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    • 专利摘要:
    The process for producing the polyimide of the present invention is carried out by diamines in a solvent containing 50 to 100% by weight of an equimolar composition of the nitrogen-containing cyclic compound represented by the following formula (1) and the phenols represented by the following formula (2): It is a method for producing a polyimide which undergoes imidization reaction with tetracarboxylic dianhydride: In the (expression (1), X is -CH 2 - or -N (CH 3) - represents the, in the formula (2), R 1 and R 2, and may be the same with each other or different, and are each, -H , -OH, -CH 3 , -C 2 H 7 , -C 3 H 7 , -C 2 H 9 , -C 5 H 11 , -C 6 H 13 , -C 7 H 15 , -C 8 H 17 , -C 9 H 19 , -C 10 H 21 , -OCH 3 , -O (C 6 H 5 ), -NO 2 , -Cl, -Br or -F.
    公开号:KR20020081434A
    申请号:KR1020027011953
    申请日:2001-03-13
    公开日:2002-10-26
    发明作者:쿠로키타카시；시부야아츠시；타마이쇼지
    申请人:미쯔이카가쿠 가부시기가이샤；
    IPC主号:
    专利说明:

    Production method of polyimide {PROCESS FOR PRODUCING POLYIMIDE}
    [3] Background Art Conventionally, polyimides have been widely used in various fields such as molding materials, composite materials, and electrical and electronic materials because of their excellent heat resistance, mechanical properties, electrical properties, and the like. In particular, the biphenyltetracarboxylic acid type polyimide has various characteristics different from the pyromellitic acid type polyimide, and thus has high usability and many studies and uses have been made. Especially, the following general formula (4)-(6):
    [4]
    [5] Since the polyimide having a repeating unit represented by Shows thermoplasticity, molded articles having various shapes can be obtained by melt molding such as press molding, extrusion molding, injection molding, etc. (GL Wilkes et al. Macromolecules, 30, pp. 1012 (1997); S. Tamai et al., Polymer, 37 (16) pp. 3683 (1996); S. Tamai et al., Polymer, 39 (10) pp. 1945 ( 1998) and the like).
    [6] Polyimide molded bodies are usually produced by sintering molding of non-thermoplastic polyimide powder or by melt molding of thermoplastic polyimide powder. For this reason, many methods for producing polyimide powder have been developed.
    [7] For example, Japanese Unexamined Patent Publication No. Hei 4-142332, Japanese Unexamined Patent Application Publication No. 2000-1545, etc., manufacture of pyromellitic acid type polyimide obtained by heating imidization in an aprotic polar solvent to obtain polyimide. A method is disclosed. The pyromellitic acid type polyimide has low solubility in a solvent, and polyimide is produced and precipitated as the reaction proceeds, so that polyimide powder can be easily obtained.
    [8] However, T. Nakano, 2nd Intern. Conf. As shown on on IP etc., the biphenyl tetracarboxylic acid type polyimide had high solubility in a solvent, and it was difficult to use said method. That is, even if it heat-imides in an aprotic polar solvent, the produced biphenyl tetracarboxylic acid type | mold polyimide does not precipitate or it contains a large amount of solvent, and since it swells, a problem that a reaction system solidifies arises.
    [9] For example, in GL Wilkes et al., Macromolecules, 30, pp. 1012 (1997), heat imidation in N-methyl-2-pyrrolidone, which is an aprotic polar solvent, is carried out by the above formula (4). A polyimide having a repeating structural unit represented is obtained. In this case, the polymer is formed and precipitated as the reaction proceeds, but the polymer concentration during the reaction is about 10% by weight. This is due to the fact that the precipitated polyimide contains a large amount of solvent and swells, so that when the polymer concentration at the time of polymerization is equal to or higher than the above concentration, the reaction system becomes clay and cannot be stirred.
    [10] In Japanese Patent Laid-Open No. 2000-103854, Japanese Patent Laid-Open No. Hei 8-121386, and the like, heat-imidization in cresol results in the repeating structural unit represented by the formula (4) or (6). Genie is obtaining polyimide. In this case, since the produced polymer is dissolved in a solvent, the polymer is precipitated using a large amount of poor solvent after the reaction.
    [11] As mentioned above, since the manufacture of the biphenyl tetracarboxylic-acid polyimide which heat-imides in a solvent is conventionally manufactured by the method of making it react at low concentration or the method of diluting with a poor solvent after making it react at high concentration, volumetric efficiency is extremely Badly, productivity was remarkably low. That is, for example, when a reactor having a capacity of 1 m 3 is used, the polyimide obtainable by the method of GL Wilkes et al. Is less than 100 kg or the method of JP 2000-103854 A. According to the present invention, the amount of polyimide obtained is less than 20 kg.
    [12] In addition, in the conventional method, since the precipitated polyimide contains a large amount of solvent, much effort has been required to remove the solvent by drying or the like.
    [13] In Japanese Unexamined Patent Publication No. 6-220194, "Polyimide Solution Composition and Manufacturing Method Thereof" is a method for directly imidizing an acid dianhydride and an aromatic diamine in an organic polar solvent. A process for producing a polyimide characterized by polycondensation in the presence of the present invention is disclosed.
    [14] The object of the said invention is the solution of the polyimide containing the soluble aliphatic compound in an organic polar solvent, The objective is to suppress the side reaction in a heat | fever imidation reaction in a solvent.
    [15] On the other hand, the manufacturing method of the polyimide which concerns on this invention can precipitate a polyimide during imidation reaction, and can obtain the reaction solution of a slurry state, and it aims at obtaining a polyimide simply by directly filtering a reaction solution. have.
    [16] For this reason, this invention differs remarkably from the said publication in the object and object of this invention.
    [17] In the above publication, the phenolic compound is used as a catalyst for suppressing side reactions, and the amount of the phenolic compound is 1/10 to 1/2 weight times (9 to 33 weight% of the total solvent amount) with respect to the organic polar solvent. Significantly less than the present invention.
    [18] Moreover, the nitrogen-containing cyclic compound represented by General formula (1) mentioned later in the manufacturing method of the high productivity of an biphenyl tetracarboxylic acid type | mold polyimide as described in this invention, and the organic polar solvent mentioned below strongly associate with phenols, As a result, it is not disclosed in the above-mentioned publication No. Hei 6-220194 about the polyimide precursor (polyamic acid) dissolving, the polyimide not dissolving, the equimolar composition having a remarkably high boiling point, and the like. For example, the above publication discloses that poly-containing N-methyl-2-pyrrolidone as an example of a polar solvent and phenol (the mixed molar ratio of N-methyl-2-pyrrolidone / phenol is 65.5 / 34.5) in the solvent. Although there is a description that the synthesis of the mead is carried out at a reaction temperature of 180 ° C., there is no description regarding the specificity regarding the boiling point of the mixed solvent of N-methyl-2-pyrrolidone and phenol, and the like. It shows a high boiling point and there is no description of not mixing with water. In addition, there is no description or suggestion in this publication that biphenyltetracarboxylic acid type polyimide can be precipitated during imidation reaction when an equimolar composition having such specific properties is used as a specific amount of solvent.
    [19] Therefore, there has been a demand for a highly productive method for producing biphenyltetracarboxylic acid type polyimide.
    [20] That is, the present invention is intended to solve the problems associated with the prior art as described above, and an object of the present invention is to provide various physical properties (molding workability, sliding properties, low water absorption, electrical properties, etc.) of polyimide derived from various structures. The present invention provides a method for producing a polyimide by a simple, easy and inexpensive effective step without impairing thermal oxidation stability, radiation resistance, or the like).
    [1] The present invention relates to a method for producing a polyimide, and more particularly, an imidization reaction between diamine and tetracarboxylic dianhydride using an equimolar composition composed of a specific nitrogen-containing cyclic compound and specific phenols as a solvent. The present invention relates to a method for producing a polyimide in which a polyimide and / or oligomer is precipitated during the imidization reaction to form a slurry in a reaction system.
    [2] The present invention also relates to such equimolar compositions.
    [272] A1 is a chart of IR spectra of N-methyl-2-pyrrolidone, m-cresol and their equimolar compositions.
    [273] A2 is a chart of the 1 H-NMR spectrum of an equimolar composition consisting of N-methyl-2-pyrrolidone and m-cresol.
    [274] A3 is a chart of 13 C-NMR spectra of equimolar compositions consisting of N-methyl-2-pyrrolidone and m-cresol.
    [275] A4 is a chart of IR spectra of N-methyl-2-pyrrolidone, p-chlorophenol and their equimolar compositions.
    [276] A5 is a chart of the 1 H-NMR spectrum of an equimolar composition consisting of N-methyl-2-pyrrolidone and p-chlorophenol.
    [277] A6 is a chart of 13 C-NMR spectra of equimolar compositions consisting of N-methyl-2-pyrrolidone and p-chlorophenol.
    [278] B1 is a chart of IR spectrum of 1,3-dimethyl-2-imidazolidinone, m-cresol and their equimolar compositions.
    [279] B2 is a chart of 1 H-NMR spectra of equimolar compositions composed of 1,3-dimethyl-2-imidazolidinone and m-cresol.
    [280] B3 is a chart of 13 C-NMR spectra of equimolar compositions consisting of 1,3-dimethyl-2-imidazolidinone and m-cresol.
    [281] B4 is a chart of IR spectra of 1,3-dimethyl-2-imidazolidinone, p-chlorophenol and their equimolar compositions.
    [282] B5 is a chart of 1 H-NMR spectra of equimolar compositions composed of 1,3-dimethyl-2-imidazolidinone and p-chlorophenol.
    [283] B6 is a chart of 13 C-NMR spectra of equimolar compositions composed of 1,3-dimethyl-2-imidazolidinone and p-chlorophenol.
    [21] Disclosure of the Invention
    [22] MEANS TO SOLVE THE PROBLEM As a result of earnestly pushing forward in order to solve the said subject, when the specific composition is used as a reaction solvent, the various physical properties (molding processability, sliding characteristic, low water absorption property) of a biphenyl tetracarboxylic-acid polyimide The inventors have found that a polyimide can be obtained by a simple, easy and inexpensive effective step without compromising electrical characteristics, thermal oxidation stability, radiation resistance, etc., and have completed the present invention.
    [23] That is, the manufacturing method of the polyimide of this invention is a diamine in the solvent containing 50-100 weight% of equimolar compositions of the nitrogen-containing cyclic compound represented by following General formula (1), and the phenols represented by following General formula (2). And imidation of the tetracarboxylic acid dianhydride with each other:
    [24]
    [25] In the (expression (1), X is -CH 2 - or -N (CH 3) - represents the, in the formula (2), R 1 and R 2, and may be the same with each other or different, and are each, -H , -OH, -CH 3 , -C 2 H 7 , -C 3 H 7 , -C 2 H 9 , -C 5 H 11 , -C 6 H 13 , -C 7 H 15 , -C 8 H 17 , -C 9 H 19 , -C 10 H 21 , -OCH 3 , -O (C 6 H 5 ), -NO 2 , -Cl, -Br or -F.
    [26] It is preferable that the said tetracarboxylic dianhydride contains a biphenyl tetracarboxylic dianhydride, and this tetracarboxylic dianhydride has biphenyl tetracarboxylic dianhydride, Preferably it is 30-100 mol with respect to the total tetracarboxylic dianhydride. It is preferable to contain%.
    [27] The polyimide obtained by the said imidation reaction is a following general formula (3):
    [28]
    [29] [In Formula (3), Y is following formula (e)-(h):
    [30]
    [31] (Wherein R may be the same or different from each other, and each of a single bond, -O-, -CO-, -SO 2- , -S-, -CH 2 -or -C (CH 3 ) 2- At least one selected from the group consisting of one).
    [32] The repeating structural unit represented by the general formula (3) is contained in a proportion of 30 to 100 mol% of the total repeating structural units, and the remaining portions other than the repeating structural unit represented by the general formula (3) are 0 to It is preferable that it is contained in the ratio of 70 mol%.
    [33] It is preferable that the said remaining part has a repeating structural unit which consists of a component unit derived from aromatic tetracarboxylic acid different from the repeating structural unit represented by the said General formula (3).
    [34] It is preferable that the repeating structural unit which consists of a component unit derived from the said aromatic tetracarboxylic acid is a repeating structural unit represented by the following general formula (a) and / or (b):
    [35]
    [36] In the formulas (a) and (b), Ar 1 is represented by the following formulas (e) to (h):
    [37]
    [38] (In formulas (f), (g) and (h), R may be the same or different from each other, and each is a single bond, -O-, -CO-, -SO 2- , -S-, -CH At least one selected from the group consisting of 2 -or -C (CH 3 ) 2- ).
    [39] In the formula (b), Ar 2 represents at least one selected from the group consisting of -O-, -CO-, -SO 2- , -S-, -CH 2 -and -C (CH 3 ) 2 . .
    [40] The polyimide having a repeating structural unit represented by the general formula (3) is preferably a polyimide having at least one repeating structural unit represented by the following general formulas (4) to (6):
    [41]
    [42] It is preferable that the compound represented by the said General formula (1) is N-methyl- 2-pyrrolidone and / or 1,3'- dimethyl- 2-imidazolidinone.
    [43] Phenols represented by the above formula (2) are phenol, o-chlorophenol, m-chlorophenol, p-chlorophenol, o-cresol, m-cresol, p-cresol, 2,3-xyleneol, 2,4 -At least one compound selected from the group consisting of xyleneol, 2,5-xyleneol, 2,6-xyleneol, 3,4-xyleneol and 3,5-xyleneol.
    [44] A solvent containing an equimolar composition of the compound represented by the formula (1) and the phenols represented by the formula (2) in an amount of 50 to 100% by weight, as the remainder of the solvent, is represented by the formula (1). It is preferable to contain the compound to be represented or the phenols represented by the formula (2) in an amount of 0 to 50% by weight.
    [45] In the method for producing the polyimide, it is possible to precipitate the polyimide and / or oligomer during the imidization reaction to make the reaction system into a slurry state.
    [46] In the manufacturing method of the said polyimide, it is preferable to perform reaction in presence of a terminal sealer.
    [47] By the said polyimide manufacturing method, a product can be precipitated in the imidation reaction, and polyimide powder can be obtained.
    [48] The concentration of the raw material monomer ((total weight of raw material monomer) / (total weight of raw material monomer + solvent weight)) consisting of diamines and tetracarboxylic dianhydride in the reaction solution is in the range of 5 to 50% by weight. desirable.
    [49] The polyimide which concerns on this invention is obtained by the said method, It is characterized by the above-mentioned.
    [50] The polyimide powder which concerns on this invention is obtained by the said method, It is characterized by the above-mentioned.
    [51] The solvent which concerns on this invention consists of equimolar compositions of the compound represented by following formula (1), and the phenols represented by following formula (2):
    [52]
    [53] In the (expression (1), X is -CH 2 - or -N (CH 3) - represents the, in the formula (2), R 1 and R 2, and may be the same with each other or different, and are each, -H , -OH, -CH 3 , -C 2 H 7 , -C 3 H 7 , -C 2 H 9 , -C 5 H 11 , -C 6 H 13 , -C 7 H 15 , -C 8 H 17 , -C 9 H 19 , -C 10 H 21 , -OCH 3 , -O (C 6 H 5 ), -NO 2 , -Cl, -Br or -F.
    [54] The said solvent may contain the other solvent, if it contains 50-100 weight% of equimolar compositions of the compound represented by the said General formula (1), and the phenols represented by the said General formula (2).
    [55] The present invention is a method for producing a polyimide which is subjected to imidation reaction in a solvent containing 50 to 100% by weight of an equimolar composition of a nitrogen-containing cyclic compound represented by the general formula (1) and a phenol represented by the general formula (2). to be. In this case, it can use suitably for manufacture of the polyimide which has a repeating structural unit represented by General formula (3).
    [56] The specific example of the manufacturing method of the polyimide of this invention is shown below.
    [57] Diamines, tetracarboxylic dianhydrides and terminal sealants are dissolved in a solvent containing 50 to 100% by weight of an equimolar composition of the nitrogen-containing cyclic compound represented by the formula (1) and the phenols represented by the formula (2). Alternatively, after dispersing, the reaction system is heated to dissolve the monomer and / or polyimide precursor (polyamic acid) in a solvent to make the reaction system uniform, and further heating of the reaction system is followed by diamines and tetracarboxylic acids. 2) An imidization reaction of the anhydrides and the terminal sealant precipitates the product polyimide and / or oligomer in the form of a powder, slurry the reaction system, and then, after completion of the reaction, the reaction solution is filtered to form a powder. The polyimide is recovered.
    [58] <Solvent>
    [59] The present invention is a solvent used for the imidization reaction, wherein a polyimide is prepared using a solvent containing 50 to 100% by weight of an equimolar composition of the nitrogen-containing cyclic compound represented by the formula (1) and the phenols represented by the formula (2). To a method of making a mead:
    [60]
    [61] (In Formula (1), X represents -CH 2 -or -N (CH 3 )-, and in Formula (2), R 1 and R 2 may be the same or different from each other, and- H, -OH, -CH 3 , -C 2 H 7 , -C 3 H 7 , -C 2 H 9 , -C 5 H 11 , -C 6 H 13 , -C 7 H 15 , -C 8 H 17 , —C 9 H 19 , —C 10 H 21 , —OCH 3 , —O (C 6 H 5 ), —NO 2 , —Cl, —Br, or —F).
    [62] <Nitrogen-containing cyclic compound represented by formula (1)>
    [63] The nitrogen-containing cyclic compound represented by the formula (1) used in the present invention is N-methyl-2-pyrrolidone and / or 1,3-dimethyl-2-imidazolidinone.
    [64] The N-methyl-2-pyrrolidone used for this invention can be prepared by using a conventionally well-known method as needed, For example, dehydrogenation of 1, 4- butanediol or the number to maleic anhydride It can obtain by making γ-butyrolactone obtained by addition etc. react with monoalkyl amines, such as monomethyl amine. Moreover, N-methyl-pyrrolidone can also use a commercial thing (made by Mitsubishi Chemical Corporation, BASF, etc.).
    [65] The l, 3-dimethyl-2-imidazolidinone used for this invention can be prepared by using a conventionally well-known method as needed, or it can also use a commercial thing (Mitsui Chemical Co., Ltd. product, etc.). have.
    [66] The nitrogen-containing cyclic compound represented by the formula (1) is known as an aprotic polar solvent and has been conventionally used as a polymerization solvent for polyimide. However, these nitrogen-containing cyclic compounds have strong affinity with the polyimide and easily dissolve the polyimide. For this reason, in the conventional polyimide manufacturing method using these nitrogen-containing cyclic compounds as a solvent, the produced polyimide does not precipitate and the reaction solution becomes viscous, and a large amount of poor solvent is used for recovery of the polyimide. Problem arises that the reaction system is solid because the produced polyimide contains a large amount of solvent and precipitates in a swollen state.
    [67] In addition, the nitrogen-containing cyclic compound represented by the formula (1) has high affinity with water and is mixed with water without limitation. Therefore, in the conventional polyimide production method using these nitrogen-containing cyclic compounds as a solvent, it is difficult to remove byproduct water from the solvent along with the production of the polyimide, resulting in a decrease in the reaction rate or the reached molecular weight. there was. Therefore, in the conventional manufacturing method of the polyimide which uses these nitrogen-containing cyclic compounds as a solvent, the method of removing the by-product water by performing reaction in presence of an azeotrope of water and a solvent was common.
    [68] <Phenols represented by the formula (2)>
    [69] Specific examples of the phenols represented by the general formula (2) used in the present invention include phenol, catechol, resorcinol, hydroquinone, o-ethylphenol, m-ethylphenol, p-ethylphenol, and octyl. Phenol, o-cresol, m-cresol, p-cresol, 2,3-xyleneol, 2,4-xyleneol, 2,5-xyleneol, 2,6-xyleneol, 3,4-xylol, 3 , 5-xyleneol, guayacol, nonylphenol, o-chlorophenol, m-chlorophenol, p-chlorophenol, o-bromophenol, m-bromophenol, p-bromophenol, o-fluoro Phenol, m-fluorophenol, p-fluorophenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, o-nitrophenol, m-nitro phenol, p-nitrophenol and the like. You may use these individually or in mixture of 2 or more types.
    [70] In the present invention, among these phenols, phenol, o-cresol, m-cresol, p-cresol, 2,3-xyleneol, 2,4-xyleneol, 2,5-xyleneol, 2,6- Xyleneol, 3,4-xyleneol, 3,5-xyleneol, o-chlorophenol, m-chlorophenol, p-chlorophenol and the like are preferably used, among which m-cresol, p-cresol and p- Chlorophenol is particularly preferably used.
    [71] In this invention, these phenols can be used 1 type or in combination or 2 or more types.
    [72] Such phenols can be prepared by using a conventionally well-known method as needed, or a commercially available thing can be used.
    [73] The phenols represented by the formula (2) are known as good solvents of polyimide and have been used as polymerization solvents of polyimides. However, in the conventional method for producing polyimide using these phenols as a solvent, the produced polyimide does not precipitate and the reaction solution becomes viscous, and a large amount of poor solvent is required to recover the polyimide. The problem is that the reaction system becomes solid because the produced polyimide contains a large amount of solvent and precipitates in a swollen state.
    [74] <Equivalent molar composition of nitrogen-containing cyclic compound represented by formula (1) and phenols represented by formula (2)>
    [75] The equimolar composition according to the present invention is a composition in which the nitrogen-containing cyclic compound represented by the general formula (1) and the phenols represented by the general formula (2) are blended in an equimolar amount.
    [76] In the equimolar composition according to the present invention, as can be seen in Examples described later, the carbonyl group of the nitrogen-containing cyclic compound represented by the formula (1) and the hydroxyl group of the phenols represented by the formula (2) Strong hydrogen bonds are formed and are strongly associated. Therefore, the affinity between the nitrogen-containing cyclic compound represented by the general formula (1) and the polyimide, or the affinity between the phenols represented by the general formula (2) and the polyimide can be relatively weakened, As a result, it is thought that dissolution of a polyimide and swelling containing a solvent are suppressed.
    [77] The equimolar composition according to the present invention has a markedly higher boiling point than that of each individual since the nitrogen-containing cyclic compound represented by the general formula (1) and the phenols represented by the general formula (2) are strongly associated with each other. Moreover, it is a liquid at room temperature.
    [78] Specifically, as can be seen in the examples described later, for example, N-methyl-2-pyrrolidone (boiling point 204 ° C, freezing point -23 ° C) and m-cresol (boiling point 202.2 ° C, freezing point 11.5) The equimolar composition of (° C) has a boiling point of 230 ° C and a freezing point of less than 0 ° C, and the equimolar composition of N-methyl-2-pyrrolidone and p-cresol (boiling point of 201.9 ° C, freezing point of 34.8 ° C) has a boiling point of 245 ° C, Freezing point is less than 0 degreeC. In the case of the former example, the boiling point of this composition is about 15-20 degreeC higher than the boiling point of N-methyl- 2-pyrrolidone and phenols, and about 40-45 degreeC in the latter example, the difference is remarkably large. Further, for example, in the case of equimolar compositions of 1,3-dimethyl-2-imidazolidinone (boiling point about 225 ° C, freezing point about 8 ° C) and m-cresol (boiling point about 202 ° C, freezing point about 12 ° C), In the case of equimolar compositions having a boiling point of 237 ° C and a freezing point of less than 0 ° C and a 1,3-dimethyl-2-imidazolidinone and p-chlorophenol (boiling point of about 217 ° C, freezing point of about 43 ° C), the boiling point of 257 ° C, Freezing point is less than 0 degreeC. In the case of the former example, it is about 12 degreeC than the boiling point of 1, 3- dimethyl- 2-imidazolidinone, 35 degreeC than the boiling point of m-cresol, and in the case of the latter example, 1, 3- dimethyl- 2-imidazolidi The difference in boiling point is very large, about 20 ° C. higher than the boiling point and 28 ° C. higher than that of p-chlorophenol.
    [79] As described above, in the present invention, as the N-methyl-2-pyrrolidone and phenols are mixed in equimolar amounts, the boiling point is remarkably increased, for example, than the boiling point of N-methyl-2-pyrrolidone or phenols. It is possible to obtain a composition having a temperature higher than or equal to C, preferably higher than or equal to 20 ° C, more preferably higher than or equal to 25 ° C, and a solidification point at room temperature in a liquid state (for example, liquid at 5 ° C). In addition, as a mixture of 1,3-dimethyl-2-imidazolidinone and phenols in equimolar moieties, there is a significant boiling point increase, for example, than the boiling point of 1,3-dimethyl-2-imidazolidinone or phenols. It is possible to obtain a composition having a temperature of 3 ° C. or higher, preferably 10 ° C. or higher, more preferably 20 ° C. or higher, particularly preferably 30 ° C. or higher, and a solidification point at room temperature in a liquid state (for example, liquid at 5 ° C.). .
    [80] In addition, in this invention, the boiling point of a solvent means the temperature when the liquidus temperature in the boiling solution and the gaseous-phase temperature of solvent vapor become the same.
    [81] In general, however, the boiling point of the non-associative mixed solvent is based on Raoult's law. Moreover, it is known that the boiling point represented by Raoul's law changes by interaction, such as hydrogen bond, between mixed solvent components. However, for example, the boiling point of the azeotropic mixture mixture of the weakly acidic phenol and the weakly basic aniline is 186.2 ° C, which is only slightly higher than the boiling point (l81.2 ° C) of the phenol and the boiling point (184.4 ° C) of the aniline, There is no significant boiling point rise as in the present invention. In addition, although the salt which consists of an acid and a base is known to be high melting | fusing point or non-volatile, For example, melting | fusing point of the salt (phenol sodium salt, trihydrate) which consists of phenols and sodium hydroxide which show weak acidity is 61-64 degreeC. The melting point of the salt consisting of N-methyl-2-pyrrolidone (a) showing weak basicity is 80 to 88 ° C., and therefore cannot be used as a solvent. As mentioned above, the property of the equimolar composition which concerns on this invention is extremely specific.
    [82] In the equimolar composition according to the present invention, the nitrogen-containing cyclic compound represented by the general formula (1) and the phenols represented by the general formula (2) are strongly associated with hydrogen bonds. Thus, unlike a common azeotrope, The composition does not depend on the pressure at the time of distillation operation or the like. And such an equimolar composition which concerns on this invention hardly changes the composition ratio even if evaporation and concentration are repeated. Therefore, even if the equimolar composition according to the present invention is used for recovery and reuse by distillation or the like, a constant composition can be maintained at all times, so that composition adjustment is unnecessary. In addition, since the equimolar composition which concerns on this invention isolate | separates into the nitrogen containing cyclic compound and phenol represented by General formula (1) in presence of a base, such as sodium hydroxide, it is represented by General formula (1) which is a raw material by distillation etc. Nitrogen-containing cyclic compounds or phenols can be recovered.
    [83] As can be seen in the examples described later, the equimolar composition according to the present invention has high polarity and is not mixed with water. Therefore, it is excellent in the solubility of the raw material and polyimide precursor (polyamic acid) at the time of polyimide manufacture, and also the removal of the water produced at the time of dehydration reaction is easy, and it is suitable as a polyimide polymerization solvent.
    [84] <Solvent containing 50 to 100% by weight of equimolar composition>
    [85] In the method for producing a polyimide of the present invention, the reaction solvent contains 50 to 100% by weight of an equimolar composition of the nitrogen-containing cyclic compound represented by the formula (1) and the phenols represented by the formula (2). Solvent is used.
    [86] The solvent in this invention mainly consists of the above-mentioned equimolar composition. The proportion in the total solvent weight of the equimolar composition is preferably 70 to 100% by weight, more preferably 80 to 100% by weight, particularly preferably 90 to 100% by weight. In addition, the solvent other than the equimolar composition contains 0 to 50% by weight, preferably 0 to 30% by weight, more preferably 0 to 20% by weight, particularly preferably 0 to 10% by weight of the total solvent weight. You may do it. By coexisting other solvents, various physical properties such as melting point, boiling point, polarity, dielectric constant, and solubility of the reaction solvent used in the present invention can be arbitrarily changed.
    [87] As another solvent which may be contained, a phenol solvent, an aprotic amide solvent, an ether solvent, an amine solvent, etc. are mentioned, for example.
    [88] As the phenol solvent, the above phenols (2) can be used, for example, phenol, o-chlorophenol, m-chlorophenol, p-chlorophenol, o-cresol, m-cresol, p-cresol, 2, 3-xyleneol, 2, 4- xyleneol, 2, 5- xyleneol, 2, 6- xyleneol, 3, 4- xyleneol, 3, 5- xyleneol, etc. are mentioned.
    [89] As an aprotic amide solvent, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, 1,3 -Dimethyl-2-imidazolidinone, N-methylcaprolactam, hexamethylphosphorotriamide, etc. are mentioned.
    [90] As the ether solvent, for example, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, tetrahydrofuran, bis [2- (2-methoxyethoxy) ethyl] ether, 1,4-dioxane, etc. are mentioned.
    [91] As the amine solvent, for example, pyridine, quinoline, isoquinoline, α-picolin, β-picolin, γ-picolin, isophorone, piperidine, 2,4-lutidine, 2,6-ruti Dean, trimethylamine, triethylamine, tripropylamine, tributylamine, etc. are mentioned.
    [92] In addition to the above solvents, dimethyl sulfoxide, dimethyl sulfone, diphenyl ether, sulfolane, diphenyl sulfone, tetramethyl urea, anisole, water, benzene, toluene, o-xylene, m-xylene, p-xylene, chloro Benzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, bromobenzene, o-dibromobenzene, m-dibromobenzene, p-dibromobenzene, o-chlorotoluene, m-chloro Toluene, p-chlorotoluene, o-bromotoluene, m-bromotoluene, p-bromotoluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentane , Hexane, heptane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride, fluorobenzene, methyl acetate, ethyl acetate, butyl acetate, methyl formate, ethyl formate and the like can be used.
    [93] As a solvent which may be contained in the manufacturing method of the polyimide of this invention, it is a solvent similar to the nitrogen-containing cyclic compound represented by General formula (1) which comprises the equimolar composition actually used, or the phenol represented by General formula (2). Particularly preferred.
    [94] <Polyimide>
    [95] The method for producing a polyimide of the present invention can be preferably applied to the production of a polyimide having a repeating structural unit represented by the following formula (3):
    [96]
    [97] In the formula (3), Y is the following formula (e) to (h):
    [98]
    [99] (Wherein R may be the same or different from each other, and each of a single bond, -O-, -CO-, -SO 2- , -S-, -CH 2 -or -C (CH 3 ) 2- At least one selected from the group consisting of:
    [100] Here, the polyimide having the repeating structural unit represented by the formula (3) is 30 to 100 mol%, preferably 50 to 100 mol of the repeating structural unit represented by the formula (3) among all the repeating structural units. %, Particularly preferably 55 to 100 mol%, and as the remaining part, for example, a repeating structural unit containing a component unit derived from aromatic tetracarboxylic acids different from the repeating structural unit represented by the above formula (3). It is preferable to have, for example, 0 to 70 mol%, preferably 0 to 50 mol%, particularly preferably 0 to 45 of the repeating structural unit represented by the following formulas (a) and / or (b) It is preferable to contain mol%.
    [101] In formulas (a) and (b), Ar 1 is represented by the following formulas (e) to (h):
    [102]
    [103] (Wherein, R may be the same or different from each other, and each of a single bond, -O-, -CO-, -SO 2- , -S-, -CH 2 -or -C (CH 3 ) 2-, respectively. At least one selected from the group consisting of:
    [104] In the formula (b), Ar 2 represents at least one selected from the group consisting of -O-, -CO-, -SO 2- , -S-, -CH 2 -and -C (CH 3 ) 2 . .
    [105] Further, the polyimide having a repeating structural unit represented by the general formula (3) is preferably a polyimide having at least one repeating structural unit represented by any one of the following general formulas (4) to (6):
    [106]
    [107] Moreover, it is preferable that the repeating structural unit which comprises the said remainder does not contain the component unit derived from the aliphatic tetracarboxylic acid and aromatic fluorine-containing tetracarboxylic acid which have an aromatic ring.
    [108] T. Nakano, 2nd Intern. Conf. As disclosed in on PI and the like, the biphenyltetracarboxylic acid type polyimide composed of the repeating structural unit represented by the formula (3) has high solubility in a solvent. Therefore, the polyimide containing 30-100 mol% of repeating structural units represented by the said General formula (3) among all the repeating structural units is a conventional method, ie, N-methyl- 2-pyrrolidone or cresol. When the imidation reaction is carried out by heating in a polar solvent, the resulting polyimide does not precipitate or precipitates in a swollen state containing a large amount of solvent, which may cause a problem that the reaction system becomes solid. Moreover, the polyimide which consists of the repeating structural unit represented by General formula (a) has low solubility to a solvent, and it is imidized by heating in a conventional method, ie, a polar solvent called N-methyl- 2-pyrrolidone or cresol. Since the produced polyimide precipitates when it reacts, the manufacturing method of this invention is not needed. In addition, the polyimide composed of the repeating structural unit represented by the formula (b) has very high solubility in a solvent, and even when the production method of the present invention is used, the produced polyimide does not precipitate or contains a large amount of solvent. Since it precipitates in the swollen state, the reaction system may be solidified.
    [109] The terminal of the polyimide manufactured by the manufacturing method of this invention may be sealed by terminal blockers, such as phthalic anhydride, aniline, maleic anhydride, and phenylethynyl phthalic anhydride. Moreover, you may have a branch in the structure of a principal chain, a side chain, or an end, and may have a structure for crosslinking, a cyclic structure, etc.
    [110] There is no restriction | limiting in the polymerization degree of the polyimide manufactured by the manufacturing method of this invention, It can select arbitrarily according to the use of a polyimide. In the conventional method for producing polyimide, when the produced polyimide is not precipitated, that is, when the produced polyimide is dissolved in a solvent, the reaction solution becomes viscous, and thus the degree of polymerization of the produced polyimide is limited. However, in the method for producing the polyimide of the present invention, since the produced polyimide precipitates and the reaction solution is in a slurry state, the reaction solution may interfere with stirring even when producing a high molecular weight polyimide. It is not as viscous as it is.
    [111] <Diamines>
    [112] In the manufacturing method of the polyimide of this invention, conventionally well-known aromatic diamine can be used preferably. Moreover, when aliphatic diamines, siloxane diamines, or fluorine-containing diamines are used, since the obtained polyimide is melt | dissolved in the solvent used for this invention, the effect made into the objective of this invention may not be acquired.
    [113] More specifically,
    [114] (1) As diamines which have one benzene ring, p-phenylene diamine, m-phenylene diamine, etc. are mentioned, for example.
    [115] (2) As diamines having two benzene rings, for example,
    [116] 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether,
    [117] 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide,
    [118] 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide,
    [119] 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone,
    [120] 4,4'diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone,
    [121] 3,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane,
    [122] 3,4'-diaminodiphenylmethane, 2,2-di (3-aminophenyl) propane,
    [123] 2,2-di (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane,
    [124] 1,1-di (3-aminophenyl) -1-phenylethane, 1,1-di (4-aminophenyl) -1-phenylethane,
    [125] 1- (3-aminophenyl) -1- (4-aminophenyl) -1-phenylethane and the like.
    [126] (3) As diamines having three benzene rings, for example,
    [127] 1,3-bis (3-aminophenoxy) benzene, l, 3-bis (4-aminophenoxy) benzene,
    [128] l, 4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene,
    [129] 1,3-bis (3-aminobenzoyl) benzene, 1,3-bis (4-aminobenzoyl) benzene,
    [130] 1,4-bis (3-aminobenzoyl) benzene, 1,4-bis (4-aminobenzoyl) benzene,
    [131] 1,3-bis (3-amino-α, α-dimethylbenzyl) benzene,
    [132] 1,3-bis (4-amino-α, α-dimethylbenzyl) benzene,
    [133] 1,4-bis (3-amino-α, α-dimethylbenzyl) benzene,
    [134] 1,4-bis (4-amino-α, α-dimethylbenzyl) benzene,
    [135] 2,6-bis (3-aminophenoxy) benzonitrile, 2, 6-bis (3-aminophenoxy) pyridine, etc. are mentioned.
    [136] (4) As diamines having four benzene rings, for example,
    [137] 4,4'-bis (3-aminophenoxy) biphenyl, 4,4'-bis (4-aminophenoxy) biphenyl,
    [138] Bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] ketone,
    [139] Bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide,
    [140] Bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone,
    [141] Bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether,
    [142] 2,2-bis [4- (3-aminophenoxy) phenyl] propane,
    [143] 2, 2-bis [4- (4-aminophenoxy) phenyl] propane, etc. are mentioned.
    [144] (5) As diamines having five benzene rings, for example,
    [145] 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene,
    [146] 1,3-bis [4- (4-aminophenoxy) benzoyl] benzene,
    [147] 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene,
    [148] 1,4-bis [4- (4-aminophenoxy) benzoyl] benzene,
    [149] 1,3-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene,
    [150] 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene,
    [151] 1,4-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene,
    [152] 1,4-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene and the like.
    [153] (6) As diamines having six benzene rings, for example,
    [154] 4,4'-bis [4- (4-aminophenoxy) benzoyl] diphenyl ether,
    [155] 4,4'-bis [4- (4-amino-α, α-dimethyl benzyl) phenoxy] benzophenone,
    [156] 4,4'-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone,
    [157] 4,4'-bis [4- (4-aminophenoxy) phenoxy] diphenyl sulfone, etc. are mentioned.
    [158] (7) As other diamines having aromatic substituents, for example,
    [159] 3,3'-diamino-4,4'-diphenoxybenzophenone, 3,3'-diamino-4,4'-dibiphenoxybenzophenone,
    [160] 3,3'- diamino-4- phenoxy benzophenone, 3,3'- diamino-4- biphenoxy benzophenone, etc. are mentioned.
    [161] In the present invention, if necessary, a part or all of the hydrogen atoms on the aromatic rings of the diamines having an aromatic ring may be a methyl group, a methoxy group, an ethynyl group serving as a crosslinking point, a benzocyclobutene-4'-yl group or a vinyl group. And diamines substituted with substituents such as allyl, cyano, isocyanate, nitrilo or isopropenyl groups can also be used.
    [162] Moreover, diamine which has substituents, such as a vinylene group, a vinylidene group, or an ethynylidene group, which become a crosslinking point in a backbone skeleton as needed can also be used.
    [163] In addition, in order to introduce a branch, triamines and tetraamines can also be used instead of diamines.
    [164] These diamines can be used individually or in combination of 2 or more types.
    [165] Tetracarboxylic dianhydride
    [166] In the manufacturing method of the polyimide of this invention, it is preferable to use biphenyl tetracarboxylic dianhydride as tetracarboxylic dianhydride. Specifically as such a biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride, 2,3', 3,4'-biphenyl tetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic acid dianhydride is mentioned. These biphenyl tetracarboxylic dianhydride can be used individually or in combination of 2 or more types. Among these, as tetracarboxylic dianhydride in this invention, 3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride is especially preferable.
    [167] In the present invention, biphenyltetracarboxylic dianhydride is preferably used as tetracarboxylic dianhydride, but other conventionally known tetracarboxylic dianhydride can be used together with biphenyltetracarboxylic dianhydride. As such other tetracarboxylic dianhydride, it is preferable to use aromatic tetracarboxylic dianhydride. Moreover, when the aliphatic tetracarboxylic acid and fluorine-containing tetracarboxylic acid which do not contain an aromatic ring are used, since the polyimide obtained is melt | dissolved in the solvent used by this invention, the effect made into the objective of this invention may not be acquired. . As aliphatic tetracarboxylic acid which does not contain such an aromatic ring, it is bicyclo (2,2,2) -octo-7-ene-2,3,5,6- tetracarboxylic dianhydride, ethylene tetracarboxylic dianhydride, for example. , Butanetetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, and the like.
    [168] Therefore, in this invention, it is preferable not to use aliphatic tetracarboxylic acid or fluorine-containing tetracarboxylic acid which does not contain an aromatic ring as another tetracarboxylic acid.
    [169] As another aromatic tetracarboxylic dianhydride which can be used with the said biphenyl tetracarboxylic dianhydride in this invention, for example,
    [170] Pyromellitic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride,
    [171] Bis (3,4-dicarboxyphenyl) sulfide dianhydride,
    [172] Bis (3,4-dicarboxyphenyl) sulfone dianhydride,
    [173] 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride,
    [174] 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride,
    [175] 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride,
    [176] 4,4'-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride,
    [177] 2,2-bis [(3,4-dicarboxyphenoxy) phenyl] propane dianhydride,
    [178] 2,3,6,7-naphthalene tetracarboxylic dianhydride,
    [179] 1,4,5,8-naphthalene tetracarboxylic dianhydride,
    [180] 2,2 ', 3,3'-benzophenone tetracarboxylic acid dianhydride,
    [181] 2,3 ', 3,4'-benzophenone tetracarboxylic dianhydride,
    [182] 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride,
    [183] Bis (2,3-dicarboxyphenyl) ether dianhydride,
    [184] Bis (2,3-dicarboxyphenyl) sulfide dianhydride,
    [185] Bis (2,3-dicarboxyphenyl) sulfone dianhydride,
    [186] l, 3-bis (2,3-dicarboxyphenoxy) benzene dianhydride,
    [187] 1,4-bis (2,3-dicarboxyphenoxy) benzene dianhydride,
    [188] 1,2,5,6-naphthalene tetracarboxylic dianhydride etc. are mentioned.
    [189] These other aromatic tetracarboxylic dianhydrides can be used individually by 1 type or in combination of 2 or more types.
    [190] In the present invention, if necessary, a part or all of the hydrogen atoms on the aromatic ring of the aromatic tetracarboxylic dianhydride are a methyl group, a methoxy group, an ethynyl group serving as a crosslinking point, a benzocyclobutene-4'-yl group, a vinyl group, Tetracarboxylic dianhydride substituted by substituents, such as an allyl group, a cyano group, an isocyanate group, a nitrilo group, or an isopropenyl group, can also be used.
    [191] Moreover, the tetracarboxylic dianhydride which has substituents, such as a vinylene group, a vinylidene group, or an ethynylidene group, which become a crosslinking point in the backbone skeleton of tetracarboxylic dianhydride can also be used.
    [192] In addition, in order to introduce a branch, it is also possible to use hexacarboxylic acid trianhydride and octacarboxylic acid tetraanhydride instead of tetracarboxylic dianhydride.
    [193] Such tetracarboxylic dianhydride can be used individually by 1 type or in combination of 2 or more types.
    [194] The amount of tetracarboxylic dianhydride used in the present invention is preferably 30 to 100 mol%, more preferably 50 to 100 mol%, particularly preferably biphenyltetracarboxylic dianhydride relative to the total amount of tetracarboxylic dianhydride. Is from 55 to 100 mol%, preferably from 0 to 70 mol%, more preferably from 0 to 50 mol%, particularly preferably from 0 to 45 mol% of other tetracarboxylic dianhydrides.
    [195] When the amount of other tetracarboxylic dianhydrides used is more than 70 mol%, the solubility of the obtained polyimide in the solvent is very high, and the produced polyimide may not precipitate even if the production method of the present invention is used. Or it may cause the problem that a reaction system solidifies because it contains a large amount of solvent and precipitates in the swollen state. In addition, when using more than 70 mol% of pyromellitic dianhydride as another tetracarboxylic dianhydride, for example, since the obtained polyimide has low solubility to a solvent, the manufacturing method of this invention is not needed. Do not.
    [196] That is, the produced polyimide also precipitates in the conventional method of performing a heat imidation reaction in a polar solvent called N-methyl-2-pyrrolidone or cresol.
    [197] <Use amount of diamine and tetracarboxylic dianhydride>
    [198] Although the usage-amount (the sum of the usage-amount of biphenyl tetracarboxylic dianhydride and the usage-amount of other tetracarboxylic dianhydride) of tetracarboxylic dianhydride used in this invention is not specifically limited, Usually, per 1 mol of diamines (diamines) used It is preferable to use the amount of 0.8-1.25 mol. The molecular weight of the polyimide obtained can be controlled by changing the molar ratio of the diamine to be used and tetracarboxylic dianhydride.
    [199] If the molar ratio (tetracarboxylic dianhydride / diamines) is less than 0.8, the molecular weight of the polyimide sufficiently expressing various properties cannot be obtained, and if the molar ratio exceeds 1.25, the molecular weight of the polyimide may be lowered. In some cases.
    [200] In addition, as mentioned later, when monoamines are used as a terminal sealing agent, the usage-amount of tetracarboxylic dianhydride is per 1 mol of total diamines (diamines) used, Preferably it is 1.01-1.25 mol, More preferably, It is 1.05-1.20 mol, Especially preferably, it is the range of 1.07-1.15 mol. In this case, when the said molar ratio (tetracarboxylic dianhydride / diamines) is less than 1.01 or more than 1.25, terminal sealing will become inadequate and may adversely affect the thermal stability and processability of the obtained polyimide.
    [201] In addition, when using the dicarboxylic acid mentioned later as an end sealing agent, its anhydride, or a derivative, tetracarboxylic acid dianhydride is used per 1 mol of total diamines (diamines), Preferably it is 0.8-0.99 mol, More preferably Preferably it is in the range of 0.85 to 0.97 moles, particularly preferably 0.90 to 0.95. In this case, when the said molar ratio (tetracarboxylic dianhydride / diamine) is less than 0.8 or more than 0.99, end sealing will become inadequate and may adversely affect the thermal stability and processability of the obtained polyimide.
    [202] The molecular weight of the polyimide can be controlled by changing the molar ratio of the diamines and tetracarboxylic dianhydrides used for producing the polyimide, and furthermore, the purity and impurity amount of the raw material, the polymerization method, the kind of the solvent, the polymerization temperature and the polymerization time. The optimal change ratio may vary depending on the like.
    [203] In addition, in order to obtain a polyimide sufficiently high in molecular weight, it is preferable to make the total moles of the total moles of the diamines (diamines) used and the total moles of the tetracarboxylic dianhydrides (tetracarboxylic dianhydrides) to be used substantially the same. In such a case, in the conventional method in which the produced polyimide does not precipitate, the viscosity of the reaction solution becomes remarkably high, making stirring difficult. However, according to the production method of the present invention, since the produced polyimide precipitates and the reaction system is in a slurry state, the reaction solution does not become viscous enough to cause agitation.
    [204] <Terminal sealant>
    [205] In the manufacturing method of the polyimide of this invention, a terminal sealant can be used as needed. The terminal sealant used is not specifically limited, Various things can be used. Among them, monoamines or dicarboxylic acid anhydrides and the like can be preferably used.
    [206] As a monoamine used as such a terminal sealer, for example, aniline,
    [207] o-toluidine, m-toluidine, p-toluidine, 2,3-xyldine, 2,4-xyldine,
    [208] 2,5-xyldine, 2,6-xyldine, 3,4-xyldine, 3,5-xyldine, o-chloroaniline,
    [209] m-chloroaniline, p-chloroaniline, o-bromoaniline, m-bromoaniline,
    [210] p-bromoaniline, o-nitroaniline, m-nitroaniline, p-nitroaniline,
    [211] o-anisidine, m-anisidine, p-anisidine, o-phenetidine, m-phenetidine, p-phenetidine,
    [212] o-aminophenol, m-aminophenol, p-aminophenol, o-aminobenzaldehyde,
    [213] m-aminobenzaldehyde, p-aminobenzaldehyde, o-aminobenzonitrile,
    [214] m-aminobenzonitrile, p-aminobenzonitrile, 2-aminobiphenyl, 3-aminobiphenyl,
    [215] 4-aminobiphenyl, 2-aminophenylphenyl ether, 3-aminophenylphenyl ether,
    [216] 4-aminophenylphenyl ether, 2-aminobenzophenone, 3-aminobenzophenone,
    [217] 4-aminobenzophenone, 2-aminophenylphenylsulfide, 3-aminophenylphenylsulfide,
    [218] 4-aminophenylphenylsulfide, 2-aminophenylphenylsulfone, 3-aminophenylphenylsulfone,
    [219] 4-aminophenylphenylsulfone, α-naphthylamine, β-naphthylamine, l-amino-2-naphthol,
    [220] 2-amino-1-naphthol, 4-amino-1-naphthol, 5-amino-1-naphthol, 5-amino-2-naphthol,
    [221] 7-amino-2-naphthol, 8-amino-1-naphthol, 8-amino-2-naphthol, 1-aminoanthracene, 2-aminoanthracene, 9-aminoanthracene, methylamine, dimethylamine, ethylamine,
    [222] Diethylamine, propylamine, dipropylamine, isopropylamine, diisopropylamine,
    [223] Butylamine, dibutylamine, isobutylamine, diisobutylamine, pentylamine, dipentylamine,
    [224] Benzylamine, cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine and the like.
    [225] Moreover, as dicarboxylic acid anhydride used as such a terminal sealing agent, For example, phthalic anhydride, 2, 3- benzophenone dicarboxylic acid anhydride,
    [226] 3,4-benzophenonedicarboxylic acid anhydride, 2,3-dicarboxyphenylphenyl ether anhydride,
    [227] 3,4-dicarboxyphenylphenyl ether anhydride, 2,3-biphenyldicarboxylic acid anhydride,
    [228] 3,4-biphenyldicarboxylic anhydride, 2,3-dicarboxyphenylphenylsulfone anhydride,
    [229] 3,4-dicarboxyphenylphenyl sulfone anhydride, 2,3-dicarboxyphenylphenyl sulfide anhydride,
    [230] 3,4-dicarboxyphenylphenylsulfide anhydride, 1,2-naphthalene dicarboxylic acid anhydride,
    [231] 2,3-naphthalene dicarboxylic acid anhydride, 1,8-naphthalene dicarboxylic acid anhydride,
    [232] 1,2-anthracene dicarboxylic acid anhydride, 2,3-anthracene dicarboxylic acid anhydride,
    [233] 1,9-anthracene dicarboxylic acid anhydride, etc. are mentioned.
    [234] These mono amine and dicarboxylic acid anhydride may be substituted by the group in which one part of the structure does not have reactivity with amine and carboxylic anhydride.
    [235] In addition, a part of the structure of such a monoamine or dicarboxylic acid anhydride may include an ethynyl group, a benzocyclobutene-4'-yl group, a vinyl group, an allyl group, a cyano group, an isocyanate group, a nitrilo group, an isopropenyl group, Monoamine or dicarboxylic anhydride substituted with substituents, such as a vinylene group, a vinylidene group, or an ethynylidene group, can also be used.
    [236] These terminal sealing agents can be used individually by 1 type or in combination of 2 or more types.
    [237] The usage-amount of the terminal sealant at the time of using such an terminal sealant is not specifically limited,
    [238] The total amount of the diamine component is [Da] (mol),
    [239] The total amount of the tetracarboxylic dianhydride component (or its ring-opening compound or derivative thereof) is calculated from [Tc] (mol),
    [240] The total amount of the mono amine component used as the terminal sealant is [Ma] (mol),
    [241] When the total amount of the dicarboxylic acid anhydride component (or its ring-opening compound or derivative thereof) used as the terminal sealant is called [Dc] (mol),
    [242] It is preferable to be in the range of 100≥ ([Dc]-[Ma]) / ([Da]-[Tc]) ≥2, more preferably 20≥ ([Dc]-[Ma]) / ([ Da]-[Tc]) ≧ 3 is preferred.
    [243] If the value of ([Dc]-[Ma]) / ([Da]-[Tc]) is less than 2, sufficient molecular end sealing cannot be performed, and thermal stability, thermal oxidation stability and molding processability of the obtained polyimide It may get worse. On the other hand, when the value of ([Dc]-[Ma]) / ([Da]-[Tc]) exceeds 100, the molecular weight control of the obtained polyimide and the washing | cleaning of an excess terminal sealing agent may become difficult.
    [244] Moreover, in the manufacturing method of this invention, it is preferable to inject | pour a terminal sealant with aromatic diamine and aromatic tetracarboxylic dianhydride at the start of reaction. In the manufacturing method of this invention, since the polymer produced | generated as the reaction progresses precipitates, when an terminal sealant is added later, a terminal may not be fully sealed.
    [245] <Catalyst>
    [246] In the manufacturing method of the polyimide of this invention, when reacting diamine and tetracarboxylic dianhydride, a well-known catalyst can be used together. When using a catalyst together, it is preferable to use a base catalyst.
    [247] As such a base catalyst, for example, pyridine, quinoline, isoquinoline,
    [248] α-picoline, β-picolin, γ-picoline, isophorone, piperidine, 2,4-lutidine, 2,6-lutidine,
    [249] Amine compounds such as trimethylamine, triethylamine, tripropylamine, tributylamine,
    [250] Organic bases such as imidazole, N, N-dimethylaniline, N, N-diethylaniline,
    [251] Inorganic bases, such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogencarbonate, sodium hydrogencarbonate, are mentioned.
    [252] As for the usage-amount of these catalysts, it is preferable to use the quantity of 0.001-0.50 mol, More preferably, 0.05-0.2 mol with respect to a total of 1 mol of diamines (diamines) used.
    [253] <Production of Polyimide>
    [254] The manufacturing method of the polyimide of this invention is especially limited as long as it is a solvent containing 50-100 weight% of equimolar compositions of the nitrogen-containing cyclic compound represented by the said General formula (1), and the phenols represented by General formula (2). Although it is not necessary, the method of heating diamines and tetracarboxylic dianhydride which are raw material monomers in the state melt | dissolved or suspended in the solvent, and thermally dehydrating imidation are preferable. At this time, the injection order and timing of diamines, tetracarboxylic dianhydride, and terminal sealant can be selected arbitrarily.
    [255] Although the density | concentration of the raw material monomer which can be used in this invention is not specifically limited, Moreover, Although it can set arbitrarily according to conditions, such as the structure and molecular weight of the polyimide to obtain, reaction temperature, the temperature at the time of filtration, In the related production method, slurry polymerization at a high concentration is possible as compared with the production method by imidization in a known phenolic single solvent.
    [256] In order to make use of this characteristic concerning the present invention, the concentration of the preferred raw material monomer with respect to the total reaction solution weight is 5 to 50% by weight, more preferably 10 to 45% by weight, more preferably 18 to 40% by weight. , Particularly preferably 23 to 37% by weight.
    [257] When the concentration of the raw material monomer is less than 5% by weight, the yield per batch decreases and the production efficiency is deteriorated, which may impair the characteristics of the present invention. Stirring of the reaction solution in the reaction process becomes difficult, and stable production may be difficult.
    [258] In addition, the said density | concentration says the density represented by ((total weight of a raw material monomer) / (total weight of a raw material monomer) + (weight of a solvent)) x 100 (%).
    [259] Known conditions can be applied to the polymerization temperature, the polymerization time and the polymerization pressure without particular limitation. That is, the reaction temperature is preferably around 80 ° C to 400 ° C, more preferably around 100 ° C to 300 ° C. In addition, the upper limit of reaction temperature is limited by the boiling point of the solvent under the pressure at the time of polymerization. In addition, although reaction time changes with the solvent to be used and other reaction conditions, it can usually implement suitably in 0.5 to 24 hours.
    [260] Moreover, in the manufacturing method which concerns on this invention, the solvent used for reaction is high boiling point, for example, even if it exceeds 200 degreeC, a polymerization reaction can be performed efficiently. Therefore, the reaction can be carried out at normal pressure and does not require a special device for the high pressure or the reduced pressure of the reaction system, thereby simplifying the process.
    [261] The polymerization reaction can be carried out in any of air, nitrogen, helium, neon, and argon atmospheres, and the atmosphere at the time of reaction is not particularly limited. However, it is preferable to use nitrogen or argon which are inert gases.
    [262] The concentration with respect to the total reaction solution weight of the polyimide obtained in this way is preferably 5 to 50% by weight, more preferably 10 to 45% by weight, more preferably 18 to 40% by weight, Especially preferably, it is 23-37 weight%.
    [263] In addition, the said density | concentration says the density | concentration represented by ((weight of polyimide) / (polyimide weight) + (weight of solvent)) x 100 (%).
    [264] <Reaction Solution State in Polymerization Process>
    [265] In the method for producing a polyimide of the present invention, a solvent containing 50 to 100% by weight of an equimolar composition of the nitrogen-containing cyclic compound represented by the formula (1) and the phenols represented by the formula (2) is used as a solvent. By using, the reaction solution state in the terminal of the imidation reaction of the polyimide manufacturing process which concerns on this invention turns into the slurry state which the polyimide precipitated in the solvent also under the conditions of normal pressure and the said reaction temperature range. . As a typical reaction state, for example, a monomer and / or a polyimide precursor are dissolved at an initial stage of the reaction to form a homogeneous solution, and then polyimide is precipitated as the reaction proceeds, and the reaction solution is in a slurry state. It becomes In addition, in this specification, the "finish" of the reaction means a step in which the reaction proceeds as described above and the polymerization and imidization of the polyimide are almost finished.
    [266] In addition, even if such a slurry reaction solution is cooled to about room temperature, the reaction solution does not become viscous and continues to be a slurry.
    [267] <Recovery of Polyimide>
    [268] In this invention, a polyimide can be obtained only by filtering the reaction solution of the slurry state obtained in this way as it is. Moreover, in order to make precipitation of a polyimide more reliable, poor solvents, such as toluene, methanol, ethanol, methyl ethyl ketone, water, and N-methyl- 2-pyrrolidone, can also be injected as needed.
    [269] In the method for producing a polyimide of the present invention, since the polyimide obtained by such an operation is usually in the form of a powder, the solvent can be easily removed and can be easily used for various applications. In addition, the solvent in the recovered polyimide can be removed by various known methods, for example, can be dried in an oven at 100 to 400 ° C. to remove the solvent.
    [270] In the production of polyimide, although it depends on the structure of the produced polyimide, in order to prevent solidification of the produced polymer, the polymerization reaction is carried out at a low concentration (for example, about 10% by weight) of the raw material to some extent. a lot of works. However, if the high boiling point mixed solvent according to the present invention is used, even if the total concentration of the polyimide raw material is imidated at a higher concentration (for example, 20% by weight or more), the reaction solution does not solidify, Since the reaction solution can be obtained in a slurry state, the productivity of the polyimide in the industrial process can be improved. In addition, the polyimide obtained in this manner has the same physical properties as those of the polyimide obtained by conventional low concentration polymerization (for example, about 10% by weight), and its molding processability, sliding characteristics, low water absorption, electrical characteristics, and heat Various physical properties such as oxidative stability and radiation resistance are not impaired.
    [271] Since the polyimide obtained by the manufacturing method of the polyimide of this invention has the physical property equivalent to the polyimide obtained by the conventionally well-known method, the conventionally well-known shaping | molding method, ie compression molding, sintering molding, extrusion molding, It can provide to injection molding, transfer molding, etc., and can provide for a conventionally well-known use.
    [284] EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited at all by these Examples.
    [285] In addition, the test method of the various tests common in an Example and a comparative example is described below.
    [286] 1) IR spectrum of equimolar composition
    [287] It measured by the liquid film method using FTS-165 by Bio-Rad.
    [288] 2) NMR spectrum of equimolar composition
    [289] The composition of the liquid was measured as it was using Unity Inova 400 manufactured by Varian.
    [290] 3) relative dielectric constant (ε ') and dielectric loss tangent (tanδ) of equimolar compositions
    [291] It measured by the LCR meter bridge method using the precision LCR meter HP4284A (made by Azirent Technology), and the measuring electrode LE-22 (made by Ando Electric Co., Ltd.). The measurement frequency is 1 MHz and the measurement conditions are 22 ± 1 ° C / 60 ± 2% RH.
    [292] 4) Intrinsic viscosity of polyimide powder
    [293] 0.50 g of the sample was dissolved in 100 ml of a mixed solvent (90:10 weight ratio) of p-chlorophenol and phenol, and then measured at 35 ° C.
    [294] 5) melt viscosity
    [295] The orifice 1.0 mm (diameter) x 10 mm (length), the load 100 kgf, and the case of special mention were made in 5 minutes of residence time by the Shimadzu Koka type flow tester (CFT 500A).
    [296] 6) 5% weight loss temperature
    [297] It measured at the temperature rise rate of 10 degree-C / min using DTA-TG (Shimatsu DT-40 series, 40M) in air.
    [298] 7) Glass transition temperature and crystal melting temperature (melting point)
    [299] It measured at the temperature rise rate of 10 degree-C / min by DSC (Shimatsu DT-40 series, DSC-41M).
    [300] Example A1
    [301] N-methyl-2-pyrrolidone was injected into a flask equipped with a sufficiently dried packed column, rectified at atmospheric pressure under a nitrogen atmosphere, and purified N-methyl-2-pyrrolidone having a boiling point of 204.5 占 폚 and a moisture content of 10 ppm or less. I made money. In addition, m-cresol (express) was rectified in the same manner to prepare a purified m-cresol having a boiling point of 202.2 占 폚 and a water content of 10 ppm or less.
    [302] In a dry box, 99.lg (1.00 mol) of the purified N-methyl-2-pyrrolidone was injected into the flask, and 108.1 g (1.00 mol) of purified m-cresol was gradually added while stirring to purify N-methyl. The equimolar composition (liquid) of 2-pyrrolidone and purified m-cresol was obtained.
    [303] When the obtained equimolar composition was heated at normal pressure and the temperature of the liquid phase and the gaseous phase at the time of boiling was measured, both liquid phase and gaseous phase were 230 degreeC. It was 25.5 degreeC higher than the boiling point (204.5 degreeC) of refine | purified N-methyl- 2-pyrrolidone, and was 27.8 degreeC higher than the boiling point (202.2 degreeC) of refine | purified m-cresol. The equimolar composition thus obtained was placed in a flask and held in 0 ° C. ice water for 3 hours, but the equimolar composition did not solidify and remained in a liquid state.
    [304] IR spectrum of the obtained equimolar composition, reagent grade N-methyl-2-pyrrolidone and m-cresol is shown in Fig. A1. Compared to those of N-methyl-2-pyrrolidone and m-cresol alone, the IR spectrum of equimolar compositions has a broadband of 3000 to 4000 cm −1 showing OH stretching vibrations indicating the presence of intramolecular and intermolecular hydrogen bonds And a band of 1671 cm -1 showing C = O stretching vibration is shifted to a low frequency. Moreover, CO stretching vibration due to association formation by hydrogen bonding is observed at 1287 cm -1 . The above result shows that C = O of N-methyl- 2-pyrrolidone and OH of m-cresol form strong hydrogen bond in equimolar composition.
    [305] 1 H- and 13 C-NMR spectra of the obtained equimolar compositions are shown in FIGS. A2 and A3. It is understood that the protons and carbon signals of equimolar compositions are equivalent to those of known N-methyl-2-pyrrolidone and m-cresol alone, and no ionic bond is formed.
    [306] The dielectric constant of the obtained equimolar composition was 24.0 and the dielectric tangent was 0.353. In addition, 5 g of pure water was mixed in a sample bottle with 5 g of the obtained equimolar composition, and the mixture was stirred vigorously, but the equimolar composition and pure water did not mix with each other and remained separated in two layers.
    [307] Example A2
    [308] 40 g of the composition obtained in Example A1 was injected into a simple evaporation distillation apparatus equipped with a decompression device, a cooling tube, an effluent receiver and a thermometer and introduced with nitrogen by a capillary tube. After the system was depressurized to 1.33 × 10 4 Pa, the temperature was gradually increased from room temperature in an oil bath, and about 10 g of the distillation solution was divided into three portions from the beginning of distillation.
    [309] The composition of the obtained fore run, middle stream, wake and the remainder (about 10 g each) was measured by gas chromatography (column: UniotrHP 80 / 10O KG-02, 3.2φ × 6 m, column temperature 180 ° C.) In each composition, N-methyl-2-pyrrolidone / m-cresol = 47.8% / 52.2% by weight (1: 1 in molar ratio), and there was no difference in each composition. In addition, the analytical curve was created using the refine | purified N-methyl- 2-pyrrolidone prepared in Example A1, and the purified m-cresol.
    [310] Example A3
    [311] In Example A2, the flask was distilled in the same manner as in Example A2 except that the inner pressure of the flask was set to 1.33 × 10 4 Pa to l.33 × 10 3 Pa, and about 10 g each of the first, midstream, wake and the remainder were each. Got it. The compositions of N-methyl-2-pyrrolidone and m-cresol contained in these were measured in the same manner as in Example A2, and the respective compositions were all N-methyl-2-pyrrolidone / m-cresol. = 47.8 wt% / 52.2 wt% (1: 1 in molar ratio), no difference was seen in each composition.
    [312] Example A4
    [313] N-methyl-2-pyrrolidone (100.0 g, 1.01 mol) and m-cresol (100.0 g, 0.925 mol) are accurately weighed and injected into a simple distillation apparatus equipped with a cooling tube, a distillation receiver and a thermometer, Simple evaporation distillation was performed at normal pressure under nitrogen atmosphere. About 20 g of the first stream was distilled off, and after the temperature at the top of the tower was stabilized at 230 ° C., the receiver was replaced with another receiver to distill to obtain about 17O g of mainrun. The composition of the obtained liquor was N-methyl-2-pyrrolidone / m-cresol = 47.8 weight% / 52.2 weight% (1: 1 in molar ratio).
    [314] Example A5
    [315] About 100 g of the liquor obtained in Example A4 was poured into a flask equipped with a cooling tube and a distillate container, boiled at atmospheric pressure under a nitrogen atmosphere, and the whole amount was recovered with a distillate container. The recovered liquid was boiled and recovered in the same manner. The composition of the obtained liquid was N-methyl-2-pyrrolidone / m-cresol = 47.8 wt% / 52.2 wt% (1: 1 in molar ratio).
    [316] Examples A6 to A8
    [317] The equimolar composition of the purified N-methyl-2-pyrrolidone and the purified m-cresol obtained in Example A1 and the purified N-methyl-2-pyrrolidone or the purified m-cresol are combined in the amounts shown in Table A1. did. The boiling point measured in the same manner as in Example A1 is shown in Table A1.
    [318] In addition, the solution shown in Table A1 was put into the flask, respectively, and it hold | maintained in 0 degreeC ice water for 3 hours, but the solution did not coagulate and remained in the liquid state.
    [319] Comparative Examples A1 to A4
    [320] The equimolar compositions of the purified N-methyl-2-pyrrolidone and the purified m-cresol obtained in Example A1, and the purified N-methyl-2-pyrrolidone or the purified m-cresol in the amounts shown in Table A1. Blended. The boiling point measured in the same manner as in Example A1 is shown in Table A1.
    [321] Example A9
    [322] p-cresol (special grade) was distilled in the same manner as in Example A1 to prepare a purified p-cresol having a boiling point of 201.9 占 폚 and a water content of 10 ppm or less.
    [323] Into a flask, 99.1 g (1.OO mole) of purified N-methyl-2-pyrrolidone prepared in Example A1 was poured into a dry box, while stirring and gradually adding 10.8 moles of purified p-cresol (1.00 mole). An equimolar composition (liquid) of purified N-methyl-2-pyrrolidone and purified p-cresol was obtained.
    [324] When the obtained equimolar composition was heated at normal pressure and the temperature of the liquid phase and the gaseous phase at the time of boiling was measured, it was 228 degreeC in both the liquid phase and the gaseous phase. This was 23.5 degreeC higher than the boiling point (204.5 degreeC) of refine | purified N-methyl- 2-pyrrolidone, and 26.1 degreeC higher than the boiling point (201.9 degreeC) of refine | purified p-cresol. The equimolar composition thus obtained was placed in a flask and held in 0 ° C ice water for 3 hours, but the equimolar composition did not solidify and remained in a liquid state.
    [325] In addition, 5 g of pure water was mixed with 5 g of the obtained equimolar composition in a sample bottle and stirred, but the equimolar composition and pure water did not mix with each other and remained separated in two layers.
    [326] Example Al0
    [327] p-chlorophenol (special grade) was distilled in the same manner as in Example A1, and purified p-chlorophenol having a boiling point of 217 占 폚 and a water content of 10 ppm or less was prepared.
    [328] Into a flask, 99.lg (1.OO mol) of purified N-methyl-2-pyrrolidone prepared in Example A1 was poured into a dry box, and 128.6 g (1.00 mol) of purified p-chlorophenol was gradually added thereto while stirring. The equimolar composition (liquid) of purified N-methyl-2-pyrrolidone and purified p-chlorophenol was obtained.
    [329] When the obtained equimolar composition was heated at normal pressure and the temperature of the liquid phase and the gaseous phase at the time of boiling was measured, it was 245 degreeC in both liquid phase and gaseous phase. It was about 41 degreeC higher than the boiling point (204.5 degreeC) of refine | purified N-methyl- 2-pyrrolidone, and 28 degreeC higher than the boiling point (217 degreeC) of refined p-chlorophenol. The equimolar composition thus obtained was placed in a flask and held in 0 ° C ice water for 3 hours, but the equimolar composition did not solidify and remained in a liquid state.
    [330] The IR spectrum of the obtained equimolar composition and reagent grade N-methyl-2-pyrrolidone and p-chlorophenol is shown in Fig. A4. Compared to those of N-methyl-2-pyrrolidone and p-chlorophenol alone, the IR spectrum of equimolar compositions has a broad spectrum of 3000 to 4000 cm −1 showing OH stretching vibrations indicating the presence of intramolecular and intermolecular hydrogen bonds. The 1671 cm <-1> band which shows a band and C = O expansion vibration is shifting to low frequency. Moreover, CO stretching vibration due to association formation by hydrogen bonding is observed at 1269 cm -1 . The above result shows that C = O of N-methyl- 2-pyrrolidone and OH of p-chlorophenol form strong hydrogen bond in equimolar composition.
    [331] 1 H- and 13 C-NMR spectra of the obtained equimolar compositions are shown in FIGS. A5 and A6. It is understood that the proton and carbon signal of the equimolar composition are equivalent to those of known N-methyl-2-pyrrolidone and p-chlorophenol alone, and no ionic bond is formed.
    [332] The dielectric constant of the obtained equimolar composition was 32.8 and the dielectric tangent was 0.434. In addition, 5 g of pure water was mixed with 5 g of the obtained equimolar composition in a sample bottle and stirred vigorously, but the equimolar composition and pure water did not mix with each other and remained separated in two layers.
    [333] Compounding amount (g)Content of equimolar composition (% by weight)Boiling point (℃) Equimolar compositionN-methyl-2-pyrrolidonem-cresol Comparative Example A10025.00202 Comparative Example A210.4014.641.6209 Example A620.904.183.6228 Example A725.000100230 Example A819.35.7077.2224 Comparative Example A39.615.4038.4213 Comparative Example A4025.000204
    [334] Equimolar compositions: equimolar compositions of purified N-methyl-2-pyrrolidone and purified m-cresol
    [335] Content: (the equimolar composition amount (g) / compounding quantity total (25 g)) * 10 (weight%)
    [336] Example Bl
    [337] 1,3-dimethyl-2-imidazolidinone is poured into a flask equipped with a sufficiently dried packed column, distilled at atmospheric pressure under a nitrogen atmosphere, and has a boiling point of 225.5 占 폚 and a water content of 10 ppm or less. 2-imidazolidinone was prepared. In addition, m-cresol (special grade) was distilled in the same manner to prepare a purified m-cresol having a boiling point of 202.2 占 폚 and a water content of 10 ppm or less.
    [338] Into a flask, 114.lg (1.OO mol) of the purified 1,3-dimethyl-2-imidazolidinone was injected into a flask, and 108.lg (1.00 mol) of purified m-cresol was added while stirring. The equimolar composition (liquid) of the purified 1,3-dimethyl-2-imidazolidinone and the purified m-cresol was obtained.
    [339] When the obtained equimolar composition was heated at normal pressure and the temperature of the liquid phase and the gaseous phase at the time of boiling was measured, both the liquid phase and the gaseous phase were 237 ° C. This was about 12 ° C. higher than the boiling point (225.5 ° C.) of the purified 1,3-dimethyl-2-imidazolidinone and about 35 ° C. higher than the boiling point (202.2 ° C.) of the purified m-cresol. The equimolar composition thus obtained was placed in a flask and held in 0 ° C ice water for 3 hours, but the equimolar composition did not solidify and remained in a liquid state.
    [340] IR spectrum of the obtained equimolar composition and reagent grade 1,3-dimethyl-2-imidazolidinone and cresol are shown in FIG. B1. A broadband of 3000 to 4000 cm -1 showing OH stretching vibrations indicating the presence of intramolecular and intermolecular hydrogen bonds in equimolar compositions compared to those of 1,3-dimethyl-2-imidazolidinone and m-cresol alone, and A 1693 cm -1 band showing C = O stretching vibration is shifted to a low frequency. The above results show that the equimolar composition forms a rigid hydrogen bond between C═O of 1,3-dimethyl-2-imidazolidinone and OH of m-cresol.
    [341] 1 H- and 13 C-NMR spectra of the obtained equimolar compositions are shown in FIGS. B2 and B3. It is understood that the protons and carbon signals of equimolar compositions are equivalent to those of known 1,3-dimethyl-2-imidazolidinone and m-cresol alone, and no ionic bond is formed.
    [342] The dielectric constant of the obtained equimolar composition was 24.1 and the dielectric tangent was 0.412. In addition, 5 g of pure water was mixed with 5 g of the obtained equimolar composition in a sample bottle and stirred vigorously, but the equimolar composition and pure water did not mix with each other and remained separated in two layers.
    [343] Example B2
    [344] 40 g of the composition obtained in Example B1 was injected into a simple evaporation distillation apparatus equipped with a decompression device, a cooling tube, an effluent receiver and a thermometer and introduced with nitrogen by a capillary tube. After the system was depressurized to 1.33 × 10 4 Pa, the temperature was gradually increased from room temperature in an oil bath, and approximately 10 g of the distillation solution was divided into three portions from the beginning of distillation.
    [345] The composition of the obtained first, middle, and downstream portions (about 10 g each) was measured by gas chromatography (column: UniotrHP 80/100 KG-02, 3.2φ × 6m, column temperature 180 ° C.) In all, 1,3-dimethyl-2-imidazolidinone / m-cresol = 51.35 wt% / 48.65 wt% (1: 1 in molar ratio), no difference was observed in each composition. In addition, the analytical curve was created using the refine | purified 1, 3- dimethyl- 2-imidazolidinone and the purified m-cresol which were prepared in Example B1.
    [346] Example B3
    [347] In Example B2, the flask was distilled in the same manner as in Example B2 except that the internal pressure of the flask was used at 1.33 × 10 3 Pa instead of 1.33 × 10 4 Pa, and about 10 g each of the first, middle, and downstream portions was rested. Got it. The compositions of 1,3-dimethyl-2-imidazolidinone and m-cresol contained in these were measured in the same manner as in Example B2, and the respective compositions were all 1,3-dimethyl-2-imide. With zolidinone / m-cresol = 51.35 wt% / 48.65 wt% (1: 1 in molar ratio), no difference was seen in each composition.
    [348] Example B4
    [349] Accurately weigh 1,3-dimethyl-2-imidazolidinone (100.0 g, 0.876 mole) and m-cresol (100.0 g, 0.925 mole) to a simple distillation unit equipped with a cooling tube, a distillation receiver and a thermometer. It injected | poured and performed simple evaporation distillation at normal pressure under nitrogen atmosphere. After distilling about 30 g of the first streams, the temperature at the top of the tower was stabilized at 237 ° C, and the distillation was carried out by replacing the receiver with another receiver to obtain about 155 g of liquor. The composition of the obtained liquor was 1, 3- dimethyl- 2-imidazolidinone / m-cresol = 51.35 weight% / 48.65 weight% (1: 1 in molar ratio).
    [350] Example B5
    [351] The liquor (100 g) obtained in Example B4 was poured into the flask provided with the cooling tube and the distillate container, boiled at normal pressure in nitrogen atmosphere, and the whole quantity was collect | recovered by the distillate container. The recovered liquid was also boiled and recovered in the same manner. The composition of the obtained solution was 1,3-dimethyl-2-imidazolidinone / m-cresol = 51.35 wt% / 48.65 wt% (1: 1 in molar ratio).
    [352] Example B6
    [353] p-cresol (special grade) was distilled in the same manner as in Example B1 to prepare a purified p-cresol having a boiling point of 201.9 占 폚 and a water content of 10 ppm or less.
    [354] In a dry box, 114.lg (1.00 mol) of the purified 1,3-dimethyl-2-imidazolidinone prepared in Example B1 was injected into a flask, and stirred, and further, 108.lg (1.00) of the purified p-cresol. Mole) was gradually added to obtain an equimolar composition (liquid) of purified N-methyl-2-pyrrolidone and purified p-cresol.
    [355] When the obtained equimolar composition was heated at normal pressure and the temperature of the liquid phase and the gaseous phase at the time of boiling was measured, it was 236 degreeC in both liquid phase and gaseous phase. This was about 11 ° C higher than the boiling point (225.5 ° C) of the purified 1,3-dimethyl-2-imidazolidinone and about 34 ° C higher than the boiling point (201.9 ° C) of the purified p-cresol. The equimolar composition thus obtained was placed in a flask and held in 0 ° C ice water for 3 hours, but the equimolar composition did not solidify and remained in a liquid state.
    [356] In addition, 5 g of pure water was mixed with 5 g of the obtained equimolar composition in a sample bottle and stirred, but the equimolar composition and pure water did not mix with each other and remained separated in two layers.
    [357] Example B7
    [358] Phenol (express) was distilled in the same manner as in Example B1 to prepare purified phenol having a boiling point of 181.2 ° C. and a water content of 10 ppm or less.
    [359] Into a flask, 114.lg (1.00 mol) of the purified 1,3-dimethyl-2-imidazolidinone prepared in Example B1 was poured into a flask and stirred, while 94.1 g (1.00 mol) of the purified phenol was gradually added thereto. The equimolar composition (liquid) of the purified 1,3-dimethyl-2-imidazolidinone and the purified phenol was obtained.
    [360] When the obtained equimolar composition was heated at normal pressure and the temperature of the liquid phase and the gaseous phase at the time of boiling was measured, both liquid phase and gaseous phase were 229 degreeC. This was about 4 ° C higher than the boiling point (225.5 ° C) of the purified 1,3-dimethyl-2-imidazolidinone and about 27 ° C higher than the boiling point (201.9 ° C) of the purified p-cresol. The equimolar composition thus obtained was placed in a flask and held in 0 ° C ice water for 3 hours, but the equimolar composition did not solidify and remained in a liquid state.
    [361] In addition, 5 g of pure water was mixed with 5 g of the obtained equimolar composition in a sample bottle and stirred vigorously, but the equimolar composition and pure water did not mix with each other and remained separated in two layers.
    [362] Example B8
    [363] p-chlorophenol (special grade) was distilled in the same manner as in Example B1, and purified p-chlorophenol having a boiling point of 217 占 폚 and a water content of 10 ppm or less was prepared.
    [364] Into a flask, 114.lg (1.OO mol) of purified 1,3-dimethyl-2-imidazolidinone prepared in Example B1 was poured into a flask and stirred, while 128.6 g (1.00 mol) of purified chlorophenol was added. It was gradually added to obtain an equimolar composition (liquid) of purified 1,3-dimethyl-2-imidazolidinone and purified chlorophenol.
    [365] When the obtained equimolar composition was heated at normal pressure and the temperature of the liquid phase and the gaseous phase at the time of boiling was measured, both the liquid phase and the gaseous phase were 257 ° C. This was about 32 degreeC higher than the boiling point (225.5 degreeC) of the refined 1, 3- dimethyl- 2-imidazolidinone, and 40 degreeC higher than the boiling point (217 degreeC) of the refined p-chlorophenol. The equimolar composition thus obtained was placed in a flask and held in 0 ° C ice water for 3 hours, but the equimolar composition did not solidify and remained in a liquid state.
    [366] IR spectrum of the obtained equimolar composition and reagent grade 1,3-dimethyl-2-imidazolidinone and p-chlorophenol are shown in Fig. B4. 1,3-dimethyl-2-imidazolidinone and p- chloro, compared to the phenolic groups, IR spectra of equimolar composition, intramolecular and 4000㎝ 3000 to representing the OH stretching vibration indicating the presence of intermolecular hydrogen bonding - A band of 1693 cm -1 showing a broadband of 1 and C = O stretching vibration is shifted to a low frequency. The above result shows that C = O of 1, 3- dimethyl- 2-imidazolidinone and OH of p-chlorophenol form strong hydrogen bond in equimolar composition.
    [367] 1 H- and 13 C-NMR spectra of the obtained equimolar compositions are shown in FIGS. B5 and B6. It is understood that protons and carbon signals of equimolar compositions are equivalent to those of known 1,3-dimethyl-2-imidazolidinone and p-chlorophenol alone, and no ionic bond is formed.
    [368] The dielectric constant of the obtained equimolar composition was 32.5 and the dielectric tangent was 0.495. In addition, 5 g of pure water was mixed with 5 g of the obtained equimolar composition in a sample bottle and stirred vigorously, but the equimolar composition and pure water did not mix with each other and remained separated in two layers.
    [369] Examples B9-B11
    [370] Equimolar compositions of the purified 1,3-dimethyl-2-imidazolidinone and purified p-chlorophenol obtained in Example B1, and purified 1,3-dimethyl-2-imidazolidinone or purified p-chlorophenol And the amount shown in Table B1. The boiling point measured in the same manner as in Example B1 is shown in Table B1.
    [371] In addition, the solution of Table B1 thus obtained was put in a flask and held for 3 hours in ice water at 0 ° C., but the solution did not solidify and remained in a liquid state.
    [372] Comparative Examples B1 and B2
    [373] The equimolar composition of the purified 1,3-dimethyl-2-imidazolidinone and the purified p-chlorophenol obtained in Example B1, and the purified 1,3-dimethylimidazolidinone or the purified p-chlorophenol are shown in Table B1. It mix | blended in the quantity shown by. The boiling point measured in the same manner as in Example B1 is shown in Table B1.
    [374] Compounding amount (g)Content of equimolar composition (% by weight)Boiling point (℃) Equimolar composition1,3-dimethyl-2-imidazolidinonep-chlorophenol Comparative Example B10025.00217 Example B919.505.578.0251 Example B1025.000100257 Example B1120.64.4082.4243 Comparative Example B2025.000225
    [375] Equimolar compositions: equimolar compositions of tablet 1,3-dimethyl-2-imidazolidinone and purified p-chlorophenol
    [376] Content: (the equimolar composition amount (g) / compounding quantity total (25 g)) * 10 (weight%)
    [377] Examples C1 to C9, Comparative Examples C1 to C9
    [378] In a vessel equipped with a stirrer, a reflux condenser, a water separator, and a nitrogen inlet tube, 799 g of a solvent having a composition shown in Table C1 (the solvent amount was only 2570 g for Comparative Example C9), and a raw material monomer of the polyimide:
    [379] (1) 146.17 g (0.500 mol) of 1,3-bis (4-aminophenoxy) benzene;
    [380] (2) 1 43.43 g (0.4875 mol) of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride;
    [381] (3) 3.703 g (25.00 mmol) phthalic anhydride
    [382] Was injected, and this mixture was heated from room temperature to 200 degreeC over 150 minutes, stirring in nitrogen atmosphere, and reaction was performed at 200 degreeC for 12 hours. The theoretical yield of the polymer in this case is 275.3 g, and the polymer concentration is 25.6% (9.7% only for Comparative Example C9).
    [383] Table C2 shows the state of the reaction solution during the temperature rise process from room temperature to 200 ° C and the reaction at 200 ° C. However, in Table C2, each symbol represents the following state:
    [384] SL: slurry
    [385] B: polyimide is dissolved
    [386] C: The polyimide remains without being precipitated or melted a little
    [387] D: The polyimide partially solidified and adhered to the wall or spring of the stirrer.
    [388] Moreover, the solution which melt | dissolved 3.703 g (25.00 mmol) of phthalic anhydride in 70 g of each solvent was dripped about the reaction solution (Examples C1-C9 and Comparative Example C9) which were stirred, and it reacted at 200 degreeC for 6 hours. .
    [389] Thereafter, the reaction system was cooled to 30 ° C, and the obtained precipitates were filtered for Examples C1 to C9. In Comparative Example C9, no precipitate was obtained at this stage, and the obtained viscous polymer solution was discharged into 10 l of toluene under vigorous stirring, and the precipitated polymer was collected by filtration.
    [390] Moreover, about Examples C1-C9, the obtained polymer was wash | cleaned with 1 L of each solvent, and then it wash | cleaned with 1 L of toluene. In addition, about the comparative example C9, the obtained polymer was wash | cleaned with 2 L of toluene. The polymer thus obtained was dried at 300 ° C for 12 hours at 50 ° C for 24 hours after preliminary drying.
    [391] For Examples C1 to C9 and Comparative Example C9, the intrinsic viscosity, glass transition temperature, 5% weight loss temperature, and melt viscosity (430 ° C / 5 minutes) of the obtained polyimide powder were measured by the above method. The results obtained are shown in Table C3.
    [392] In addition, as can be seen from Examples C1 to C9, when the solvent according to the present invention is used, a high concentration (not attainable in a conventional solvent system as shown in Comparative Example C (Comparative Examples C2, C4, C6 or C8)) Polyimide can be sufficiently synthesized even in about 25% by weight, and the polyimide obtained by the method of the present invention can be obtained by low concentration polymerization (Comparative Example C9; about 10% by weight) in a conventional solvent system. Has the same physical properties as
    [393] Moreover, according to the manufacturing method which concerns on this invention, since a reaction system becomes a slurry state, isolation of a polyimide can be performed only by filtration, and it becomes a simple process. Moreover, compared with the polyimide obtained by the conventional method, this polyimide maintains favorable heat resistance, without changing any physical property.
    [394] Equimolar composition (A)Solvent (B)Compounding ratio (A) / (B) [weight / weight] Example C1m-cresol / N-methyl-2-pyrrolidonenot used100/0 Example C2m-cresol75/25 Example C350/50 Comparative Example C125/75 Comparative Example C20/100 Example C4N-methyl-2-pyrrolidone75/25 Example C550/50 Comparative Example C325/75 Comparative Example C40/100 Example C6p-cresol75/25 Example C750/50 Comparative Example C525/75 Comparative Example C60/100 Example C8N, N'-dimethylimidazolidinone75/25 Example C950/50 Comparative Example C725/75 Comparative Example C80/100 Comparative Example C9m-cresol0/100
    [395] TemperatureRoom temperature50 ℃100 ℃150 ℃200 ℃ Elapsed time0 hours3 hours6 hours9 hours12 hours Example C1SLSLBCSLSLSLSLSL Example C2SLSLBCSLSLSLSLSL Example C3SLSLBSLSLSLSLSLSL Comparative Example C1SLSLSLDDStirring becomes difficult Comparative Example C2SLSLSLBStirring becomes difficult and the system solidifies Example C4SLSLBCSLSLSLSLSL Example C5SLSLBCSLSLSLSLSL Comparative Example C3SLSLBBSystem precipitates and solidifies rapidly around 180 ℃ Comparative Example C4SLSLBBSystem precipitates and solidifies rapidly around 190 ℃ Example C6SLSLBCSLSLSLSLSL Example C7SLSLBCSLSLSLSLSL Comparative Example C5SLSLSLDDDComparative Example C6SLSLSLBStirring becomes difficult and the system solidifies Example C8SLSLBCSLSLSLSLSL Example C9SLSLBCSLSLSLSLSL Comparative Example C7SLSLBBSystem precipitates and solidifies rapidly around 190 ℃ Comparative Example C8SLSLBBSystem precipitates and solidifies rapidly around 200 ℃ Comparative Example C9SLSLSLBBBBBB
    [396] TemperatureIntrinsic Viscosity [] / g]Glass transition temperature [℃]Melting point [℃]5% weight loss temperature [℃]Melt viscosity [Pasec] (430 ° C / 5 minutes) Example C10.93192395563660 Example C20.92192396565680 Example C30.92193396565670 Example C40.95192395564650 Example C50.94192395563640 Example C60.92192395562660 Example C70.90193396565690 Example C80.93192396565680 Example C90.96193395564680 Comparative Example C90.98193396565720
    [397] Examples C10 to C12, and Comparative Examples Cl0 and C11
    [398] In a container equipped with a stirrer, a reflux condenser, a water separator, and a nitrogen inlet tube, 2437 g of a solvent having the composition shown in Table C4 and a raw material monomer of the polyimide:
    [399] (1) 4,4'-bis (3-aminophenoxy) biphenyl, 368.43 g (1.000 mol);
    [400] (2) pyromellitic dianhydride, 102.52 g (0.470 mol);
    [401] (3) 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride, 138.28 g (0.470 mol); And
    [402] (4) phthalic anhydride, 17.77 g (120.0 mmol)
    [403] Was injected, and this mixture was heated from room temperature to 200 degreeC over 150 minutes, stirring in nitrogen atmosphere, and reaction was performed at 200 degreeC for 4 hours. In this case, the theoretical yield of the polymer was 591.0 g and the polymer concentration was 19.5%.
    [404] Table C5 shows the state of the reaction solution during the temperature rise process from room temperature to 200 ° C and the reaction at 200 ° C. In Table C5, each symbol represents the following state.
    [405] SL: Polyimide precipitates and the reaction solution is in a slurry state
    [406] B: polyimide is dissolved
    [407] C: The polyimide remains without being precipitated or melted a little
    [408] D: The polyimide partially solidified and adhered to the wall or spring of the stirrer.
    [409] Moreover, 17.77 g (120.0 mmol) of phthalic anhydrides were injected | poured with respect to the stirring solution (Examples C10-C12 and Comparative Example C10), and reaction was performed at 200 degreeC for 4 hours.
    [410] Then, it cooled to 30 degreeC and the obtained precipitate was filtered about Examples C10-C12. In Comparative Example C10, no precipitate was obtained at this stage. The resulting viscous polymer solution was discharged into 10 L of toluene with vigorous stirring, and the precipitated polymer was collected by filtration.
    [411] Moreover, about Examples C10-C12, the obtained polymer was wash | cleaned with 1 L of each solvent, and then it wash | cleaned with 1 L of toluene. In addition, about the comparative example C10, the obtained polymer was wash | cleaned with 2 L of toluene. Thus obtained polymer was dried under reduced pressure at 200 ° C for 12 hours at 50 ° C for 24 hours after preliminary drying.
    [412] For Examples C10 to C12 and Comparative Example C10, the intrinsic viscosity, glass transition temperature, and 5% weight loss temperature of the obtained polyimide powder were measured by the above method. The results obtained are shown in Table C6.
    [413] Equimolar composition (A)Solvent (B)Compounding ratio (A) / (B) [weight / weight] Example C10m-, p-mixed cresol / N-methyl-2-pyrrolidonenot used100/0 Example C11m-, p-mixed cresol75/25 Comparative Example C100/100 Example C12N-methyl-2-pyrrolidone75/25 Comparative Example C110/100
    [414] TemperatureRoom temperature50 ℃100 ℃150 ℃200 ℃ Elapsed time0 hours1 hours2 hours3 hours4 hours Example C10SLSLBCSLSLSLSLSL Example C11SLSLBCSLSLSLSLSL Comparative Example C10SLSLSLBBBBBB Example C12SLSLBSLSLSLSLSLSL Comparative Example C11SLSLBBSystem precipitates and solidifies rapidly around 190 ℃
    [415] TemperatureIntrinsic Viscosity [] / g]Glass transition temperature [℃]5% weight loss temperature [℃] Example C100.44239556 Example C110.45238557 Comparative Example C100.46239555 Example C120.44238555
    [416] From the results of these Examples C1 to C12, according to the production method according to the present invention, since the reaction system is in a slurry state, isolation of the polyimide is possible only by filtration, and thus a simple process. Moreover, compared with the polyimide obtained by the conventional method, this polyimide maintains favorable heat resistance, without changing physical properties at all.
    [417] Example C13
    [418] In Example C10, instead of phthalic anhydride injected first and phthalic anhydride injected second with the stirrable reaction solution, respectively, 0.66 g (72.00 mmol) of phthalic anhydride and 11.92 g (48.00 mmol) of 4-phenylethynylphthalic anhydride, respectively. Except having changed to, the polyimide was obtained on the conditions similar to Example C10. The glass transition temperature of the obtained polyimide powder was 238 degreeC.
    [419] Moreover, this powder was melt | dissolved in the furnace of 360 degreeC, it hold | maintained for 4 hours, and obtained the polyimide of lump state. The glass transition temperature of this polyimide was 246 degreeC.
    [420] Examples D1 to D9, and Comparative Examples D1 to D9
    [421] In a vessel equipped with a stirrer, a reflux condenser, a water separator, and a nitrogen inlet tube, 799 g of a solvent having a composition shown in Table D1 (a solvent amount of 2570 g only for Comparative Example D9) and a raw material monomer of a polyimide:
    [422] (1) 1,3-bis (4-aminophenoxy) benzene, 146.17 g (0.500 mol);
    [423] (2) 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride, 143.43 g (0.4875 mol); And
    [424] (3) phthalic anhydride, 3.703 g (25.00 mmol)
    [425] Was injected, and this mixture was heated from room temperature to 200 degreeC over 150 minutes, stirring in nitrogen atmosphere, and reaction was performed at 200 degreeC for 12 hours. In this case, the theoretical yield of the polymer was 275.3 g and the polymer concentration was 25.6% (9.7% only for Comparative Example D9).
    [426] Table D2 shows the state of the reaction solution during the temperature rise process from room temperature to 200 ° C and the reaction at 200 ° C. In Table D2, each symbol represents the following state.
    [427] SL: slurry
    [428] B: polyimide is dissolved
    [429] C: The polyimide remains without being precipitated or melted a little
    [430] D: The polyimide partially solidified and adhered to the wall or spring of the stirrer.
    [431] Moreover, the solution which melt | dissolved 3.703 g (25.00 mmol) of phthalic anhydride in 70 g of each solvent was dripped about the stirring solution (Examples D1-D9, Comparative Example D9), and reaction was performed at 200 degreeC for 6 hours. .
    [432] Then, the inside of the reaction system was cooled to 30 degreeC, and the obtained precipitate was filtered about Examples D1-D9. In Comparative Example D9, no precipitate was obtained at this stage. The resulting viscous polymer solution was discharged into 10 l of toluene under vigorous stirring, and the precipitated polymer was collected by filtration.
    [433] Moreover, about Examples D1-D9, the obtained polymer was wash | cleaned with 1 L of each solvent, and then with 1 L of toluene. In addition, about the comparative example D7, the obtained polymer was wash | cleaned with 2 L of toluene. The polymer thus obtained was dried at 300 ° C for 12 hours at 50 ° C for 24 hours after preliminary drying.
    [434] In Examples D1 to D9 and Comparative Example D9, the intrinsic viscosity, glass transition temperature, 5% weight loss temperature, and melt viscosity (430 ° C / 5 minutes) of the obtained polyimide powder were measured by the above method. The results obtained are shown in Table D4.
    [435] In addition, as can be seen from Examples D1 to D9, when the solvent according to the present invention is used, it is possible to use a high concentration (not attainable in a conventional solvent system as shown in Comparative Example D (Comparative Examples D2, D4, D6 or D8)). Polyimide can be sufficiently synthesized even in about 25% by weight, and the polyimide obtained by the method of the present invention can be obtained by low concentration polymerization in a conventional solvent system (Comparative Example D9; about 10% by weight). Has the same physical properties as
    [436] Moreover, according to the manufacturing method which concerns on this invention, since a reaction system becomes a slurry state, isolation of a polyimide can be performed only by filtration, and it becomes a simple process. Moreover, compared with the polyimide obtained by the conventional method, this polyimide maintains favorable heat resistance, without changing any physical property.
    [437] Equimolar composition (A)Solvent (B)Compounding ratio (A) / (B) [weight / weight] Example D1m-cresol / 1,3-dimethyl-2-imidazolidinonenot used100/0 Example D2m-cresol75/25 Example D350/50 Comparative Example D125/75 Comparative Example D20/100 Example D4N-methyl-2-pyrrolidone75/25 Example D550/50 Comparative Example D325/75 Comparative Example D40/100 Example D6p-cresol75/25 Example D750/50 Comparative Example D525/75 Comparative Example D60/100 Example D81,3-dimethyl-2-imidazolidinone75/25 Example D950/50 Comparative Example D725/75 Comparative Example D80/100 Comparative Example D9m-cresol0/100
    [438] TemperatureRoom temperature50 ℃100 ℃150 ℃200 ℃ Elapsed time0 hours3 hours6 hours9 hours12 hours Example D1SLSLBCSLSLSLSLSL Example D2SLSLBCSLSLSLSLSL Example D3SLSLBCSLSLSLSLSL Comparative Example D1SLSLSLDStirring becomes difficult Comparative Example D2SLSLSLBStirring becomes difficult and the system solidifies Example D4SLSLBCSLSLSLSLSL Example D5SLSLBCSLSLSLSLSL Comparative Example D3SLSLBBSystem precipitates and solidifies rapidly around 190 ℃ Comparative Example D4SLSLBBSystem precipitates and solidifies rapidly around 190 ℃ Example D6SLSLBCSLSLSLSLSL Example D7SLSLBCSLSLSLSLSL Comparative Example D5SLSLSLDStirring becomes difficult Comparative Example D6SLSLSLBStirring becomes difficult and the system solidifies Example D8SLSLBCSLSLSLSLSL Example D9SLSLBCSLSLSLSLSL Comparative Example D7SLSLBBSystem precipitates and solidifies rapidly around 190 ℃ Comparative Example D8SLSLBBSystem precipitates and solidifies rapidly around 190 ℃ Comparative Example D9SLSLSLBBBBBB
    [439] TemperatureIntrinsic Viscosity [] / g]Glass transition temperature [℃]Melting point [℃]5% weight loss temperature [℃]Melt viscosity [Pasec] (430 ° C / 5 minutes) Example D10.96192395564700 Example D20.97192396564690 Example D30.97194396565680 Example D40.98192395562680 Example D50.97192395565670 Example D60.94192395564660 Example D70.94193395564670 Example D80.95192396564690 Example D90.97192396564710 Comparative Example D90.98193395565720
    [440] Examples D10 to D12 and Comparative Examples D10 and D11
    [441] Into a vessel equipped with a stirrer, a reflux condenser, a water separator, and a nitrogen inlet tube, 2437 g of a solvent having the composition shown in Table D4 was injected, and a raw material of polyimide:
    [442] (1) 4,4'-bis (3-aminophenoxy) biphenyl, 368.43 g (1.000 mol);
    [443] (2) pyromellitic dianhydride, 102.52 g (0.470 mol);
    [444] (3) 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride, 138.28 g (0.470 mol); And
    [445] (4) phthalic anhydride, 17.77 g (120.0 mmol)
    [446] Was injected, and this mixture was heated from room temperature to 200 degreeC over 150 minutes, stirring in nitrogen atmosphere, and reaction was performed at 200 degreeC for 4 hours. In this case, the theoretical yield of the polymer was 591.0 g and the polymer concentration was 19.5%.
    [447] Table D5 shows the state of the reaction solution during the temperature rise process from room temperature to 200 ° C and the reaction at 200 ° C. However, in Table D5, each symbol represents the following states.
    [448] SL: Polyimide precipitates and the reaction solution is in a slurry state
    [449] B: polyimide is dissolved
    [450] C: The polyimide remains without being precipitated or melted a little
    [451] D: The polyimide partially solidified and adhered to the wall or spring of the stirrer.
    [452] Moreover, 17.77 g (120.0 mmol) of phthalic anhydrides were injected | thrown-in with respect to the stirring solution (Examples D10-D12, Comparative Example D10), and reaction was performed at 200 degreeC for 4 hours.
    [453] Then, it cooled to 30 degreeC and the obtained precipitate was filtered about Examples D10-D12. In Comparative Example D10, no precipitate was obtained at this stage. The resulting viscous polymer solution was discharged into 10 L of toluene with vigorous stirring, and the precipitated polymer was collected by filtration.
    [454] Moreover, about Examples D10-D12, the obtained polymer was wash | cleaned with 1 L of each solvent, and then with 1 L of toluene. In addition, about the comparative example D10, the obtained polymer was wash | cleaned with 2 L of toluene. Thus obtained polymer was dried under reduced pressure at 200 ° C for 12 hours at 50 ° C for 24 hours after preliminary drying.
    [455] For Examples D10 to D12 and Comparative Example D10, the intrinsic viscosity, glass transition temperature, and 5% weight loss temperature of the obtained polyimide powder were measured by the above method. The results obtained are shown in Table D6.
    [456] Equimolar composition (A)Solvent (B)Compounding ratio (A) / (B) [weight / weight] Example D10m-, p-mixed cresol / 1,3-dimethyl-2-imidazolidinonenot used100/0 Example D11m-, p-mixed cresol75/25 Comparative Example D100/100 Example D121,3-dimethyl-2-imidazolidinone75/25 Comparative Example D110/100
    [457] TemperatureRoom temperature50 ℃100 ℃150 ℃200 ℃ Elapsed time0 hours1 hours2 hours3 hours4 hours Example D10SLSLBCSLSLSLSLSL Example D11SLSLBCSLSLSLSLSL Comparative Example D10SLSLSLBBBBBB Example D12SLSLBCSLSLSLSLSL Comparative Example D11SLSLBBSystem precipitates and solidifies rapidly around 190 ℃
    [458] TemperatureIntrinsic Viscosity [] / g]Glass transition temperature [℃]5% weight loss temperature [℃] Example D100.45237557 Example D110.45238557 Comparative Example D100.44238557 Example D120.44238556
    [459] From these results, according to the production method according to the present invention, since the reaction system is in a slurry state, isolation of the polyimide is possible only by filtration, which results in a simple process. Moreover, compared with the polyimide obtained by the conventional method, this polyimide maintains favorable heat resistance, without changing physical properties at all.
    [460] Example D13
    [461] In Example D10, instead of phthalic anhydride first injected and phthalic anhydride second injected into the stirrable reaction solution, respectively, 0.66 g (72.00 mmol) of phthalic anhydride and 11.92 g (48.00 mmol) of 4-phenylethynylphthalic anhydride, respectively. Except having changed to, the polyimide was obtained on the conditions similar to Example D10. The glass transition temperature of the obtained polyimide powder was 238 degreeC. Moreover, this powder was melt | dissolved in the furnace of 360 degreeC, it hold | maintained for 4 hours, and obtained the polyimide of lump state. The glass transition temperature of this polyimide was 245 degreeC.
    [462] Examples El and E2 and Comparative Examples El to E12
    [463] The reaction was carried out in accordance with Example C1, except that 1031 g of the solvent having the composition shown in Table E1 was used. However, about Comparative Examples E5 to E8, reaction was performed at the boiling point temperature (180-200 degreeC) of a solvent under reflux of a solvent. In this case, the theoretical yield of the polymer was 275.3 g and the polymer concentration was 21.1%.
    [464] The temperature rise process from room temperature to the reaction temperature and the reaction solution state in the reaction process are shown in Table E2. However, in Table E2, each symbol represents the following state:
    [465] SL: slurry
    [466] B: polyimide is dissolved
    [467] C: The polyimide remains without being precipitated or melted a little
    [468] D: The polyimide partially solidified and adhered to the wall or spring of the stirrer.
    [469] In addition, to the stirring solution (Examples E1 and E9, Comparative Examples E3, E4, E8 and E10), a solution in which 3.703 g (25.00 mmol) of phthalic anhydride was dissolved in 70 g of each solvent was added dropwise thereto. The reaction was carried out for 6 hours.
    [470] Then, after cooling the inside of a reaction system to 30 degreeC, the obtained precipitate was filtered, and it wash | cleaned with 1 L of each solvent, and then with 1 L of toluene. The polymer thus obtained was dried at 300 ° C for 12 hours at 50 ° C for 24 hours after preliminary drying.
    [471] The intrinsic viscosity, glass transition temperature, 5% weight loss temperature, and melt viscosity (430 ° C./5 minutes) of the obtained polyimide powder were measured by the above method. The results obtained are shown in Table E3.
    [472] As can be seen from Comparative Examples El, E2, E5 to E7, E9, E11, and E12, the monomer- and / or polyimide precursor is dissolved using a solvent containing no equimolar composition, so that the solution becomes uniform. In this case, the reaction solution rapidly forms a jelly or solid state by the precipitate formed as the imidation progresses. In addition, as can be seen from Comparative Examples E3, E4, E8, and E10, when the monomer- and / or polyimide precursor is not dissolved using a solvent containing no equimolar composition, and the reaction proceeds in a slurry state. The polymerization degree (intrinsic viscosity) of the obtained polyimide is unusually high, and thermal stability (weight reduction temperature) and melt fluidity (melt viscosity) are remarkably bad.
    [473] SolventCompounding ratio (A) / (B) [weight / weight]Equimolar composition (wt%) Solvent (A)Solvent (B) Example E1m-cresolN-methyl-2-pyrrolidone50/5095.8 Example E2N, N'-dimethylimidazolidinone50/5097.4 Comparative Example E1Diphenyl ether75/25- Comparative Example E250/50- Comparative Example E325/75- Comparative Example E40/100- Comparative Example E5o-dichlorobenzene75/25- Comparative Example E650/50- Comparative Example E725/75- Comparative Example E80/100- Comparative Example E9Benzyl alcohol50/50- Comparative Example E100/100- Comparative Example E11Dimethyl sulfoxide50/50- Comparative Example E120/100-
    [474] Equal molar composition: Equal molar composition of nitrogen-containing cyclic compound and phenols
    [475] Content: (the equimolar composition amount (g) / compounding quantity total (25 g)) * 10 (weight%)
    [476] TemperatureRoom temperature50 ℃100 ℃150 ℃200 ℃ * Elapsed time0 hours3 hours6 hours9 hours12 hours Example E1SLSLBCSLSLSLSLSL Example E2SLSLBCSLSLSLSLSL Comparative Example E1SLSLBBCThe whole system is in a jelly state and it is difficult to stir Comparative Example E2SLSLSLCThe whole system is in a jelly state and it is difficult to stir Comparative Example E3SLSLSLSLSLSLDDD Comparative Example E4SLSLSLSLSLSLSLSLSL Comparative Example E5SLSLBBBThe whole system is in a jelly state and it is difficult to stir Comparative Example E6SLSLBBSystem precipitates and solidifies rapidly around 170 ℃ Comparative Example E7SLSLSLSLSystem solidifies rapidly around 160 ° C Comparative Example E8SLSLSLSLSLSLSLSLSL Comparative Example E9SLSLSLBSystem solidifies rapidly around 180 ℃ Comparative Example E10SLSLSLSLSLSLSLSLSL Comparative Example E11SLSLBBSystem precipitates and solidifies rapidly around 190 ℃ Comparative Example E12SLSLBBSystem precipitates and solidifies rapidly around 170 ℃
    [477] *: Comparative Examples E5 to E8 are 200 to 180 ° C.
    [478] TemperatureIntrinsic Viscosity [] / g]Glass transition temperature [℃]5% weight loss temperature [℃]Melt viscosity [Pasec] (430 ° C / 5 minutes) Example E10.93192562680 Example E20.92192562650 Comparative Example E31.101965473240 Comparative Example E41.6519852415600 Comparative Example E81.58196550During melt Comparative Example E101.85195544During melt
    [479] Examples E4 to E7, Comparative Examples E13 to E15, and Reference Example 1
    [480] The reaction was carried out in accordance with Example C10, except that 1098 g of the solvent having the composition shown in Table E4 was used. In this case, the theoretical yield of the polymer was 591.0 g and the polymer concentration was 35.0%.
    [481] The temperature rise process from room temperature to the reaction temperature and the reaction solution state in the reaction process are shown in Table E5. However, in Table E5, each symbol represents the following state:
    [482] SL: slurry
    [483] B: polyimide is dissolved
    [484] C: The polyimide remains without being precipitated or melted a little
    [485] D: The polyimide partially solidified and adhered to the wall or spring of the stirrer.
    [486] Moreover, 17.77 g (120.0 mmol) of phthalic anhydrides were injected | thrown-in to the stirring solution (Examples E4-E7) which were stirred, and reaction was performed at 200 degreeC for 4 hours.
    [487] Then, the inside of the reaction system was cooled to 30 degreeC, the obtained precipitate was collect | recovered by filtration, and it wash | cleaned with 1 L of each solvent, and then with 1 L of toluene. The polymer thus obtained was dried at 200 ° C. for 12 hours under nitrogen gas flow after 50 ° C. and 24 hours of preliminary drying.
    [488] The intrinsic viscosity, glass transition temperature, 5% weight loss temperature, and melt viscosity (420 ° C./5 minutes) of the obtained polyimide powder were measured by the above method. The results obtained are shown in Table E4.
    [489] As can be seen from Examples E4 to E7, when the equimolar composition content in the solvent used is high, the polyimide can be sufficiently synthesized even under extremely high concentration conditions of about 35% by weight of the polymer. Polyimide has good physical properties.
    [490] SolventCompounding ratio (A) / (B) [weight / weight]Equimolar composition (wt%) Solvent (A)Solvent (B) Reference Example 1m- and p-mixed cresolsN-methyl-2-pyrrolidone75/2552.3 Example E450/5095.8 Comparative Example E1325/7547.9 Comparative Example E14N, N'-dimethylimidazolidinone80/2038.9 Example E560/4077.9 Example E650/5097.4 Example E740/6082.2 Comparative Example E1520/8041.1
    [491] Equal molar composition: Equal molar composition of nitrogen-containing cyclic compound and phenols
    [492] Content: (the equimolar composition amount (g) / compounding quantity total (25 g)) * 10 (weight%)
    [493] TemperatureRoom temperature50 ℃100 ℃150 ℃200 ℃ * Elapsed time0 hours3 hours6 hours9 hours12 hours Reference Example E1SLSLBBThe whole system is in a jelly state and it is difficult to stir Example E4SLSLSLBSLSLSLSLSL Comparative Example E13SLSLBCSystem solidifies rapidly at around 170 ℃ Comparative Example E14SLSLBBThe whole system is in a jelly state and it is difficult to stir Example E5SLSLSLBCSLSLSLSL Example E6SLSLSLBSLSLSLSLSL Example E7SLSLBBSLSLSLSLSL Comparative Example E15SLSLBBSystem precipitates and solidifies rapidly around 160 ℃
    [494] TemperatureIntrinsic Viscosity [] / g]Glass transition temperature [℃]5% weight loss temperature [℃]Melt viscosity [Pasec] (430 ° C / 5 minutes) Example E40.42236553200 Example E50.44238557220 Example E60.42237555220 Example E70.41237554200
    [495] Examples E8 and E9
    [496] Polyimide was synthesize | combined according to Example C10 except having changed reaction temperature to 200 degreeC and Example E9 to 230 degreeC. After initiating the reaction, a part of the reaction slurry liquid was collected at 3, 6 and 9 hours, filtered and dried, and then the intrinsic viscosity of the obtained sample was measured. The results are shown in Table E7.
    [497] As can be seen from this result, the reaction time can be shortened by making the reaction temperature higher than 200 ° C.
    [498] Example E8, reaction temperature 200 ° CExample E9, reaction temperature 230 ° C. Response time (hrs)369369 Intrinsic viscosity (㎗ / g)0.370.390.400.400.400.40
    [499] Examples El0 to E13, Comparative Examples E17 to E26, and Reference Example E2
    [500] Into a vessel equipped with a stirrer, a reflux condenser, a water separator, and a nitrogen inlet tube, the raw materials of the solvent and polyimide shown in Table E8 were injected, and the mixture was stirred from room temperature to 200 ° C. over 150 minutes while stirring under a nitrogen atmosphere. It heated and reacted at 200 degreeC for 4 hours. In addition, the polymer concentration at the time of this superposition | polymerization is 25.0%.
    [501] Table E9 shows the state of the reaction solution during the temperature rise process from room temperature to 200 ° C and the reaction at 200 ° C.
    [502] Moreover, 17.77 g (120.0 mmol) of phthalic anhydrides were injected | thrown-in, and reaction was performed at 200 degreeC for 4 hours.
    [503] Then, the inside of the reaction system was cooled to 30 degreeC, the precipitate was collect | recovered by filtration, and it wash | cleaned with 1 L of each solvent, and then it wash | cleaned with 1 L of toluene. In addition, for Comparative Examples E19, E21, E23, and E25, no precipitate was obtained at this stage. Thus, a viscous polymer solution was vigorously discharged into 10 l of toluene under vigorous stirring, and the precipitated polymer was recovered by filtration and 2 l of toluene. It washed with. Thus obtained polymer was dried under reduced pressure at 200 ° C for 12 hours at 50 ° C for 24 hours after preliminary drying.
    [504] In Examples El0 to E13 and Comparative Examples El7, E19, E21, E23 and E25, the intrinsic viscosity and the glass transition temperature of the obtained polyimide powder were measured by the above method. The results obtained are shown in Table E9.
    [505] PDMA / BPDA composition ratio / molBAB (g)PMDA (g)BPDA (g)PA (g)Theoretical Polymer Quantity (g)menstruum Equimolar composition (g)m, p-mixed cresol (g)N-methyl-2-pyrrolidone (g) Reference Example E210/0368.43 (1.000 moles)205.03 (0.940 mol)0.00 (0.000 mol)17.77 (0.120 mole)555.211666 Comparative Example E17 1666Comparative Example E18 1666 Example E107/3368.43 (1.000 moles)143.52 (0.658 mole)82.97 (0.282 mole)17.77 (0.120 mole)576.671730 Comparative Example E19 1730Comparative Example E20 1730 Example E115/5368.43 (1.000 moles)102.52 (0.470 mole)138.28 (0.470 mole)17.77 (0.120 mole)590.971773 Comparative Example E21 1773Comparative Example E22 1773 Example E123/7368.43 (1.000 moles)61.51 (0.282 mole)193.60 (0.658 mole)17.77 (0.120 mole)605.281816 Comparative Example E23 1816Comparative Example E24 1816 Example E130/10368.43 (1.000 moles)0.00 (0.000 mol)276.57 (0.940 mole)17.77 (0.120 mole)626.741880 Comparative Example E25 1880Comparative Example E26 1880
    [506] BAB: 4,4'-bis (3-aminophenoxy) biphenyl
    [507] BPDA: 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride
    [508] PMDA: pyromellitic dianhydride PA: phthalic anhydride
    [509] PDMA / BPDA composition ratio / molmenstruumReaction statusPhysical properties of the obtained polymer Temperature rise processReactionIntrinsic viscosity (㎗ / g)Glass transition temperature (℃) Reference Example E210/0Equimolar compositionPrecipitation solidification after melting--- Comparative Example E17m, p-mixed cresolPrecipitation after dissolutionSlurry Form0.43250 Comparative Example E18N-methyl-2-pyrrolidonePrecipitation solidification after melting--- Example E107/3Equimolar compositionPrecipitation after dissolutionSlurry Form0.42237 Comparative Example E19m, p-mixed cresolMelt at 80 ℃Dissolution0.44238 Comparative Example E20N-methyl-2-pyrrolidonePrecipitation solidification after melting--- Example E115/5Equimolar compositionPrecipitation after dissolutionSlurry Form0.42232 Comparative Example E21m, p-mixed cresolMelt at 80 ℃Dissolution0.43232 Comparative Example E22N-methyl-2-pyrrolidonePrecipitation solidification after melting--- Example E123/7Equimolar compositionPrecipitation after meltingSlurry Form0.41229 Comparative Example E23m, p-mixed cresolMelt at 80 ℃Dissolution0.44230 Comparative Example E24N-methyl-2-pyrrolidonePrecipitation solidification after melting--- Example E130/10Equimolar compositionPrecipitation after meltingSlurry Form0.42224 Comparative Example E25m, p-mixed cresolMelt at 80 ℃Dissolution0.44225 Comparative Example E26N-methyl-2-pyrrolidonePrecipitation solidification after melting---
    [510] BAB: 4,4'-bis (3-aminophenoxy) biphenyl
    [511] BPDA: 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride
    [512] PMDA: pyromellitic dianhydride PA: phthalic anhydride
    [513] Equimolar compositions: equimolar compositions of m, p-mixed cresols and N-methyl-2-pyrrolidone
    [514] From the results of Comparative Example E17 and Reference Example E2, the polyimide using pyromellitic dianhydride as tetracarboxylic dianhydride, when an equimolar composition is used as a solvent, polyimide precipitates with progress of imidization, and the reaction solution It is not preferable because it solidifies. Moreover, when cresol is used as a solvent, this polyimide will precipitate polyimide with advancing of imidation, and will be in a favorable slurry state.
    [515] On the other hand, a polyimide containing 30 mol% or more of biphenyltetracarboxylic dianhydride as tetracarboxylic dianhydride has a large amount for the recovery of the polymer because polyimide does not precipitate even if imidization proceeds when cresol is used as a solvent. Although a poor solvent of is required, when an equimolar composition is used as a solvent, with the progress of imidation, a polyimide precipitates and it becomes a favorable slurry state.
    [516] From these results, according to the manufacturing method of the biphenyl tetracarboxylic-acid polyimide which concerns on this invention, since the reaction system becomes a slurry state, isolation of a polyimide is only filtration, and it becomes a simple process. Moreover, compared with the polyimide obtained by the conventional method, this polyimide maintains favorable heat resistance, without changing physical properties at all.
    [517] Examples E14 to E15, Comparative Examples E27 to E39, Reference Examples E3 to E5
    [518] Into a vessel equipped with a stirrer, a reflux condenser, a water separator, and a nitrogen inlet tube, the raw materials of the solvent and polyimide shown in Table E10 are injected, and the mixture is stirred from room temperature to 200 ° C. over 2 hours with stirring under a nitrogen atmosphere. It heated and reacted at 200 degreeC for 4 hours. In addition, the polymer concentration at the time of this superposition | polymerization is 25.0%.
    [519] The state of the reaction solution in the temperature rising process from room temperature to 200 ° C and the reaction at 200 ° C is shown in Table El0.
    [520] From these results, bicyclo (2,2,2) -octo-7-ene-2,3, as bis (3,4-dicarboxyphenoxy) ether dianhydride or aliphatic tetracarboxylic dianhydride as tetracarboxylic dianhydride. When 5, 6-tetracarboxylic acid dianhydride is used, since the solvent solubility of the obtained polyimide is too high, even if an equimolar composition is used as a solvent, the polyimide which can be obtained does not precipitate.
    [521] Diamine A (g) B (g)Tetracarboxylic acid dianhydride C (g) D (g)PA (g)menstruumReaction status KindsVolume (g)Temperature rise processReaction Example E14APB29.23 (0.100 mole)---BPDA27.95 (0.095 mole)---PA1.48 (0.010 mole)Equimolar composition165Precipitation after meltingSlurry Form Comparative Example E27m, p-mixed cresolMelt at 80 ℃Dissolution Comparative Example E28N-methyl-2-pyrrolidonePrecipitation solidification after melting- Reference Example E3APB29.23 (0.100 mole)---BTDA30.61 (0.095 mole)---PA1.48 (0.010 mole)Equimolar composition172Precipitation solidification after melting- Comparative Example E30m, p-mixed cresolAfter dissolution, it becomes gum state and cannot be stirred Comparative Example E31N-methyl-2-pyrrolidonePrecipitation solidification after melting- Reference Example E4APB29.23 (0.100 mole)---ODPA29.47 (0.095 mole)---PA1.48 (0.010 mole)Equimolar composition169Melt at 80 ℃Dissolution Comparative Example E33m, p-mixed cresolMelt at 80 ℃Dissolution Comparative Example E34N-methyl-2-pyrrolidonePrecipitation solidification after melting- Reference Example E5APB29.23 (0.100 mole)---BPDA13.98 (0.048 mole)BCD11.79 (0.048 mole)PA1.48 (0.010 mole)Equimolar composition159Melt at 80 ℃Dissolution Comparative Example E36m, p-mixed cresolMelt at 80 ℃Dissolution Comparative Example E37N-methyl-2-pyrrolidoneMelt at 80 ℃Dissolution Example E15APB14.62 (0.050 mole)DSDA12.42 (0.050 mol)BPDA27.95 (0.095 mole)---PA1.48 (0.010 mole)Equimolar composition159Precipitation solidification after meltingSlurry Form Comparative Example E38m, p-mixed cresolMelt at 80 ℃Dissolution Comparative Example E39N-methyl-2-pyrrolidonePrecipitation solidification after melting-
    [522] APB: 1,3-bis (3-aminophenoxy) benzene
    [523] BPDA: 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride
    [524] DSDA: bis (4- (3-aminophenoxy) phenyl) sulfone
    [525] BTDA: Benzophenonetetracarboxylic acid dianhydride
    [526] PA: phthalic anhydride
    [527] ODPA: bis (3,4-dicarboxyphenoxy) ether dianhydride
    [528] BCD: Bicyclo (2,2,2) -octo-7-ene-2,3,5,6-tetracarboxylic acid dianhydride
    [529] Equimolar compositions: equimolar compositions of m, p-mixed cresols and N-methyl-2-pyrrolidone
    [530] The polyimide obtained by the manufacturing method of the present invention is, for example, in the field of semiconductor containers, such as IC packaging trays, IC manufacturing trays, IC sockets, wafer carriers, and the like; In the field of electrical and electronic parts, in addition to connectors, sockets, bobbins, etc., production jigs such as hard disk carriers, liquid crystal display carriers, crystal oscillator production trays, and the like; In the field of office equipment parts, a separation tank for a copy machine, an adiabatic bearing for a copy machine, a gear for a copy machine, and the like; In the field of automotive parts, a thrust washer, a transmission ring, a piston ring, an oil seal ring and the like; In the field of industrial equipment parts, bearing retainers, pump gears, conveyor chains, slide bushes for stretch machines, etc .; In addition, it can be used for various fields, such as a film and a fiber.
    [531] In addition, a solvent containing a specific amount of the equimolar composition or equimolar composition according to the present invention has a high boiling point and a low solidification point, and has a moderate polarity (for example, dielectric constant of 20 (the same as that of acetone) to 33 (the same as methanol). Degree)), and because it has a unique property of not mixing with water, it can be used simply under the reaction conditions at a high temperature with the use as an organic solvent under the normal reaction conditions. For example, solvents for ink and paint, detergents for dissolving polyimide synthesis solvents in the production of polymers such as various organic and inorganic reactions, polyimide, solvents for extraction and purification of various chemical products, dyes and pigments, and the like. And solvents for paints and adhesives in which a refrigerant, a heat medium, and a polymer are dissolved, and a plasticizer of a polymer. Among these, for example, the production of the polyimide may be performed under high temperature conditions such that the polymerization temperature is 200 ° C or higher at normal pressure, and the solvent containing a specific amount of the equimolar composition or the equimolar composition according to the present invention. Is especially useful as an organic solvent for polyimide synthesis.
    [532] Moreover, since the solvent containing a specific amount of this equimolar composition or the said equimolar composition which concerns on this invention has a high boiling point, when using as a solvent of superposition | polymerization or reaction, reaction temperature can be raised, and reaction time can be shortened. .
    [533] Moreover, when using the equimolar composition which concerns on this invention or the solvent containing a specific amount of the said equimolar composition as a refiner | solvent, in the crystallization operation which melt | dissolves at high temperature and precipitates at low temperature, it is large by increasing the temperature difference of the said high temperature and said low temperature. Since solubility difference can be obtained, the refinement | purification yield of a target object can be improved.
    [534] Effects of the Invention
    [535] According to the method for producing a polyimide of the present invention, a slurry reaction solution in which polyimide is precipitated can be obtained, and the polyimide can be obtained by simply filtering the reaction solution as it is, so that the polyimide can be easily and inexpensively processed. Mid can be obtained. Moreover, according to the production method according to the present invention, even if the polymerization reaction is carried out at a high concentration of the polyimide production raw material, the reaction solution is in a slurry state without solidification, so that the productivity of the polyimide can be improved, Various physical properties (molding processability, sliding properties, low water absorption, electrical properties, thermal oxidation stability, radiation resistance, etc.) of the resulting polyimide are not impaired.
    权利要求:
    Claims (19)
    [1" claim-type="Currently amended] Imidation reaction between diamines and tetracarboxylic dianhydride in a solvent containing 50 to 100% by weight of an equimolar composition of the nitrogen-containing cyclic compound represented by the following formula (1) and the phenols represented by the following formula (2) Manufacturing method of polyimide to perform:

    In the (expression (1), X is -CH 2 - or -N (CH 3) - represents the, in the formula (2), R 1 and R 2, and may be the same with each other or different, and are each, -H , -OH, -CH 3 , -C 2 H 7 , -C 3 H 7 , -C 2 H 9 , -C 5 H 11 , -C 6 H 13 , -C 7 H 15 , -C 8 H 17 , -C 9 H 19 , -C 10 H 21 , -OCH 3 , -O (C 6 H 5 ), -NO 2 , -Cl, -Br or -F.
    [2" claim-type="Currently amended] The method for producing a polyimide according to claim 1, wherein the tetracarboxylic dianhydride contains biphenyltetracarboxylic dianhydride.
    [3" claim-type="Currently amended] The said tetracarboxylic dianhydride contains biphenyl tetracarboxylic dianhydride in 30-100 mol% with respect to all the tetracarboxylic dianhydride, The manufacture of the polyimide of Claim 1 or 2 characterized by the above-mentioned. Way.
    [4" claim-type="Currently amended] The method for producing a polyimide according to any one of claims 1 to 3, wherein the polyimide obtained by the imidization reaction has a repeating structural unit represented by the following general formula (3):

    [In Formula (3), Y is following formula (e)-(h):

    (Wherein R may be the same or different from each other, and each of a single bond, -O-, -CO-, -SO 2- , -S-, -CH 2 -or -C (CH 3 ) 2- At least one selected from the group consisting of:
    [5" claim-type="Currently amended] The repeating structural unit represented by the above-mentioned general formula (3) is contained in 30 to 100 mol% of all the repeating structural units, and is represented by the said general formula (3) in any one of Claims 1-4. Method for producing a polyimide, characterized in that the remaining portion different from the repeating structural unit is contained in a ratio of 0 to 70 mol%.
    [6" claim-type="Currently amended] 6. The polyimide of claim 5, wherein the remaining portion, which is a repeating structural unit different from the repeating structural unit represented by the general formula (3), has a repeating structural unit composed of a component unit derived from an aromatic tetracarboxylic acid. Manufacturing method.
    [7" claim-type="Currently amended] The method for producing a polyimide according to claim 6, wherein the repeating structural unit composed of a component unit derived from the aromatic tetracarboxylic acid is a repeating structural unit represented by the following formulas (a) and / or (b);

    [In Formulas (a) and (b), Ar 1 is the following Formulas (e) to (h):

    (In formulas (f), (g) and (h), R may be the same or different from each other, and each is a single bond, -O-, -CO-, -SO 2- , -S-, -CH At least 1 selected from the group consisting of 2 -or -C (CH 3 ) 2- ),
    In the formula (b), Ar 2 represents at least one selected from the group consisting of —O—, —CO—, —SO 2 —, —S—, —CH 2 — or —C (CH 3 ) 2 . ].
    [8" claim-type="Currently amended] The polyimide which has a repeating structural unit represented by the said General formula (3), The repeating structural unit in any one of Claims 1-7 is represented by either of following General formula (4)-(6). Method for producing a polyimide, characterized in that at least one kind of genie is a polyimide:

    [9" claim-type="Currently amended] The compound represented by the formula (1) is N-methyl-2-pyrrolidone and / or 1,3'-dimethyl-2-imidazolidinone according to any one of claims 1 to 8. Method for producing a polyimide, characterized in that.
    [10" claim-type="Currently amended] The phenols represented by the general formula (2) include phenol, o-chlorophenol, m-chlorophenol, p-chlorophenol, o-cresol, m-cresol and p according to any one of claims 1 to 9. At least one selected from the group consisting of: cresol, 2,3-xyleneol, 2,4-xyleneol, 2,5-xyleneol, 2,6-xyleneol, 3,4-xyleneol and 3,5-xyleneol It is 1 type of compounds, The polyimide manufacturing method characterized by the above-mentioned.
    [11" claim-type="Currently amended] The solvent according to any one of claims 1 to 10, wherein the solvent containing an equimolar composition between the compound represented by the formula (1) and the phenols represented by the formula (2) in an amount of 50 to 100% by weight, A method for producing a polyimide, characterized by containing the compound represented by the formula (1) or the phenols represented by the formula (2) in an amount of 0 to 50% by weight as the remaining part of the solvent.
    [12" claim-type="Currently amended] The method for producing a polyimide according to any one of claims 1 to 11, wherein a polyimide and / or oligomer is precipitated during the imidization reaction to make the reaction system slurry.
    [13" claim-type="Currently amended] The process for producing a polyimide according to any one of claims 1 to 12, wherein the reaction is carried out in the presence of a terminal sealant.
    [14" claim-type="Currently amended] The method for producing a polyimide according to any one of claims 1 to 13, wherein a product is precipitated during the imidization reaction to obtain a polyimide powder.
    [15" claim-type="Currently amended] The concentration of a raw material monomer consisting of diamines and tetracarboxylic dianhydride in the reaction solution ((total weight of raw material monomer) / (total weight of raw material monomer + solvent weight) according to any one of claims 1 to 14). ) Is in the range of 5 to 50% by weight.
    [16" claim-type="Currently amended] The polyimide obtained by the method of any one of Claims 1-15.
    [17" claim-type="Currently amended] It is obtained by the method of any one of Claims 1-15, The polyimide powder characterized by the above-mentioned.
    [18" claim-type="Currently amended] A solvent comprising an equimolar composition of a compound represented by the following formula (1) with a phenol represented by the following formula (2):

    In the (expression (1), X is -CH 2 - or -N (CH 3) - represents the, in the formula (2), R 1 and R 2, and may be the same with each other or different, and are each, -H , -OH, -CH 3 , -C 2 H 7 , -C 3 H 7 , -C 2 H 9 , -C 5 H 11 , -C 6 H 13 , -C 7 H 15 , -C 8 H 17 , -C 9 H 19 , -C 10 H 21 , -OCH 3 , -O (C 6 H 5 ), -NO 2 , -Cl, -Br or -F.
    [19" claim-type="Currently amended] 19. The solvent according to claim 18, comprising 50 to 100% by weight of an equimolar composition of the compound represented by the formula (1) and the phenols represented by the formula (2).
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    同族专利:
    公开号 | 公开日
    EP1273611A1|2003-01-08|
    EP1273611A4|2004-05-12|
    CN1418234A|2003-05-14|
    KR100503225B1|2005-07-22|
    US20030158370A1|2003-08-21|
    WO2001068742A1|2001-09-20|
    CN1164652C|2004-09-01|
    US6916898B2|2005-07-12|
    JP5246983B2|2013-07-24|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2000-03-13|Priority to JPJP-P-2000-00073971
    2000-03-13|Priority to JP2000073973
    2000-03-13|Priority to JPJP-P-2000-00073974
    2000-03-13|Priority to JPJP-P-2000-00073973
    2000-03-13|Priority to JP2000073972
    2000-03-13|Priority to JPJP-P-2000-00073972
    2000-03-13|Priority to JP2000073971
    2000-03-13|Priority to JP2000073974
    2001-03-13|Application filed by 미쯔이카가쿠 가부시기가이샤
    2002-10-26|Publication of KR20020081434A
    2005-07-22|Application granted
    2005-07-22|Publication of KR100503225B1
    优先权:
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    JP2000073972|2000-03-13|
    JPJP-P-2000-00073972|2000-03-13|
    JPJP-P-2000-00073971|2000-03-13|
    JP2000073973|2000-03-13|
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