI but also be essentially halogen-free. As used herein, the phrase "essentially halogen-free" is as defined by IEC 61249-2-21 or UL 746H. In accordance with the International Electrotechnical Commission's halogen use restriction (IEC 61249-2-21), a composition should include no more than 900 parts per million (ppm) of chlorine and bromine each, and also no more than 1500 ppm of the total content of bromine, chlorine, and fluorine. In accordance with UL 746H, a composition should include no more than 900 ppm of chlorine, bromine, and fluorine each, and also no more than 1500 ppm of the total content of chlorine, bromine, and fluorine. The bromine, chlorine, and fluorine content in ppm units can be calculated from the composition or measured by elemental analysis techniques.

[0020] Accordingly, another aspect of the present disclosure is a method for producing an N-alkylphthalimide composition. The method first includes reacting 3-nitrophthalic acid to form a 3-nitrophthalic anhydride composition. The 3-nitrophthalic acid is essentially free of 4-nitrophthalic acid, resulting in a 3-nitrophthalic anhydride that is essentially free of 4-nitrophthalic anhydride, a 3-nitro-N-alkylphthalimide composition that is essentially free of 4-nitro-N-alkylphthalimide, a 3,3'-aromatic bis(etherimide) composition that is essentially free of both 3,4'-aromatic bis(etherimide) and 4,4'-aromatic bis(etherimide), and a polyetherimide that is essentially free of 3,4' or 4,4' linkages in the chain. As used herein, the term "essentially free" means that the presence of the component is undetectable by analytical methods such as NMR, LC-MC, HPLC, and GC-MS.

[0021] In some embodiments, the 3-nitrophthalic acid can contain very low levels of 4-nitrophthalic acid. In fact, the isomeric purity of the 3-nitro-phthalic acid starting material is related to the isomeric purity of the downstream synthetic intermediates and polyetherimides. Those skilled in the art will understand that the purity of 3-nitrophthalic acid can vary by supplier and can contain very low levels (i.e., ppm levels) of 4-nitrophthalic acid, and that while the polyetherimide incorporates limited amounts of 3,4' and 4,4' linkages on the polymer chain, such low levels of 4-nitrophthalic acid can ultimately provide a polyetherimide with the desired flow properties.

[0022] The cyclization of 3-nitrophthalic acid can optionally be achieved by heating 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 such that the 3-nitrophthalic acid begins to melt. The 3-nitrophthalic acid can be partially or completely melted. As the anhydride is formed, water is produced by the reaction mixture. This is removed from the reaction mixture as the reaction proceeds. When the reaction is complete or nearly so, the production of water slows or stops.

[0023] In a preferred embodiment, 3-nitrophthalic anhydride is prepared in the absence of a solvent. Advantageously, under solvent-free conditions, the conversion of 3-nitrophthalic acid to 3-nitrophthalic anhydride is complete after about 1 hour. This is a significantly shorter reaction time than the conversion of 4-chlorophthalic acid to 4-chlorophthalic anhydride, which has a reaction time in the range of 6 - 10 hours when water is efficiently removed from the reactor. If a solvent is used, either the solvent can be removed or the reaction mixture comprising 3-nitrophthalic anhydride and the solvent can proceed to the next step without isolating the 3-nitrophthalic anhydride. The solvent-free approach is preferred because it avoids the use of a solvent, which is an additional expense, and the reaction proceeds at a lower temperature, thus reducing the energy usage for this step.

[0024] 3-Nitro-N-(C 1~13 A method for producing an alkyl)phthalimide composition involves reacting 3-nitrophthalic anhydride with an 1~13 alkylamine. This reaction can be carried out with heating and optionally in the presence of a solvent. The conversion of 3-nitrophthalic anhydride to nitro-N-(C 1~13 alkyl)phthalimide can be carried out by heating 3-nitrophthalic acid in the absence of a solvent such that the 3-nitrophthalic acid begins to melt. The 3-nitrophthalic acid can be partially or completely melted. Similar to the previous step, 3-nitro-N-(C 1~13As the (alkyl)phthalimide is formed, water is produced by the reaction mixture. This is removed from the reaction mixture as the reaction proceeds. When the reaction is complete, the production of water ceases. Preferably, 3-nitro-N-(C 1~13 alkyl)phthalimide is essentially free of 4-nitro-N-(C 1~13 alkyl)phthalimide. As used herein, "essentially free of 4-nitro-N-(C 1~13 alkyl)phthalimide" means that the presence of 4-nitro-N-(C 1~13 alkyl)phthalimide is not detectable from the 3-nitro-N-alkylphthalimide composition by an analytical method (e.g., LC-MS, HPLC, GC-MS). Suitable HPLC conditions can be found in U.S. Patent No. 4,902,809.

[0025] Depending on the purity of the 3-phthalic acid, the 3-nitro-N-(C 1~13 alkyl)phthalimide composition may contain low amounts of 3-nitro-N-(C 1~13 alkyl)phthalimide, such as less than 20,000 ppm, less than 10,000 ppm, less than 5,000 ppm, less than 2,500 ppm, less than 1,000 ppm, less than 500 ppm, or less than 100 ppm of 4-nitro-N-(C 1~13 alkyl)phthalimide. In some embodiments, the presence of 4-nitro-N-alkylphthalimide is not detectable from the 3-nitro-N-alkylphthalimide composition by an analytical method (e.g., LC-MS, HPLC, GC-MS). Suitable HPLC conditions can be found in U.S. Patent No. 4,902,809. When the presence of 4-nitro-N-(C 1~13 alkyl)phthalimide is undetectable by an analytical method, N-(C 1~13 alkyl)phthalimide is essentially free of 4-nitro-N-(C 1~13 alkyl)phthalimide.

[0026] Anhydride formation and phthalimide formation can be carried out at temperatures below 250 °C, such as about 150 - 250 °C or 150 - 225 °C. Temperatures outside the temperature ranges disclosed above can also be used. However, lower temperatures can result in reaction rates that are too slow to be cost-effective.

[0027] The pressure range of the nitration process can vary from vacuum to above atmospheric pressure. However, such conditions depend on the type of reactor employed. Otherwise, the process is generally carried out at atmospheric pressure.

[0028] 3 - nitro - phthalic acid to 3 - nitro - N-(C 1~13 The yield from the conversion to 3 - nitro - N - (alkyl) phthalimide compositions can be improved. The % yield can be at least 60%, or 65%, or 70%, or 75%, or 80% based on the weight of 3 - nitro - phthalic acid.

[0029] Accordingly, another aspect of the present disclosure is a method for producing an aromatic bis(etherimide) monomer. The method includes reacting a dialkali metal salt of a dihydroxy aromatic compound with a nitro - N - alkyl phthalimide composition under effective conditions to form a product mixture comprising the aromatic bis(etherimide) monomer.

[0030] The specific conditions for reacting a dialkali metal salt of a dihydroxy aromatic compound with a 3-nitro-N-alkylphthalimide composition to provide an aromatic bis(etherimide) will depend on considerations such as the specific dihydroxy aromatic compound, the specific components of the nitro-N-alkylphthalimide composition, the solvent, and the presence or absence of a phase transfer catalyst. For example, the reaction can be at a temperature of about 25 to 250 °C, such as 100 to 250 °C, or 115 to 200 °C, or 100 to 125 °C, or 115 to 125 °C. The reaction can be at atmospheric pressure, above atmospheric pressure, or below atmospheric pressure. For example, the reaction can be at a pressure of 0 to 70 kPa, or 30 to 70 kPa, or 50 to 70 kPa, or 10 to 30 kPa, or 10 to 40 kPa, or 10 to 50 kPa, or 10 to 60 kPa, or 20 to 40 kPa, or 20 to 50 kPa, or 20 to 60 kPa, or 30 to 50 kPa, or 30 to 60 kPa, or 40 to 60 kPa.

[0031] The reaction mixture can have a solids content of 1 to 90 wt%, or 10 to 90 wt%, or 10 to 80 wt%, or 10 to 70 wt%, or 10 to 60 wt%, or 40 to 90 wt%, or 50 to 90 wt%, or 60 to 90 wt%, or 10 to 50 wt%, or 20 to 50 wt%, or 30 to 50 wt%, or 10 to 40 wt%, or 10 to 30 wt%, or 20 to 40 wt%, depending on the nature of the N-alkyl group, based on the total weight of the reaction mixture. In some embodiments, the reaction mixture can have a solids content of 20 to 30 wt% or 22 to 26 wt% based on the total weight of the reaction mixture. As used herein, "solids content" refers to the weight of the non-solvent components divided by the total weight of the reaction mixture, whether dissolved or in solid form.

[0032] A composition of 1 molar equivalent of a dialkali metal salt and 2 molar equivalents of nitro-N-alkylphthalimide can be used, although either higher or lower amounts will not substantially impair the formation of the desired aromatic bis(etherimide). However, in some embodiments, 2 moles of nitro-N-alkylphthalimide composition per mole of the dialkali metal salt are preferred. In some embodiments, the molar ratio of dialkali metal salt to nitro-N-alkylphthalimide composition can be 1:1.5 to 1:2.5, or 1:1.7 to 1:2.3, or 1:1.8 to 1:2.2, or 1:1.9 to 1:2.1.

[0033] In some embodiments, the reaction for preparing the aromatic bis(etherimide) is carried out in the presence of a solvent. Any organic solvent that does not react with the reactants during the formation of the aromatic bis(etherimide) can be used in the reaction. In some embodiments, the solvent comprises a nonpolar organic solvent. Suitable nonpolar organic solvents include, but are not limited to, toluene, benzene, chlorobenzene, bromobenzene, dichlorobenzene (e.g., ortho-, meta-, or para-dichlorobenzene), trichlorobenzene (e.g., 1,2,4-trichlorobenzene), xylene (including m-xylene, o-xylene, p-xylene, and combinations including at least one of the foregoing), anisole, ethylbenzene, propylbenzene, and mesitylene, or combinations thereof. In some embodiments, the solvent can be a nonpolar organic solvent such as toluene, benzene, chlorobenzene, ortho-dichlorobenzene, 1,2,4-trichlorobenzene, and xylene, or combinations thereof. In some embodiments, the solvent preferably comprises toluene.

[0034] The solvent may include a bipolar aprotic solvent. Suitable bipolar aprotic solvents may include, but are not limited to, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, 1-cyclohexyl-2-pyrrolidone, N-isopropyl-pyrrolidone, tetramethylurea, dimethylformamide, sulfolane, and N-methylcaprolactam, or combinations thereof. In some embodiments, the solvent may be a combination of a nonpolar organic solvent and a bipolar aprotic solvent. For example, the nonpolar organic solvent and the bipolar aprotic solvent may 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.

[0035] The solids content of the product mixture containing the aromatic bis(etherimide) can be 5 to 90 wt%, or 10 to 90 wt%, or 10 to 80 wt%, or 10 to 70 wt%, or 10 to 60 wt%, or 10 to 50 wt%, or 10 to 40 wt%, or 10 to 30 wt%, or 10 to 20 wt%, or 5 to 80 wt%, or 5 to 70 wt%, or 5 to 60 wt%, or 5 to 50 wt%, or 5 to 40 wt%, or 5 to 30 wt%, or 5 to 20 wt%, or 10 to 90 wt%, or 10 to 80 wt%, or 10 to 70 wt%, or 10 to 60 wt%, or 10 to 50 wt%, or 10 to 40 wt%, or 10 to 30 wt%, or 10 to 20 wt%, or 20 to 90 wt%, or 20 to 80 wt%, or 20 to 70 wt%, or 20 to 60 wt%, or 20 to 50 wt%, or 20 to 40 wt%, or 20 to 30 wt%.

[0036] In some embodiments, the reaction can be in the presence of a phase transfer catalyst. A wide 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 is hexa(C 1~12 alkyl)guanidinium salt, tetra(C 1~12(alkyl)ammonium salts, tetra(C 1~12 (alkyl)phosphonium salts, or tetra(C 6~20 (aryl)phosphonium salts. For example, phase transfer 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, and hexaethylguanidinium chloride. Pyridinium salts, such as bis-aminopyridinium salts, may also be used.

[0037] The phase transfer catalyst may be a quaternary salt or a bis-quaternary salt. Quaternary salts that can be used include the catalyst of the formula (R 3 )4Q + X, wherein each R 3 is the same or different and is 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, wherein X is Cl - , Br - , C 1~8 alkoxy, or C 6~18 aryloxy.

[0038] Bis-quaternary salts that can be used include the formula (R 4 ) k Q + (R 3 ) m + Q(R 4 )k (X 2 )2 where each R 3 is independently a divalent C 1~60 hydrocarbon group, and all Rs 3 together contain 4 to 54 carbon atoms, each R 4 is independently a C 1~12 hydrocarbon group, Q is nitrogen or phosphorus, preferably nitrogen, X 2 is an organic or inorganic anionic atom or group, k is an integer from 1 to 3, m is 4 - k, where at least three of the R 3 and R 4 groups attached to each Q atom are aliphatic or alicyclic. Specifically, each R 3 is a divalent C 1~18 alkylene, C 3~8 cycloalkylene, or C 6~18 aromatic group, such as ethylene, propylene, trimethylene, tetramethylene, hexamethylene, octamethylene, decamethylene, dodecamethylene, cyclohexylene, phenylene, tolylene, or naphthylene, or a divalent heterocyclic group derived from a compound such as pyridine or indole. In some embodiments, each R 3~12 is C 3 alkylene, specifically C 1~12 alkylene. Preferably, only one R 3~8 group is present (i.e., m is 1 and each k is 3), which contains 5 to 10, specifically 6 carbon atoms. Exemplary R 3 groups are methyl, ethyl, n - propyl, isopropyl, n - butyl, isobutyl, n - hexyl, n - heptyl, cyclopentyl, cyclohexyl, methylcyclohexyl, phenyl, tolyl, 2-(1,4 - dioxanyl), and 2 - furyl. Preferably, all R 4 groups are alkyl, such as C 4 n - alkyl groups. X 1~4 2 ​can be any anion that is stable under the conditions of use. Suitable anions include chloride, bromide, sulfate, p-toluenesulfonate, and methanesulfonate, preferably bromide. The value of the integer k can be from 1 to 3, and the value of m is 4 - k. In some embodiments, each k is 3 and m is 1. In some embodiments, R 3 and R 4 groups are all aliphatic. Exemplary bis-quaternary salts of this type are those in which R 3 is a polymethylene chain from trimethylene to dodecamethylene, each R 4 is either n-butyl or n-hexyl, Q is nitrogen, X 2 is bromide, each k is 2, m is 2, those in which each R 3 is ethylene, R 4 is n-butyl, Q is nitrogen, X 2 is bromide, each k is 1, m is 3, compounds, and those in which R 3 is hexamethylene, each R 4 is n-butyl, Q is phosphorus, X 2 is bromide, each k is 3, m is 1.

[0039] Quaternary salts that can be used as phase transfer catalysts include quaternary salts of dihydroxy aromatic compounds described in U.S. Patent No. 5,756,843 to Webb et al. For example, the quaternary salt of a dihydroxy aromatic compound can be of formula A + (O-Z-O)2H3, wherein A is a monocationic carbon and nitrogen or phosphorus-containing group (i.e., a group having a single positive charge containing carbon and nitrogen or carbon and phosphorus). Group A contains 1 to 6 C 2~12 alkyl groups. In some embodiments, A preferably contains nitrogen. In some embodiments, A is tetra(C 2~12 alkyl)ammonium or tetra(C 2~12(Alkyl)phosphonium groups, such as tetraethylammonium, tetra-n-butylammonium, tetra-n-butylphosphonium, and diethyldi-n-butylammonium. In some embodiments, A is preferably hexa(C 2~12 (Alkyl)guanidinium groups, such as hexaethylguanidinium, hexa-n-butylguanidinium, or tetraethyldi-n-butylguanidinium. Z is an aromatic C 6~24 monocyclic or polycyclic moiety, optionally substituted by 1 to 6 C 1~8 alkyl groups, 1 to 8 halogen atoms, or combinations thereof. In some embodiments, Z is of the following formula (IIa). Z is 2,2-(4-phenylene)isopropylidene (i.e., the dihydroxyaromatic compound from which Z is derived is 2,2-bis-(4-hydroxyphenyl)propane or bisphenol A). The quaternary salt of the dihydroxyaromatic compound can be prepared, for example, by reaction of an alkali metal hydroxide and a quaternary salt of formula A + X of the dihydroxyaromatic compound of formula HO-Z-OH. Group X can be as described above, a halide, or bromide, or chloride, most preferably chloride. Typical reaction temperatures are preferably about 1 to 125 °C, preferably about 10 to 50 °C, under an inert atmosphere such as nitrogen or argon.

[0040] In some embodiments, the phase transfer catalyst is preferably a hexa(C 1~12 (Alkyl)guanidinium salt, such as hexaethylguanidinium chloride.

[0041] The phase transfer catalyst can be present in an amount of 0.1 to 10 mole percent (mol%), 0.5 to 10 mol%, 0.5 to 5.0 mol% based on the total moles of the dialkali metal salt of the dihydroxyaromatic compound. In some embodiments, the phase transfer catalyst can be present in an amount of 0.1 to 2.5 mol% or 0.5 to 2.5 mol%. In the disclosed method, the amount of catalyst required is 4-hydroxy-3,5-dinitro-N-(C 1~13It has been found that it can be less than the conventional approach in which alkyl) phthalimide (DNPI) is formed as a by-product.

[0042] The aromatic bis(etherimide) can be recovered from the product mixture and purified by various procedures. One procedure involves dissolving the aromatic bis(etherimide) in an organic solvent such as toluene and then washing or extracting with an alkaline solution containing 0.1 to 10 wt% or 1 to 5 wt% alkali to remove by-products such as monimide, phase transfer catalysts, and unreacted starting materials. In some embodiments, the volume ratio of the alkaline solution to the organic phase (e.g., aromatic bis(etherimide) in an organic solvent) during washing or extraction 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.

[0043] The aromatic bis(etherimide) prepared according to the above method can be obtained in a yield of more than 75%, more than 80%, or more than 85%, or more than 90%.

[0044] After recovery, the aromatic bis(etherimide) as indicated by the yellowness index (YI) can be of high or low color. The YI is a value calculated from spectrophotometric color data, which describes the color of the test sample as being colorless or white (low YI) versus more yellow (high YI). The handling and preparation of the sample 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 methylene chloride and measuring the YI of the resulting solution, for example, by an Xrite 7000 Color Eye device (Xrite, Incorporated). In some embodiments, the YI of the aromatic bis(etherimide) can be 15 or less, or 10 or less, for example, 1 to 15 or 1 to 10. In a preferred embodiment, the YI of the aromatic bis(etherimide) determined according to ASTM D-1925 at a thickness of 3.2 mm can be 5 or less. For example, the aromatic bis(etherimide) can have a YI of 1 to 15, or 1 to 10, 5 to 15, or 5 to 10, or 1 to 9, or 1 to 8, or 1 to 7, or 1 to 6, or 1 to 5, or 1 to 4, or 1 to 3, or 2 to 9, or 2 to 8, or 2 to 7, or 2 to 6, or 2 to 5, or 2 to 4, or 3 to 9, or 3 to 8, or 3 to 7, or 3 to 6, or 3 to 5, or 4 to 9, or 4 to 8, or 4 to 7, or 4 to 6, or 5 to 9, or 5 to 8, or 5 to 7, or 6 to 9, or 6 to 8, or 7 to 9 as determined according to ASTM D-1925.

[0045] In one embodiment, a method for producing an aromatic bis(etherimide) preferably involves 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 effective conditions to form a product mixture containing the aromatic bis(etherimide), where the nitro-N-alkylphthalimide composition is 3-nitro-N-(C 1~13 alkyl)phthalimide, and optionally, 4-nitro-N-(C1~13 contains an alkyl)phthalimide, and the aromatic bis(etherimide) has a YI of less than 15, or less than 10, or less than 5 as determined according to ASTM D-1925.

[0046] In some embodiments, the aromatic bis(etherimide) composition is essentially 4-hydroxy-3,5-dinitro-N-(C 1~13 alkyl)phthalimide-free both before isolation of the aromatic bis(etherimide) composition from the reaction mixture and after isolation of the aromatic bis(etherimide) composition from the reaction mixture. This means that the presence of 4-hydroxy-3,5-dinitro-N-(C 1~13 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. Patent No. 4,902,809.

[0047] The dialkali metal salt of the dihydroxy aromatic compound has the formula (I), M +- O-Z-O -+ M (I) wherein M is an alkali metal and Z is an aromatic C 6~24 monocyclic or polycyclic moiety, optionally substituted by 1 to 6 C 1~8 alkyl groups, 1 to 8 halogen atoms, or combinations thereof. The alkali metal M can be, for example, lithium, sodium, potassium, or combinations thereof. In some embodiments, M is sodium. Exemplary groups Z include groups derived from aromatic dihydroxy compounds of formula (II),

Chemical formula

Chemical formula

[0048] The nitro-N-alkylphthalimide composition comprises 3-nitro-N-(C 1~13 alkyl)phthalimide of formula (III-a), and optionally, 4-nitro-N-(C 1~13 alkyl)phthalimide of formula (III-b),

Chemical formula

[0049] The 3,3'-aromatic bis(etherimide) composition includes a 3,3'-aromatic bis(etherimide) of formula (IV-a), and optionally, a 3,4'-aromatic bis(etherimide) of formula (IV-b), and a 4,4'-aromatic bis(etherimide) of formula (IV-c), [Chemical formula] wherein R 1 is a C 1~13 alkyl group or a C 1~4 alkyl group, preferably a methyl group, and Z is as described in formula (I). In some embodiments, Z is a divalent group of formula (IIa) 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). In some embodiments, the aromatic bis(etherimide) includes 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.

[0050] A method for the production of polyetherimide is further disclosed. Advantageously, the disclosed method can provide N-(C 1~13 alkyl)-3,3'-aromatic bis(etherimide) as the main product rather than a by-product as in the conventional method. This enables control of the ratio of the repeating units derived from N-(C 1~13 alkyl)-3,3'-aromatic bis(etherimide), the repeating units derived from N-(C 1~13 alkyl)-3,4'-aromatic bis(etherimide), and the repeating units derived from N-(C 1~13 alkyl)-4,4'-aromatic bis(etherimide). Thus, the flow characteristics can be adjusted by controlling the ratio of the repeating units incorporated into the polyetherimide. In some embodiments, the polyetherimide consists essentially of N-(C 1~13N-(C(alkyl)-3,4'-aromatic bis(etherimide) and N-(C 1~13 It may be desirable that the repeating units derived from N-(C(alkyl)-4,4'-aromatic bis(etherimide) are not contained (i.e., not detectable by the analytical method). As an additional advantage, the polyetherimide derived from N-(C 1~13 alkyl)-3,3-aromatic bis(etherimide) prepared according to the disclosed method may have a lower halogen content compared to polyetherimide prepared according to conventional methods. In certain embodiments, the polyetherimide derived from N-(C 1~13 alkyl)-3,3-aromatic bis(etherimide) prepared according to the disclosed method is essentially halogen-free as defined by IEC 61249-2-21 or UL 746H.

[0051] In other embodiments, it may be desirable for the polyetherimide to include a predetermined amount of repeating units other than those derived from N-(C 1~13 alkyl)-3,3'-aromatic bis(etherimide) using the disclosed method. Therefore, in addition to the N-(C 1~13 alkyl)-3,3'-aromatic bis(etherimide) prepared using the disclosed method, N-(C 1~13 alkyl)-3,3'-aromatic bis(etherimide), N-(C 1~13 alkyl)-3,4'-aromatic bis(etherimide), and N-(C 1~13 alkyl)-4,4'-aromatic bis(etherimide) mixtures prepared according to conventional methods may be added to achieve a predetermined ratio of monomers.

[0052] The method for preparing polyetherimide is the N-(C prepared according to the above method 1~13An alkyl)-3,3'-aromatic bis(etherimide) composition (IV) is contacted in the presence of phthalic anhydride and a catalyst to provide an aromatic bis(ether phthalic anhydride) composition comprising 3,3'-aromatic bis(ether phthalic anhydride) of formula (V-a) and optionally 3,4'-aromatic bis(ether phthalic anhydride) of formula (V-b) and 4,4'-aromatic bis(ether phthalic anhydride) of formula (V-c), wherein, as described above, Z is an aromatic C [Chemical formula] In the formula, as described above, Z is an aromatic C 6~24 a monocyclic or polycyclic moiety and optionally 1 to 6 C 1~8It may include being substituted by an alkyl group, 1 to 8 halogen atoms, or a combination containing them. In some embodiments, Z is 2,2-(4-phenylene)isopropylidene. Exemplary examples of aromatic bis(ether phthalic anhydride) include 3,3'-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl ether dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)benzophenone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride, 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride, 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl ether dianhydride, 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(2,3-dicarboxyphenoxy)benzophenone dianhydride, 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl sulfone dianhydride, 4-(2,3-dicarboxyphenoxy)-4'-(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, as well as various combinations thereof.

[0053] The catalyst can be a tertiary amine. Tertiary amines that can be used as catalysts include aliphatic tertiary amines such as triethylamine and tributylamine, cycloaliphatic tertiary amines such as N,N-diethyl-cyclohexylamine, and aromatic tertiary amines such as N,N-dimethylaniline. In some embodiments, the catalyst is C1~20 It contains a trialkylamine, such as triethylamine and tributylamine, or a combination thereof. In certain embodiments, the catalyst is triethylamine. In some embodiments, the contacting can occur in the presence of 0.5 to 15 mole percent of the catalyst relative to the anhydride.

[0054] The 3,3'-aromatic bis(etherimide) composition and phthalic anhydride are contacted under conditions generally known to be effective to provide a 3,3'-aromatic bis(ether phthalic anhydride) composition that includes 3,3'-aromatic bis(ether phthalic anhydride), and optionally 3,4'-aromatic bis(ether phthalic anhydride) and 4,4'-aromatic bis(ether phthalic anhydride). For example, the phthalic anhydride can be present in a molar excess, such as a 3 to 8 molar excess of phthalic anhydride relative to the aromatic bis(etherimide). The contacting can further be 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 embodiments, the solvent can include a solvent mixture, such as water and toluene. The contacting can occur at a temperature of 100 to 300 °C, or 100 to 280 °C, or 100 to 250 °C, or 110 to 240 °C, or 120 to 230 °C, or 130 to 220 °C, or 150 to 210 °C, or 150 to 250 °C, or 170 to 260 °C. The contacting can occur at a pressure above atmospheric pressure, such as 200 to 700 pounds per square inch (psi), or 200 to 400 psi, or 200 to 600 psi, or 300 to 500 psi, or 300 to 600 psi, or 300 to 700 psi, or 400 to 600 psi, or 500 to 700 psi. The contacting of the aromatic bis(etherimide) and phthalic anhydride can preferably be carried out with agitation (e.g., stirring) for 0.5 to 3 hours.

[0055] A method for producing a polyetherimide further comprises contacting a 3,3'-aromatic bis(etherphthalic anhydride) composition of formula (V) with an organic diamine of formula (VI) to H2N-R-NH2(VI) provide a polyetherimide. In formula (VI), R is a substituted or unsubstituted divalent organic group, such as a substituted or unsubstituted C 6~20 aromatic hydrocarbon group, a substituted or unsubstituted straight or branched C 4~20 alkylene group, a substituted or unsubstituted C 3~8 cycloalkylene group, specifically a halogenated derivative of any of the foregoing. Specifically, in particular, one or more divalent groups of the following formulae,

Chemical formula

[0056] Examples of 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-dimethylhexamethylenediamine, 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-diaminotoluene, m-xylylenediamine, p-xylylenediamine, 2-methyl-4,6-diethyl-1,3-phenylene-diamine, 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-aminophenyl)propane, 2,4-bis(p-amino-t-butyl)toluene, bis(p-amino-t-butylphenyl)ether, bis(p-methyl-o-aminophenyl)benzene, bis(p-methyl-o-aminopentyl)benzene, 1,3-diamino-4-isopropylbenzene, bis(4-aminophenyl)sulfide, bis-(4-aminophenyl)sulfone (also known as 4,4'-diaminodiphenylsulfone (DDS)), and bis(4-aminophenyl)ether. Any of the foregoing C 1~4 alkylated or poly(C 1~4)Alkylation derivatives, such as polymethylated 1,6 - hexanediamine, can be used. Any of the aforementioned positional isomers can also be used. Combinations of these compounds can also be used. In some embodiments, the organic diamine is m - phenylenediamine, p - phenylenediamine, 4,4’ - diaminodiphenyl sulfone, 3,4’ - diaminodiphenyl sulfone, 3,3’ - diaminodiphenyl sulfone, or combinations thereof.

[0057] Contact of the 3,3’ - aromatic bis(ether phthalic anhydride) composition with the organic diamine can be in the presence of a solvent such as N - methylpyrrolidone, dimethylacetamide, dimethylformamide, cresol, veratrole, phenetole, dimethyl sulfoxide, trichloromethane, acetone, methanol, ethanol, toluene, benzene, chlorobenzene, bromobenzene, dichlorobenzene, trichlorobenzene (e.g., 1,2,4 - trichlorobenzene), xylene (including m - xylene, o - xylene, p - xylene, and combinations containing at least one of the aforementioned), anisole, ethylbenzene, propylbenzene, and mesitylene, etc., or combinations thereof. A sufficient amount of solvent is generally utilized 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 embodiments, the solids content can be 15 - 60%.

[0058] In some embodiments, the contacting can be in the presence of an end-capping agent. The end-capping agent limits the molecular weight growth rate and can thus be used to control the molecular weight of the polyetherimide. Exemplary end-capping agents include certain monoamines (such as aniline), and anhydrides (such as phthalic anhydride). In one embodiment, the end-capping agent is phthalic anhydride such that the resulting polyetherimide contains phthalimide as an end-cap of the polymer chain. However, it should be understood that the polyetherimide disclosed herein can have any desired weight average molecular weight (Mw) and can be produced by any end-cap.

[0059] The contacting of the 3,3'-aromatic bis(ether phthalic anhydride) composition with the organic diamine can be at a temperature of 100 - 250 °C, or 120 - 230 °C, or 150 - 210 °C, or 150 - 250 °C, and can preferably be carried out for 0.5 - 10 hours with agitation (such as stirring). To avoid harmful oxidation reactions, the contacting of the aromatic bis(ether phthalic anhydride) with the organic diamine can be blanketed under an inert gas. Examples of such gases are dry nitrogen, helium, and argon. Dry nitrogen may be preferred in some cases. The reaction can be carried out at atmospheric pressure to above atmospheric pressure.

[0060] Alternatively, a method for the production of polyetherimide comprises hydrolyzing an aromatic bis(ether imide) composition of formula (IV) prepared by the above method under effective conditions to provide a corresponding aromatic tetracarboxylic acid composition comprising an aromatic tetracarboxylic acid of formula (VII-a), and optionally, an aromatic tetracarboxylic acid of formula (VII-b), an aromatic tetracarboxylic acid of formula (VII-c), or a combination thereof,

Chemical formula

[0061] Hydrolyzing a 3,3'-aromatic bis(etherimide) composition to provide the corresponding tetracid can be under effective conditions for providing an aromatic tetracid composition, as described, for example, in U.S. Patent No. 3,879,428. For example, the aromatic bis(etherimide) can be hydrolyzed in an aqueous alkali solution containing, for example, 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, and pressure. The organic amine by-products can be removed by standard procedures such as steam distillation and decantation (when butyl-derived materials are used). In addition, the rate of hydrolysis is accelerated by carrying out the reaction above atmospheric pressure and at a temperature of 100 to 220 °C. For example, the hydrolysis can be at a temperature of 120 to 220 °C, or 140 to 220 °C, or 160 to 220 °C, or 180 to 220 °C, or 200 to 220 °C, or 100 to 210 °C, or 100 to 190 °C, or 100 to 170 °C, or 100 to 150 °C, or 100 to 130 °C. The hydrolysis can be at a pressure of 0 MPa to 2 MPa. The hydrolyzed bis(etherimide) can be acidified with an acidic aqueous solution containing, for example, a mineral acid such as sulfuric acid and hydrochloric acid to provide the tetracid.

[0062] The aromatic tetracarboxylic acid composition can be condensed (i.e., dehydrated) under effective conditions for providing an aromatic bis(etherphthalic anhydride) composition of formula (V). Condensing the aromatic tetracarboxylic acid composition to provide the corresponding aromatic bis(etherphthalic anhydride) composition can be under effective conditions for providing the aromatic bis(etherphthalic anhydride) composition. For example, the aromatic tetracarboxylic acid can be condensed by refluxing in the presence of a dehydrating agent, such as acetic anhydride. In some embodiments, a temperature of 100 to 225 °C and a pressure of 0 MPa to 1 MPa can be used. The aromatic bis(etherphthalic anhydride) composition can optionally be isolated using any generally known isolation technique, such as filtration. Alternatively, the aromatic bis(etherphthalic anhydride) composition can be used directly in the preparation of polyetherimide without further purification or isolation.

[0063] A method for the production of polyetherimide from an aromatic tetracarboxylic acid composition (VII) can further include contacting an aromatic bis(etherphthalic anhydride) composition (V) (obtained by dehydrating the aromatic tetracarboxylic acid composition as described above) with an organic diamine of formula (VI) to provide a polyetherimide. The contacting can be in the presence of a solvent or an end-capping agent as described above. Alternatively, in some embodiments, the polyetherimide can be prepared by directly contacting the aromatic tetracarboxylic acid composition (VII) with the organic diamine (VI) to provide a polyetherimide (i.e., dehydration of the tetracarboxylic acid to provide the corresponding aromatic bis(etherphthalic anhydride) is not required).

[0064] The polyetherimide prepared according to either of the above methods for the production of polyetherimide may 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 may have a YI of 40 to 120, or 40 to 110, or 40 to 100, or 40 to 90, or 40 to 80, or 40 to 70, or 40 to 60, or 40 to 50. In some embodiments, the polyetherimide may have a YI of 45 to 120, or 45 to 100, or 45 to 90, or 45 to 80, or 45 to 70, or 45 to 60, or 45 to 55. In other embodiments, the polyetherimide may have a YI of 50 to 120, or 50 to 100, or 50 to 90, or 50 to 80, or 50 to 70, or 50 to 60. In yet other embodiments, the polyetherimide may have a YI of 60 to 120, or 60 to 100, or 60 to 90, or 60 to 80, or 60 to 70, or 70 to 120, or 70 to 100, or 70 to 90, or 70 to 80, or 80 to 120, or 80 to 100. In any of the foregoing embodiments, the YI of the polyetherimide may be determined according to ASTM D1925 at a thickness of 3.2 millimeters.

[0065] The polyetherimide prepared according to either of the above methods for the production of polyetherimide may have a melt volume flow rate measured at 337 °C / 6.6 kgf or 367 °C / 6.6 kgf of 1 to 50 cubic centimeters / 10 minutes (cc / 10 min), preferably 2 to 30 cc / 10 min, as determined according to ASTM D1238.

[0066] The polyetherimide includes the repeating unit of formula (VIII-a) and optionally the repeating unit of formula (VIII-b), the repeating unit of formula (VIII-c), or a combination thereof.

Chemical formula

[0067] The polyetherimide prepared according to the above method contains repeating units of formula (VIII-a) and optionally formula (VIII-b), formula (VIII-c), or combinations 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 certain embodiments, in formula (VIII), R is m-phenylene, p-phenylene, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, or combinations thereof, and Z is a divalent group of formula (II-a), wherein Q is 2,2-isopropylidene.

[0068] There is further disclosed a molded article comprising the polyetherimide prepared as described above. The molded article comprising the polyetherimide can be prepared by a number of methods including molding, foam molding, extrusion molding, thermoforming, spinning, or mold molding. The molded article can be in the form of, for example, fibers, hollow fibers, hollow tubes, sheets, films, multilayer sheets, multilayer films, parts by mold molding, profiles by extrusion molding, coated parts, foams, filaments, or powders. In some embodiments, the molded article is a fiber, film, sheet, foam, filament, molded article by mold molding, molded article by extrusion molding, or powder.

[0069] The molded article comprising the polyetherimide can be prepared by a number of methods including molding, foam molding, extrusion molding, thermoforming, spinning, or mold molding. The molded article can be in the form of, for example, fibers, hollow fibers, hollow tubes, sheets, films, multilayer sheets, multilayer films, parts by mold molding, profiles by extrusion molding, coated parts, foams, filaments, or powders. In some aspects, the molded article is a fiber, film, sheet, foam, filament, molded article by mold molding, molded article by extrusion molding, or powder.

Examples

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

[0071] <Example 1> [Synthesis of 3-Nitro-N-methylphthalimide (3-NPI) from 3-Nitrophthalic Acid] The reaction was carried out on 5 g and 25 g scales. 3-Nitrophthalic acid (3-NP acid) was heated at 210 °C. As the 3-NP acid began to melt, the anhydride ring started to form and water was evolved. After 1 hour, the conversion of 3-NP acid to 3-NP anhydride was complete and the temperature was lowered to 165 °C with stirring. Monomethylamine gas (MMA) was introduced into the reaction vessel. MMA reacts with the anhydride in the ring-opening reaction and the ring-opened intermediate undergoes in situ ring-closing, thus evolving water. When no more water was being generated by the reaction, complete conversion to 3-NPI was indicated. The reaction mixture was cooled to afford a solid. The solid was flaked to give flaky 3-NPI. The crude product was 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.

[0072]

Table 1

[0073] [Synthesis of 3,3'-Bisphenol A Bis(imide Ether) (3,3-BPABI)] The crude product obtained in the above table was processed in two batches. 3-NPI was dissolved in toluene at 75 - 85 °C. Once the 3-NPI was completely dissolved, the solution was washed with 2% sodium bicarbonate (aq.) solution, then washed with water, and then the organic layer containing 3-NPI in toluene was dried with 1 mol% hexaethylguanidinium chloride (HEG-Cl) until the water content was less than 200 ppm. A solution of pre-dried 3-NPI (45.5 g, 0.217 mol) in toluene (275 mL) and a solution of pre-dried salt of BPA (BPANa2, 25 g, 0.1096 mol) in toluene (275 mL) were combined with stirring. The pre-dried salt of BPA was prepared as described in U.S. Patent No. 7,902,407 and U.S. Patent No. 395,786. The reaction proceeded to completion in 1 hour. An aliquot was taken out for LC-MS analysis. The results of the first batch were labeled as 1-RM, and the results of the second batch were labeled as 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 as 1-P, and the results of the second batch were labeled as 2-P.

[0074] The abbreviations in Table 2 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.

[0075] [Table 2]

[0076] <Comparative Example 1> 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.

[0077]

Table 3

[0078] The conversion of 3-chlorophthalic anhydride to 3-chlorophthalimide (3-ClPI) can be achieved using two methods.

[0079] 3-Chlorophthalic anhydride was dissolved in ortho-dichlorobenzene. To this solution, aqueous monomethylamine was added with stirring. While stirring the reaction mixture with heating below 70 °C, bulk water was removed. Once the bulk water was removed (145 °C), drying was continued to remove the water generated by ring closure, and the solvent was removed by heating distillation (180 °C) to provide 3ClPI.

[0080] Alternatively, 3-chlorophthalic anhydride was melted and MMA gas was passed through the melt to provide an open-ring amide intermediate. In situ ring closure provided 3ClPI.

[0081] [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 water content to less than 200 ppm. An aqueous BPA salt solution in toluene (1400 kg) was added in portions to the dried solution. The reaction was continued for 6 - 10 hours to ensure maximum conversion. The reaction mixture was washed with 2% NaHCO3(aq.) to remove unreacted starting materials and impurities.

[0082] In reaction batches C1 - C5, 3 - ClPI was almost completely consumed or completely consumed, but due to the presence of 4 - chlorophthalic anhydride in the starting materials, the reaction resulted in significantly higher levels of 3,4 - BI and 4,4 - BI than the process of Example 1.

[0083] Starting from 400 kg of 3 - NPI (1.89 kmol) and 55 kg of MMA (1.77 kmol), the above procedure was repeated on a commercial scale. After the reaction was complete, the reaction mixture was washed twice with 2% NaHCO3(aq.). The resulting product 3 - NPI (367 kg) was characterized by LC - MS and advanced to the next step without further purification.

[0084] 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 - nitrophthalic acid), 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 amounts of each component were measured using LC - MS.

[0085]

Table 4

[0086] As shown in the table above, 3 - NPI was almost completely consumed, and the by - products 4 - hydroxy - 3,5 - dinitro - N - methylphthalimide, 4 - nitrophthalimide, and phthalimide were not detected.

[0087] 3-NPI (367 kg, 1.78 kmol) was dissolved in toluene (3.1 kL). The temperature of the solution was increased to 75 - 85 °C to completely dissolve 3-NPI. The heated solution was washed with 20 kg of 2% NaHCO3 and then with 1.5 L of water. HEG-Cl (2 mol%) was added to the resulting organic layer and the material was dried. BPANa2 in toluene (total volume 3.1 L) was added in two portions. After completion of the reaction, the reaction mixture was washed with water and then with 1% NaOH (aq.). The solvent was removed and the product was characterized by LC-MS. N-Methyl-3,3-aromatic bis(etherimide) was obtained in 99.98% yield. N-Methyl-3,4’-aromatic bis(etherimide) and N-Methyl-4,4’-aromatic bis(etherimide) were present at 700 ppm and 500 ppm, respectively.

[0088] This disclosure further encompasses the following aspects.

[0089] Aspect 1a. A method for the preparation of a 3-nitro-N-(C 1~13 alkyl)phthalimide composition, comprising reacting 3-nitrophthalic acid, optionally in the presence of a solvent, under effective conditions to provide 3-nitro-phthalic anhydride and water, wherein the water is removed from the reaction mixture during the reaction, and contacting the 3-nitro-phthalic anhydride with a C 1~13 alkylamine, optionally in the presence of a solvent, under effective conditions to provide 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.

[0090] Aspect 1b. The 3-nitro-N-(C 1~13 alkyl)phthalimide composition has less than 20,000 ppm, less than 10,000 ppm, less than 5,000 ppm, less than 2,500 ppm, or less than 1,000 ppm of 4-nitro-N-(C 1~13The method of embodiment 1a comprising (alkyl) phthalimide.

[0091] Embodiment 2. 3-Nitro-N-(C 1~13 The method of embodiment 1a or 1b, wherein the percent yield of the 3-nitro-N-(C(alkyl)phthalimide composition is at least 60%, 65%, 70%, 75%, or 80% based on the weight of 3-nitrophthalic acid.

[0092] Embodiment 2a. 3-Nitro-N-(C 1~13 The method of embodiment 1a or 1b, wherein the percent yield of the 3-nitro-N-(C(alkyl)phthalimide composition is at least 60%, 65%, or 70% based on or based on 25 g or less of 3-nitrophthalic acid.

[0093] Embodiment 2b. 3-Nitro-N-(C 1~13 The method of embodiment 1a or 1b, wherein the percent yield of the 3-nitro-N-(C(alkyl)phthalimide composition is at least 70%, 75%, or 80% based on or based on 5 g or less of 3-nitrophthalic acid.

[0094] Embodiment 3a. A method for the preparation of an N-(C(alkyl)-3,3'-aromatic bis(etherimide) composition, comprising reacting a dialkali metal salt of a dihydroxyaromatic compound with a 3-nitro-N-(C(alkyl)phthalimide composition prepared according to embodiment 1a or 1b under effective conditions to form a product mixture comprising N-(C(alkyl)-3,3'-aromatic bis(etherimide), and optionally, N-(C(alkyl)-3,4'-aromatic bis(etherimide), N-(C(alkyl)-4,4'-aromatic bis(etherimide), or a combination thereof. 1~13 a dialkali metal salt of a dihydroxyaromatic compound with a 3-nitro-N-(C 1~13 alkyl) phthalimide composition and reacting under effective conditions to form an N-(C 1~13 alkyl)-3,3’-aromatic bis(etherimide), and optionally, N-(C 1~13 alkyl)-3,4’-aromatic bis(etherimide), N-(C 1~13 alkyl)-4,4’-aromatic bis(etherimide), or a combination thereof comprising an N-(C 1~13 alkyl)-3,3’-aromatic bis(etherimide) composition.

[0095] Embodiment 3b. N-(C 1~13N-(C(alkyl))-3,4'-aromatic bis(etherimide), N-(C 1~13 (alkyl))-4,4'-aromatic bis(etherimide), or a combination thereof, is a method of embodiment 3a comprising an N-(C(alkyl))-3,3'-aromatic bis(etherimide) composition of less than 20,000 ppm, less than 10,000 ppm, less than 5000 ppm, less than 2500 ppm, or less than 1000 ppm as determined by LC-MS. 1~13 Method of embodiment 3a comprising an N-(C(alkyl))-3,3'-aromatic bis(etherimide) composition.

[0096] Embodiment 4. The reaction of 3-nitrophthalic acid to provide 3-nitrophthalic anhydride is carried out with heating in the absence of a solvent, or the reaction of 3-nitrophthalic anhydride with a C(alkyl)amine to provide a 3-nitro-N-(C(alkyl))phthalimide composition is carried out in the absence of a solvent, or a combination thereof, in any of the methods of embodiments 1a - 3b. 1~13 C(alkyl)amine for providing a 3-nitro-N-(C(alkyl))phthalimide composition 1~13 Method of any of embodiments 1a - 3b, wherein the reaction of 3-nitrophthalic anhydride with a C(alkyl)amine to provide a 3-nitro-N-(C(alkyl))phthalimide composition is carried out in the absence of a solvent, or a combination thereof.

[0097] Embodiment 5. The reaction of 3-nitrophthalic acid to provide 3-nitrophthalic anhydride and the reaction of 3-nitrophthalic anhydride with a C(alkyl)amine to provide a 3-nitro-N-(C(alkyl))phthalimide composition are a continuous process in any one of the methods of embodiments 1 - 4. 1~13 C(alkyl)amine for providing a 3-nitro-N-(C(alkyl))phthalimide composition 1~13 Method of any one of embodiments 1 - 4, wherein the reaction of 3-nitrophthalic acid to provide 3-nitrophthalic anhydride and the reaction of 3-nitrophthalic anhydride with a C(alkyl)amine to provide a 3-nitro-N-(C(alkyl))phthalimide composition are a continuous process.

[0098] Embodiment 6. The dialkali metal salt of the dihydroxyaromatic compound has the formula M +- O-Z-O -+ M wherein 3-nitro-N-(C(alkyl))phthalimide has the formula (III-a), 4-nitro-N-(C(alkyl))phthalimide has the formula (III-b), 1~13 wherein N-(C(alkyl))-3,3'-aromatic bis(etherimide) has the formula (IV-a), N-(C(alkyl))- 1~13 alkyl)-3,3'-aromatic bis(etherimide) has the formula (IV-a), N-(C(alkyl))- [Chemical formula] N-(C(alkyl))- 1~13 alkyl)-3,3'-aromatic bis(etherimide) has the formula (IV-a), N-(C(alkyl))-1~13 The alkyl)-3,4'-aromatic bis(etherimide) has the formula (IV-b), and N-(C 1~13 The alkyl)-4,4'-aromatic bis(etherimide) has the formula (IV-c), [Chemical formula] In the above formula, M is an alkali metal, and Z is an aromatic C 6~24 monocyclic or polycyclic moiety, optionally substituted by 1 to 6 C 1~8 alkyl groups, 1 to 8 halogen atoms, or a combination thereof, and R 1 is a monovalent C 1~13 alkyl group, preferably methyl, according to any one of Methods 3a, 3b, 4, or 5.

[0099] Aspect 7. Z has the formula [Chemical formula] is a divalent group, in which Q is -O-, -S-, -C(O)-, -SO2-, -SO-, or -C where y is an integer from 1 to 5 y H 2y - or a halogenated derivative thereof, preferably, Z is 2,2-(4-phenylene) isopropylidene, according to the method of Aspect 5 or 6.

[0100] Aspect 8. Further comprising isolating the 3,3-aromatic bis(etherimide) composition, wherein the isolated aromatic bis(etherimide) has a yellowness of less than 10 as determined according to ASTM D-1925 at a thickness of 3.2 mm, according to any one of Aspects 3a, 3b, 4, 5, 6, or 7.

[0101] Aspect 9a. A 3-nitro-N-(C 1~13 alkyl)phthalimide composition prepared according to the method of Aspect 1a or 1b.

[0102] Aspect 9b. 3-nitro-N-(C 1~-13 alkyl)phthalimide, and optionally, 4-nitro-N-(C1~13 3-nitro-N-(C(alkyl)phthalimide 1~13 (alkyl)phthalimide composition, wherein the 3-nitro-N-(C 1~13 (alkyl)phthalimide composition contains less than 20,000 ppm, less than 10,000 ppm, less than 5,000 ppm, less than 2,500 ppm, or less than 1,000 ppm of 4-nitro-N-(C 1~13 (alkyl)phthalimide, composition.

[0103] Aspect 10a. A 3,3'-aromatic bis(etherimide) composition comprising 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 contains less than 20,000 ppm, less than 10,000 ppm, less than 5,000 ppm, less than 2,500 ppm, or less than 1,000 ppm of 3,4'-aromatic bis(etherimide) or 4,4'-aromatic bis(etherimide), composition.

[0104] Aspect 10b. A 3,3'-aromatic bis(etherimide) composition prepared according to any one of the methods of Aspects 3 to 8.

[0105] Aspect 11. A method for the production of a polyetherimide, comprising contacting a 3,3'-aromatic bis(etherimide) composition prepared by any one of the methods of Aspects 3 to 8 with phthalic anhydride in the presence of a catalyst and under effective conditions to provide a 3,3'-aromatic bis(etherphthalic anhydride) of formula (V-a), and optionally a 3,4'-aromatic bis(etherphthalic anhydride) of formula (V-b), a 4,4'-aromatic bis(etherphthalic anhydride) of formula (V-c), or a 3,3'-bis(etherphthalic anhydride) composition containing a combination thereof,

Chemical formula

[0106] Embodiment 12. A method for the production of a polyetherimide, comprising hydrolyzing under conditions effective an aromatic bis(etherimide) prepared by the method of any one of embodiments 3-8 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; [ka] condensing an aromatic bis(ether tetraacid) composition under conditions effective to provide a 3,3'-aromatic bis(ether phthalic anhydride) composition comprising a 3,3'-aromatic bis(ether phthalic anhydride), and optionally a 3,4'-aromatic bis(ether phthalic anhydride), a 4,4'-aromatic bis(ether phthalic anhydride), or a combination thereof; [ka] In the formula, Z is an aromatic C 6~24 A monocyclic or polycyclic moiety, optionally having 1 to 6 C 1~8An alkyl group, or from 1 to 8 halogen atoms, or a combination thereof, and contacting a 3,3'-bis(etherphthalic anhydride) composition with an organic diamine of the formula (H2N-R-NH2), wherein R is C 6~20 An aromatic hydrocarbon group or a halogenated derivative thereof, a linear or branched C 2~20 An alkylene group or a halogenated derivative thereof, or C 3~8 A cycloalkylene group or a halogenated derivative thereof, and a method comprising the same.

[0107] Aspect 13a. 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,

Chemical formula

[0108] Aspect 13b. A polyetherimide prepared according to the method of Aspect 11 or 12.

[0109] Aspect 14. A molded article comprising the polyetherimide of Aspect 13a or 13b, wherein the molded article is in the form of a fiber, film, sheet, foam, filament, molded article by molding, molded article by extrusion, or powder.

[0110] Aspect 15. A method for manufacturing the molded article of Aspect 14, the method comprising molding, casting, or extruding the composition to provide the molded article.

[0111] The composition, method, and molded article may alternatively comprise, consist of, or consist essentially of any suitable materials, steps, or components disclosed herein. The composition, method, and molded article may additionally or alternatively be manufactured so as to be lacking in, or substantially free of, any materials (or species), steps, or components that are otherwise not necessary to achieve the functions or objectives of the composition, method, and molded article.

[0112] All ranges disclosed herein include their endpoints, and the endpoints are combinable independently of each other (e.g., a range of "up to 25 wt%, or more specifically 5 wt% to 20 wt%" includes the endpoints and all intermediate values of the range of "5 wt% to 25 wt%", etc.). "Combinations" include blends, mixtures, alloys, reaction products, and the like. Terms such as "first" and "second" do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. Unless otherwise indicated herein or clearly contradicted by the context, the terms "a", "an", and "the" do not denote a limitation of quantity and should be construed to cover both the singular and the plural. Unless expressly stated otherwise, "or" means "and / or". References herein to "some embodiments", "an embodiment", etc. mean that the specific elements described in connection with the embodiment are included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it should be understood that the described elements can be combined in any suitable manner in various embodiments. "Combinations thereof" is open-ended and includes any combination including at least one of the listed components or characteristics, optionally together with other like or equivalent components or characteristics not listed.

[0113] Unless otherwise specified herein to the contrary, all test standards are the most recent standards in effect as of the filing date of this application, or, if priority is claimed, as of the filing date of the earliest priority application in which the test standard appears.

[0114] Unless otherwise defined, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. All cited patents, patent applications, and other references are hereby incorporated by reference in their entirety. However, if the terms of this application conflict or are contrary to the terms of the reference being incorporated, the terms of this application shall control over the contrary terms of the incorporated reference.

[0115] Compounds are described using standard nomenclature. For example, any position not substituted by any of the indicated groups is understood to have its valence satisfied by the indicated bond or a hydrogen atom. A dash ("-") not between two letters or symbols is used to indicate the point of attachment of a substituent. For example, -CHO is attached via the carbon of the carbonyl group.

[0116] The term "alkyl" means a branched or straight-chain unsaturated aliphatic hydrocarbon group such as methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, s-pentyl, and n- and s-hexyl. "Alkenyl" means a straight-chain or branched-chain monovalent hydrocarbon group having at least one carbon-carbon double bond (e.g., ethenyl (-HC=CH2)). "Alkoxy" means an alkyl group linked through oxygen (i.e., alkyl-O-), such as methoxy, ethoxy, and sec-butyloxy groups. "Alkylene" means a straight-chain or branched-chain saturated divalent aliphatic hydrocarbon group (e.g., methylene (-CH2-) or propylene (-(CH2)3-)). "Cycloalkylene" means a divalent cyclic alkylene group -C n H 2n-xmeans that, in the formula, x is the number of hydrogens replaced by cyclization. "Cycloalkenyl" means a monovalent group having one or more rings and one or more carbon-carbon double bonds within the ring, where all ring members are carbon (e.g., cyclopentyl and cyclohexyl). "Aryl" means an aromatic hydrocarbon group containing the specified number of carbon atoms, such as phenyl, tropone, indanyl, or naphthyl. "Arylene" means a divalent aryl group. "Alkylarylene" means an arylene group substituted by an alkyl group. "Arylalkylene" means an alkylene group substituted by an aryl group (e.g., benzyl). The prefix "halo" means a group or compound that includes one or more of fluoro, chloro, bromo, or iodo substituents. Combinations of different halo groups (e.g., bromo and fluoro) or only chloro groups may be present. The prefix "hetero" means that a compound or group includes at least one ring member that is a heteroatom (e.g., 1, 2, or 3 heteroatoms), where each heteroatom is independently N, O, S, Si, or P. "Substituted" means that a compound or group is substituted by at least one (e.g., 1, 2, 3, or 4) substituent, which are each independently, in place of hydrogen, 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 3~12It can be heteroaryl, provided that the normal valence of the atom being substituted is not exceeded. The number of carbon atoms indicated in the group excludes any substituents. For example, -CH2CH2CN is a C2 alkyl group substituted by nitrile.

[0117] Although specific embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are not currently foreseen or that may be the case may occur to the applicant or other persons skilled in the art. Accordingly, the appended claims as filed or as they may be amended are intended to embrace all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

1. 3-nitro-N-(C １～１３ A method for preparing an alkyl)phthalimide composition, 3-nitrophthalic acid is reacted with 3-nitrophthalic anhydride and water under conditions that are effective in the presence of a solvent, wherein the water is removed from the reaction mixture during the reaction. The aforementioned 3-nitrophthalic anhydride C １～１３ By contacting the alkylamine with, optionally, a solvent, 3-nitro-N-(C) １～１３ Alkyl)phthalimide, and optionally 4-nitro-N-(C １～１３ The 3-nitro-N-(C) containing alkyl)phthalimide １～１３ To provide an alkyl phthalimide composition, Methods that include...

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

3. N-(C) １～－１３ A method for preparing alkyl-3,3'-aromatic bis(etherimide) compositions, According to claim 1, the 3-nitro-N-(C １～１３ To prepare an alkyl phthalimide composition, The dialkali metal salt of the dihydroxy aromatic compound is contacted with the 3-nitro-N-(C １～１３ alkyl)phthalimide composition under effective conditions to form a product mixture comprising the N-(C １～１３ alkyl)-3,3'-aromatic bis(etherimide), and optionally, the N-(C １～１３ alkyl)-3,4'-aromatic bis(etherimide), the N-(C １～１３ alkyl)-4,4'-aromatic bis(etherimide), or a combination thereof, and the N-(C １～１３ alkyl)-3,3'-aromatic bis(etherimide) composition containing the same. Methods that include...

4. The reaction of 3-nitrophthalic acid to provide the 3-nitrophthalic anhydride is carried out with heating in the absence of a solvent, or The aforementioned 3-nitro-N-(C １～１３ C for providing an alkyl)phthalimide composition １～１３ The contact of the alkylamine with the 3-nitrophthalic anhydride is carried out in the absence of a solvent, or The combination of those, The method according to claim 3.

5. The reaction of 3-nitrophthalic acid to provide the 3-nitrophthalic anhydride, and the 3-nitro-N-(C １～１３ C for providing an alkyl)phthalimide composition １～１３ The method according to claim 1, wherein the contact of the alkylamine with the 3-nitrophthalic anhydride is a continuous process.

6. The dialkali metal salt of the dihydroxyaromatic compound is formula M ＋－ O-Z-O －＋ M And, The aforementioned 3-nitro-N-(C １～１３ Alkyl)phthalimide is of formula (III-a), and the 4-nitro-N-(C １～１３ Alkyl)phthalimide is given by formula (III-b), 【Chemistry 1】 Said N-(C １～１３ Alkyl)-3,3'-aromatic bis(etherimide) is of formula (IV-a), and the N-(C １～１３ Alkyl)-3,4'-aromatic bis(etherimide) is of formula (IV-b), and the N-(C １～１３ Alkyl)-4,4'-aromatic bis(etherimide) is represented by formula (IV-c), 【Chemistry 2】 In the above formula, M is an alkali metal, Z is aromatic C ６～２４ It is a monocyclic or polycyclic part, and optionally contains 1 to 6 Cs. １～８ Substituted by alkyl groups, 1 to 8 halogen atoms, or combinations thereof, R １ is monovalent C １～１３ It is an alkyl group. The method according to claim 3.

7. Z is an expression 【Transformation 3】 It is a divalent group, In the formula, Q is -O-, -S-, -C(O)-, -SO ２ -, -SO-, or -C where y is an integer from 1 to 5 ｙ H ２ｙ -or its halogenated derivative, The method according to claim 5.

8. The method according to claim 3, further comprising isolating the 3,3-aromatic bis(etherimide) composition, wherein the isolated aromatic bis(etherimide) has a yellowness of less than 10 as determined according to ASTM D-1925 at a thickness of 3.2 mm.

9. 3-nitro-N-(C １～１３ Alkyl)phthalimide, and optionally 4-nitro-N-(C １～１３ 3-nitro-N-(C) containing alkyl phthalimide １～１３ Alkyl)phthalimide composition, wherein the 3-nitro-N-(C １～１３ Alkyl)phthalimide compositions contain less than 20,000 ppm, less than 10,000 ppm, less than 5,000 ppm, less than 2,500 ppm, or less than 1,000 ppm of 4-nitro-N-(C １～１３ A composition containing alkyl phthalimide.

10. A 3,3'-aromatic bis(etherimide) composition comprising 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 3,4'-aromatic bis(etherimide), 4,4'-aromatic bis(etherimide), or a combination thereof in amounts less than 20,000 ppm, less than 10,000 ppm, less than 5,000 ppm, less than 2,500 ppm, or less than 1,000 ppm.

11. A method for producing polyetherimide, According to claim 3, the N-(C １～１３ To prepare an alkyl-3,3'-aromatic bis(etherimide) composition, The present invention provides a 3,3'-bis(etherphthalic anhydride) composition comprising a 3,3'-aromatic bis(etherphthalic anhydride) of formula (V-a), and optionally a 3,4'-aromatic bis(etherphthalic anhydride) of formula (V-b), a 4,4'-aromatic bis(etherphthalic anhydride) of formula (V-c), or a combination thereof, obtained by contacting the 3,3'-aromatic bis(etherimide) composition with a phthalic anhydride in the presence of a catalyst and under effective conditions. 【Chemistry 4】 In the formula, Z is aromatic C ６～２４ It is a monocyclic or polycyclic part, and optionally contains 1 to 6 Cs. １～８ Substitution by alkyl groups, 1 to 8 halogen atoms, or combinations thereof, The 3,3'-bis(etherphthalic anhydride) composition is given by formula H ２ N-R-NH ２ This involves contacting it with an organic diamine, In the formula, R is C ６～２０ Aromatic hydrocarbon groups or their halogenated derivatives, linear or branched C ２～２０ Alkylene group or its halogenated derivative, or C ３～８ It is a cycloalkylene group or a halogenated derivative thereof. Methods that include...

12. A method for producing polyetherimide, According to claim 3, the N-(C １～１３ To prepare an alkyl-3,3'-aromatic bis(etherimide) composition, To provide a corresponding aromatic bis(ethertetraic acid) composition comprising aromatic bis(ethertetraic acid) of formula (VII-a), and optionally aromatic bis(ethertetraic acid) of formula (VII-b), aromatic bis(ethertetraic acid) of formula (VII-c), or a combination thereof, by hydrolyzing an aromatic bis(etherimide) composition under effective conditions, 【Transformation 5】 The present invention provides an aromatic bis(etherphthalic anhydride) composition comprising 3,3'-aromatic bis(etherphthalic anhydride) of formula (V-a), and optionally 3,4'-aromatic bis(etherphthalic anhydride) of formula (V-b), 4,4'-aromatic bis(etherphthalic anhydride) of formula (V-c), or a combination thereof, obtained by condensing the aforementioned aromatic bis(ethertetraic acid) composition under effective conditions. 【Transformation 6】 In the formula, Z is aromatic C ６～２４ It is a monocyclic or polycyclic part, and optionally contains 1 to 6 Cs. １～８ It is substituted with an alkyl group or 1 to 8 halogen atoms, The 3,3'-bis(etherphthalic anhydride) composition is given by formula H ２ N-R-NH ２ This involves contacting it with an organic diamine, In the formula, R is C ６～２０ Aromatic hydrocarbon groups or their halogenated derivatives, linear or branched C ２～２０ Alkylene group or its halogenated derivative, or C ３～８ It is a cycloalkylene group or a halogenated derivative thereof. Methods that include...

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, 【Transformation 7】 During the ceremony, Z is aromatic C ６～２４ It is a monocyclic or polycyclic part, and optionally contains 1 to 6 Cs. １～８ Substituted by alkyl groups, 1 to 8 halogen atoms, or combinations thereof, R is C ６～２０ Aromatic hydrocarbon groups or their halogenated derivatives, linear or branched C ２～２０ Alkylene group or its halogenated derivative, or C ３～８ A cycloalkylene group or its halogenated derivative, Here, the polyetherimide includes repeating units of formula (VIII-b), repeating units of formula (VIII-c), or combinations thereof in amounts of less than 20,000 ppm, less than 10,000 ppm, less than 5,000 ppm, less than 2,500 ppm, or less than 1,000 ppm. Polyetherimide.

14. A molded article comprising the polyetherimide described in claim 13, wherein the molded article is in the form of a fiber, film, sheet, foam, filament, molded article by molding, molded article by extrusion, or powder.

15. A method for producing a molded article according to claim 14, comprising providing the molded article by molding, casting, or extruding the composition.

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