TW201132679A - Polyamide-imide having nadiimide and production method thereof - Google Patents

Abstract

The invention provides a production method for polyamide-imide having a nadiimide framework, which reacts a dicarboxylic acid having an imide framework represented by the following general formula (1) with a diisocyanate ester compound represented by the general formula (II). Formula (I) (proviso in the formula, R.sup.1 is a divalent organic group selected from aliphatic groups, cycloaliphatic groups and aromatic groups) Formula (II) OCN-R.sub.2-NCO (proviso, in the formula, R.sup.2 is a divalent organic group selected from aliphatic groups, cycloaliphatic groups and aromatic groups). Accordingly, the invention provides a novel production method for polyamide-imide having a imide framework excellent in thermal resistance and transparency.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing a polyamidoximine having a Nadiimide structure which is a polymer having high heat resistance and transparency. [Prior Art] In the past, an epoxy resin used in an optoelectronic device or the like has been widely used for mounting processes of an electronic substrate, heat resistance or mechanical properties under high temperature operation, or general versatility. However, in recent years, high-intensity laser light or blue light, near-ultraviolet light has been widely used in the field of photovoltaic devices, and resins having excellent transparency, heat resistance, and light resistance have been required since then. Generally, the epoxy resin has high transparency under visible light, but sufficient transparency cannot be obtained in the ultraviolet to near-ultraviolet region. Further, the cured product composed of the alicyclic epoxy resin and the acid anhydride has high transparency in the near-ultraviolet region, but has a problem that it is easily colored by heat or light. In addition, various types of epoxy resins are discussed in order to improve heat resistance and ultraviolet ray resistance (see, for example, Patent Documents 1 to 4). On the other hand, heat-resistant resins such as polyamides and polyimides are excellent in heat resistance, insulating properties, light resistance, and mechanical properties, and are soluble in various solvents and have excellent workability. A surface protective film or an interlayer insulating film or the like as a semiconductor element is widely used. In particular, since the polyamine having an alicyclic structure is excellent in transparency in the ultraviolet light region, S: -5-201132679 has been reviewed as a material for photovoltaic devices and various displays (for example, refer to Patent Document 5). The above polyamine having an alicyclic structure has been described as being produced by reacting a dicarboxylic acid having an alicyclic structure with a diamine and then reacting with a diamine. Further, a method of producing a polyfluorene having an alicyclic structure is also known as a method of changing a dicarboxylic acid into a hydrazine halide (for example, refer to Patent Document 6). [Prior Art Document] Patent Document Patent Document 1: Special Opening 2007 Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 6] Japanese Patent Laid-Open No. Hei. No. Hei. No. 2008-3 1 406. SUMMARY OF THE INVENTION However, the method for producing polyamine as described in Patent Document 5 is by The amine is produced by polymerizing a dicarboxylic acid or a derivative thereof, but the reaction of the diamine with the dicarboxylic acid requires a high temperature of from 240 ° C to 350 ° C. The method for producing polyimine according to Patent Document 6 requires a treatment apparatus because a harmful halogen-based gas is generated during the reaction. Therefore, there is a problem of manufacturing cost, and an industrially simple manufacturing method is required. The present invention has been developed to solve the above problems. Specifically, the present invention relates to a method for producing -6-201132679 polyamidoquinone imine having a melon structure having excellent heat resistance and transparency. [Means for Solving the Problem] That is, the present invention is as follows. The present invention relates to a method for producing a polyamidoquinone imine having a Nadiimide structure, which is characterized in that a dicarboxylic acid having a mercaptoamine structure represented by the following formula (1) is used. ]

(However, in the formula, R1 is a divalent organic group selected from an aliphatic group, an alicyclic group and an aromatic group), and is reacted with a diisocyanate compound represented by the following formula (Π), OCN-R2- NCO (II) (wherein, R2 is a divalent organic group selected from an aliphatic group, an alicyclic group, and an aromatic group). The present invention relates to a process for producing a polyamidoximine having a mercaptoamine structure, wherein a dicarboxylic acid derivative having a sulfonamide structure represented by the above formula (I) is contained in the following (1) and (2) The method of the step is obtained; (1) Step: a diiminamide compound represented by the following formula (ΙΠ),

S 201132679 [Chemical 2]

(However, R1 is a divalent organic group selected from an aliphatic group, an alicyclic group, and an aromatic group), and a formic acid ester in the presence of a catalyst system containing a ruthenium compound, a cobalt compound, and a halide salt By reacting, a dicarboxylic acid derivative having a mercaptoamine structure represented by the following formula (IV) is obtained, [Chemical 3]

(IV) (However, in the formula, R1 is a divalent organic group selected from an aliphatic group, an alicyclic group and an aromatic group, and R3 and R4 are each independently an alkyl group having 1 to 4 carbon atoms), (2) Step: Hydrolysis of a dicarboxylic acid derivative having a mercaptoamine structure represented by the above formula (IV) to obtain a dicarboxylic acid having a mercaptoamine structure represented by the above formula (I). The present invention relates to a process for producing a polyamidoximine having a mercaptoamine structure, wherein the bis-indenamine compound represented by the above formula (III) is obtained by a method comprising the following (a-Ι) step, (a-Ι) step: 5 - norbornene represented by the following general formula (V) - 2,3- -8- 201132679

Reaction with a diisocyanate compound represented by the following formula (VI), OCN-R1 - NCO (VI) (however, R1 is a divalent organic group selected from an aliphatic group, an alicyclic group and an aromatic group) The diiminamide compound represented by the above formula (III) is obtained. Further, the present invention relates to a process for producing a polyamidoximine having a mercaptoamine structure, wherein the above ruthenium compound is a nail complex having both a carbonyl ligand and a halogen ligand in the molecule. The present invention relates to a process for producing a polyamidoquinone imine having a melon structure, wherein the above halide salt is a quaternary ammonium salt. The present invention relates to a process for producing a polyamidoquinone imine having a melon structure, wherein the above catalyst system further contains a basic compound. The present invention relates to a process for producing a polyamidoquinone imine having a mercaptoamine structure wherein the above basic compound is a tertiary amine. The present invention relates to a process for producing a polyamidoquinone imine having a mercaptoamine structure, wherein the above catalyst system further contains a phenol compound. The present invention relates to a process for producing a polyamidoquinone imine having a mercaptoamine structure, wherein the above catalyst system further contains an organohalogen compound. [Effects of the Invention] The polyamidamine imine having a mercaptoamine structure obtained by the production method of the present invention can be used as an electronic component for semiconductors and liquid crystals, and is an optical fiber or an optical fiber because of its excellent heat resistance and transparency. An optical material represented by a lens or the like can be used as a material related to a display or a medical material. The disclosure of the present application is related to the subject matter described in Japanese Patent Application No. 201-74542, the entire disclosure of which is hereby incorporated by reference. [Embodiment] Hereinafter, the present invention will be described in detail. <1> Polyamidoquinone imine having a melamine structure of the present invention One embodiment of the present invention relates to a method for producing a polyamidoximine having a Nadiimide structure, which is characterized by a dicarboxyl p having a mercaptoamine structure represented by the following general formula (I), [Chemical 5] 0 II HO-C-

(However, R1 is a divalent organic group selected from an aliphatic group, an alicyclic group, and an aromatic group), and is reacted with a diisocyanate compound represented by the following formula (Π), -10-201132679, 〇CN-R2-NCO (II) (wherein R2 is a divalent organic group selected from an aliphatic group, a lipid steroid group, and an aromatic group). (Diisocyanate compound represented by the formula (II)) The diisocyanate compound represented by the formula (II) in the invention is an aliphatic group or an alicyclic group as long as R2 in the above formula (II) The divalent organic group selected from the aromatic group and having two isocyanate machines are not particularly limited. As the aliphatic diisocyanate compound in which R2 in the above formula (II) is an aliphatic group, for example, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate or lysine diisocyanate can be used. Etc., these may be used alone or in combination of two or more. The alicyclic diisocyanate compound in which R2 in the above formula (II) is an alicyclic group can be, for example, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate or cyclohexyldiene. Isocyanate or the like, these may be used singly or in combination of two or more. As the aromatic diisocyanate compound in which R2 in the above formula (II) is an aromatic group, for example, 4,4'-diphenylmethane diisocyanate, toluene diisocyanate 'xylene diisocyanate, 4, 4' can be used. -diphenyl ether diisocyanate, 4,4'-[2,2-bis(4-phenoxyphenyl)propylidene] diisocyanate, biphenyl-4,4'-diisocyanate, biphenyl-3, 3'-diisocyanate, biphenyl_3,4,-diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, 2,2,-dimethylbiphenyl-4,4 '-Diisocyanate, 3,3'-diethylbiphenyl_4,4,·diisocyanate

-11 - S 201132679 Ester, 2,2'-diethylbiphenyl-4,4'-diisocyanate '3,3,·diphenyl-4,4'-diisocyanate, 2,2'-dimethoxy Benzene _4,4,· vinegar, naphthalene-1,5-diisocyanate 'naphthalene_2,6-diisocyanate, 1-isocyanate, 4-chloro-6-methyl_1,3-extension Phenyl diisocyanate or the like may be used singly or in combination of two or more. It is also possible to mix two or more kinds of aliphatic isocyanated cyclic isocyanate compounds and aromatic isocyanate compounds (having a general formula represented by the formula (1) The dicarboxylic acid of the amine structure) The second having the mercaptoamine structure represented by the above formula (I) is obtained by the method comprising the following steps (1) and (2), (1) Step: Making the following The sub-compound represented by the above formula (III): [Chemical 6] methoxybiisocyanate, 3-phenylene ester, etc., and the compound and the fat are used. Good carboxylic acid > guanamine structure

(wherein, R1 is an aliphatic group, an alicyclic group, and a selected divalent organic group), and reacts with a formate ester in the presence of a ruthenium compound, a cobalt compound, and a halogen catalyst system, and The formula (IV) represents a dicarboxylic acid derivative of a guanamine structure: the aromatic group salt has a sub-12-201132679 [Chem. 7]

N-R1—Ν'

=〇

.CMMO \J/ (However, R1 is a divalent organic group selected from an aliphatic group, an alicyclic group and an aromatic group, and R3 and R4 are each independently an alkyl group having 1 to 4 carbon atoms), 2) Step: Hydrolyzing a diacid derivative having a mercaptoamine structure represented by the above formula (IV) to obtain a diacid having a mercaptoamine structure represented by the above formula (I). The following describes each step. (1) Step: a step of obtaining a dicarboxylic acid derivative having a mercaptoamine structure represented by the above formula (IV) can be carried out as a reaction with a bis-indenine compound represented by the above formula (III) The formic acid ester used in the raw material in the case of the dicarboxylic acid derivative having a mercaptoamine structure represented by the formula (IV) is not particularly limited, and may be, for example, methyl formate, ethyl formate, propyl formate or isopropyl formate. Butyl formate, isobutyl formate, amyl formate, isoamyl formate, allyl formate, ethyl formate, benzyl formate, and the like are suitably selected and used. From the viewpoint of cost and reactivity, it is preferably a linear alkyl carboxylic acid ester such as methyl formate or ethyl formate, more preferably methyl formate. Further, the ester portion of the formate corresponds to R3 and R4 in the above formula (IV). R1 in the above formula (III) and formula (IV) is the same as R1 in the above formula (1) and after -13-201132679 in the formula (VI). The catalyst system in which the bis-indenine compound represented by the above formula (III) is reacted with a formate includes a ruthenium compound, a cobalt compound and a halide salt. Here, the "catalyst system" means not only the catalyst itself. Also included are additives, sensitizers, etc. that assist the role of the catalyst. The above hydrazine compound is not particularly limited as long as it contains a hydrazine compound. Specific examples of preferred ruthenium compounds are [Ru(CO)3C12]2, [Ru(CO)2C12]„, [Ru(CO)3C13]·, [Ru3(CO)i 丨Cl]·, [Ru4( CO) 13Cir or the like has a carbonyl group and a halogen ligand, and the like, wherein, in terms of improving the reaction rate, it is more preferably [Ru(CO)3C12]2, [1^( (:0)2(:12]1>, etc. The above ruthenium compound can be RuC13 or Ru3(CO)12.

RuC12(C8H12), Ru(CO)3(C8H8), Ru(CO)3(C8H12), and

Ru(C8Hlf))(C8H12) or the like as a precursor compound, or a pre-reaction compound before or during the reaction of obtaining a dicarboxylic acid derivative having a mercaptoamine structure represented by the above formula (IV) The above hydrazine compound is prepared and introduced into the reaction system. The amount of the ruthenium compound to be used is preferably from 1/1 〇〇〇〇 to 1 equivalent, more preferably from 1/1 00 0 to 1/5, based on the bis-indenamine compound represented by the formula (III). 0 equivalents. When the manufacturing cost is considered, the use of the ruthenium compound is as small as possible. However, when it is less than 1/10,000 eq, the reaction is extremely slow. The above cobalt compound is not particularly limited as long as it contains cobalt. Specific examples of the preferred cobalt compound are C(2)(CO)8, Co(CO)4, C〇4(CO)12-14-201132679, and the like, and a cobalt compound having a _based ligand: acetic acid, propionic acid a cobalt compound having a carboxylic acid compound on a ligand such as cobalt, cobalt benzoate or cobalt citrate; cobalt phosphate or the like. Among them, from the viewpoint of improving the reaction rate, it is more preferably c〇2(co)8, cobalt acetate, cobalt citrate or the like. The amount of the cobalt compound used is from 1/100 to 10 equivalents, preferably from 1/10 to 5 equivalents, based on the above hydrazine compound. The ratio of the above-mentioned cobalt compound to the above-mentioned cerium compound is less than 1/100, or more than 10, and there are dicarboxylic acid derivatives having a mercaptoamine structure represented by the above formula (IV) (hereinafter also referred to as The amount of "ester compound" produced is remarkably lowered. The halide salt is not particularly limited as long as it is a compound composed of a halide ion such as a chloride ion, a bromide ion or an iodide ion and a cation. The above cation may be any of an inorganic ion and an organic ion. Further, the above halide salt may contain one or more halogen ions in the molecule. The inorganic ion constituting the halide salt may also be a metal ion selected from the group consisting of alkali metals and alkaline earth metals. Specifically, it is exemplified by lithium, sodium, potassium, rubidium, planer, calcium, strontium or the like. Further, the organic ion is preferably an organic group derived from an organic compound or more. Examples thereof include ammonium, scaly, pyrrolidine, pyridyl, imidazole, and imine gun plasmas, and the hydrogen atom of the plasma may be substituted with a hydrocarbon group such as an alkyl group or an aryl group. Although not particularly limited, specific examples of preferred organic ions are tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, tetraamylammonium, tetrahexylammonium tetraheptylammonium, and tetra Octyl ammonium, trioctylmethyl ammonium, benzyl trimethyl ammonium, benzyl triethyl ammonium, benzyl tributyl ammonium,

S -15- 201132679 Tetramethyl rust, tetraethyl sulphate, tetraphenyl hydrazine, benzyl triphenyl sulphate, butyl methyl pyrrolidine iron, octyl methyl pyrrolidine key, bis(triphenylphosphine) imine Key plasma. Among them, from the viewpoint of improving the reaction rate, it is more preferably an ion of a quaternary ammonium salt such as butylmethylpyrrolidium chloride, bis(triphenylphosphine)imide, or trioctylmethylammonium chloride. . The halide salt used in the present invention is not necessarily a solid salt, and an ionic liquid containing a halide ion which is liquid in a temperature range near room temperature or below 1 °C can also be used. Specific examples of the cation used in the ionic liquid are exemplified by 1-ethyl-3-methylimidazole, 1-propyl-3-methylimidazole, and 1-butyl-3-methylimidazole. 1-pentyl-3-methylimidazolium, b-hexyl-3-methylimidazolium,bheptyl-3-methylimidazolium- 1-octyl-3-methylimidazole gun 1- 1-mercapto-3_ Methyl imidazole, 1-dodecyl-3-methylimidazole, 1-tetradecyl-3-methylimidazole, 1-hexadecyl-3-methylimidazole, .1- Octadecyl-3-methylimidazolium, 1-ethyl-2,3-dimethylimidazole gun '1-butyl-2,3-dimethylimidazolium iron, bupyl-2,3-di Methyl imidazole, 1-ethylpyridine, 1-butylpyridyl, 1-hexylpyridinium, 8-methyl-1,8-diazabicyclo[5.4.0]-7·undecene , 8-ethyl-1,8-diazabicyclo[5.4.0]-7-undecene, 8-propyl-1,8-diazabicyclo[5·4·0]-7- Undecene, 8-butyl-1,8-diazabicyclo[5.4·0]-7-deca-carbene, 8-pentyl-1,8-diazabicyclo[5·4.0]- 7-Deca-carbene, 8-hexyl-1,8-diazabicyclo[5.4.0]-7-~1-carbene, 8-heptyl-indole, 8-diazabicyclo[5.4. 0]-7-undecene, 8 - an organic ion such as octyl-1,8-diazabicyclo [5·4·0]-7- eleven carbon. In the present invention, the above-mentioned halide salt may be used singly or in combination of a plurality of groups -16 to 201132679. Among the above halide salts, preferred halide salts are chloride salts, bromine salts, and iodide salts, and the cation is an organic ion. Although not particularly limited, specific examples of preferred halide salts in the present invention are chlorinated butylmethylpyrrolidine gun, bis(triphenylphosphine)imide iodide, trioctylmethylammonium chloride. Wait. The amount of the halide salt added is, for example, from 1 to 1,000 equivalents, preferably from 2 to 50 equivalents, per equivalent of the hydrazine compound. By increasing the amount of addition of more than one equivalent, the reaction rate can be effectively increased. On the other hand, when the amount added exceeds 1 当量 equivalent, the effect of promoting the reaction cannot be further improved even if the amount of addition is further increased. The reaction of the bis-indenine compound represented by the formula (ΠΙ) with a formic acid ester of the present invention is carried out by adding a basic compound or a phenol compound as needed in a catalyst system containing the above-mentioned cerium compound, a cobalt compound and a halide salt. Any one or two or more of the organic halogen compounds can further enhance the reaction promoting effect by the above catalyst system. The basic compound used in the present invention may be an inorganic compound or an organic compound. Specific examples of the basic inorganic compound are carbonates of alkali metals and alkaline earth metal metals, and hydrogencarbonate 'hydroxide salts' alkoxides. Specific examples of the basic organic compound are a primary amine compound, a secondary amine compound, a tertiary amine compound, a pyridine compound, an imidazole compound, a quinoline compound, and the like. Among the above basic compounds, a tertiary amine compound is preferred from the viewpoint of the reaction promoting effect. Specific examples of preferred tertiary amine compounds -17 to 201132679 which can be used in the present invention are exemplified by trialkylammonium, N-alkylpyrrolidine, quinuclidine, and triethylenediamine. The amount of the basic compound to be added is not particularly limited, but is, for example, 1 to 1,000 equivalents, preferably 2 to 200 equivalents based on the hydrazine compound. When the amount of addition is 1 equivalent or more, the tendency to promote the effect is more prominent. Further, when the amount of addition exceeds 1,000 equivalents, the effect of promoting the reaction cannot be further improved even if the amount of addition is further increased. The phenol compound used in the present invention is not particularly limited. Specific examples of the phenol compound which can be used are phenol, cresol, alkylphenol, methoxyphenol, phenoxyphenol, chlorophenol, trifluoromethylphenol, hydroquinone, and catechol. The amount of the phenol compound to be added is not particularly limited, but is, for example, 1 to 1,000 equivalents, preferably 2 to 200 equivalents based on the ruthenium compound. When the amount of addition is 1 equivalent or more, the tendency to promote the effect is more prominent. Further, when the amount added exceeds 1,000 equivalents, the reaction-promoting effect tends to be further improved even if the amount of addition is further increased. The organohalogen compound used in the present invention is not particularly limited. Specific examples of the organohalogen compound which can be used are exemplified by methyl halide, dihalomethane, dihaloethane, trihalomethane, tetrahalogenated carbon, halogenated benzene and the like. The amount of the organohalogen compound to be added is not particularly limited, but is, for example, 1 to 1000 equivalents, preferably 2 to 200 equivalents based on the hydrazine compound. When the amount of addition is 1 equivalent or more, the tendency to promote the effect is more apparent. Further, when the amount added exceeds 1,000 equivalents, even if the amount of addition is further increased, there is a tendency that the reaction promotion cannot be further improved. -18- 201132679 The reaction of the bis-indenylamine compound represented by the formula (III) with the formic acid ester in the present invention can be carried out especially without using a solvent. However, a solvent can also be used as needed. The solvent which can be used is not particularly limited as long as it is a compound which can be used as a raw material, that is, a bis-indenamine compound represented by the formula (ΠΙ) and a formate. Specific examples of the solvent which can be suitably used are n-pentane, n-hexane, n-heptane, cyclohexane, benzene, toluene, o-xylene, p-xylene, m-xylene, ethylbenzene, cumene. , tetrahydrofuran, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethylimidazolidinone, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol Alcohol dimethyl ether, tetrahydronaphthalene, and the like. In the present invention, the reaction of the bis-indenine compound represented by the formula (ΠΙ) with the formic acid ester is preferably carried out at a temperature ranging from 80 ° C to 200 ° C. The above reaction is preferably carried out in a temperature range of from 100 ° C to 160 ° C. By carrying out the reaction at a temperature higher than 80 ° C, the reaction rate is accelerated, and the reaction efficiency proceeds satisfactorily. On the other hand, by controlling the reaction temperature to 200 ° C or lower, the decomposition of the formate used as a raw material can be suppressed. When the formic acid ester is decomposed, since the addition of the ester group of the bis-indenine compound represented by the general formula (III) cannot be achieved, the excessively high reaction temperature is unsatisfactory. When the reaction temperature exceeds the boiling point of any of the bis-indenamine compound or the formic acid ester represented by the formula (III) used as a raw material, it is necessary to carry out the reaction in a pressure-resistant container. The termination of the reaction can be confirmed by a known analytical technique such as gas chromatography or NMR. The dicarboxylic acid derivative having the mercapto structure of -19-201132679 represented by the above formula (IV) obtained by the above method can be directly used for the production of polyamidoximine, but preferably by distillation under reduced pressure. Wait for the use. (2) Step: a step of obtaining a dicarboxylic acid having a mercaptoamine structure represented by the above formula (I). The dicarboxylic acid having a mercaptoamine structure represented by the formula (I) in the present invention may be as described above. The dicarboxylic acid derivative having a mercaptoamine structure represented by the above formula (IV) obtained in the step (1) is obtained by hydrolysis. The method of hydrolyzing the dicarboxylic acid derivative having a mercaptoamine structure represented by the above formula (IV) into a dicarboxylic acid having a mercaptoamine structure represented by the general formula (I) is not particularly limited, and for example, it can be used. Acid hydrolysis, alkali hydrolysis, and the like as described in Japanese Patent No. 259 1 492 or JP-A-2008-31 406. Alternatively, the acid component or the alkali component may be added without being added, and the mixture may be heated at a high temperature of 140 ° C or higher in the presence of moisture in a heat-resistant container. The termination of the reaction by the above method can be confirmed by a known analytical technique such as gas chromatography, liquid chromatography, or NMR. The dicarboxylic acid having a mercaptoamine structure represented by the formula (1) can be used as a raw material of polyamidoximine by distillation, recrystallization, reprecipitation or the like. (Synthesis of a bis-indenine compound represented by the formula (III)) The bis-indenylamine compound represented by the above formula (III) can be obtained by the synthesis method of U) shown below. The synthesis method of (a) which obtains the bis-indenylamine compound represented by the above formula (III) comprises the following step (a-1). (a-Ι) in the step (a-Ι), 5-norbornene represented by the following formula (V) - -20- 201132679

Reacts with a diisocyanate compound represented by the following formula (VI), OCN-Ri_N c〇(VI) (but 'wherein R1 is a divalent organic group selected from an aliphatic group, an alicyclic group and an aromatic group) ). In the step (a-Ι), the reaction of 5-norbornene-2,3-diresin anhydride ' represented by the above formula (v) with the diisocyanate compound represented by the above formula (VI) is obtained. The bis-indenamine compound represented by the formula (III). The diisocyanate compound represented by the formula (VI) used in the above (a-Ι) step can be the same as the diisocyanate compound (expressed by the above formula (II)) which is a raw material for the synthesis of polyamidoximine. By. In the step (a-Ι), the reaction of 5-norbornene-2,3-dicarboxylic acid hydrazone f represented by the general formula (v) with the diisocyanate compound represented by the above formula (VI) is not particularly remarkable. The number of equivalents of the isocyanate group of the diisocyanate compound represented by the formula (11) is limited to the number of equivalents of the acid anhydride group of the 5-norbornene-2,3-residual anhydride represented by the formula (V) Good for ~2〇, better for 1.0~1_7, and better for io~ι·5, preferably 1〇~13. When it is less than 1 ’, there will be unreacted 5 _ borneol thin _2, 3- phthalic anhydride is easy to remain -21 - 201132679 tendency. When the amount is more than 2.0, the isocyanate compound tends to cause side reactions, and it is difficult to increase the molecular weight of the obtained polyamidoximine, and the heat resistance of the mechanical properties tends to decrease. The reaction temperature in the (a-Ι) step is preferably from 80 to 200 ° C, more preferably from 90 to 190 ° C, most preferably from 100 to 180 ° C. The reaction time can be appropriately selected depending on the size of the batch and the reaction conditions employed. The diiminamide compound obtained in the step (a-1) may be subjected to distillation, recrystallization, reprecipitation or the like, but may be carried out in a subsequent step (dicarboxylic acid ester having a mercaptoamine structure represented by the general formula (I). The reaction solution is used directly in the synthesis). In the step (a-Ι), a solvent can be used for the reaction of 5-norbornene-2,3-dicarboxylic acid anhydride represented by the formula (V) with the diisocyanate compound represented by the above formula (VI). The solvent which can be used is a compound which can be used as a raw material (5-norbornene-2,3-dicarboxylic anhydride represented by the formula (V) and a diisocyanate compound represented by the formula (VI)) There are no special restrictions. Specific examples of the solvent which can be suitably used may be N-methylpyrrolidone, N,N'-dimethylacetamide, N,N'-dimethylformamide, i,3-dimethyl-3. a nitrogen-containing solvent such as 4,5,6-tetrahydro-2(1H)-pyrimidinone; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, An ether solvent such as triethylene glycol diethyl ether; a sulfur-containing solvent such as dimethyl hydrazine, diethyl hydrazine, dimethyl milling or cyclobutyl; γ-butyrolactone, fibrin acetate, etc. An ester solvent; a ketone solvent such as cyclohexanone or methyl ethyl ketone. The solvent is used in an amount of 100 parts by mass relative to the total amount of the 5-isborne _-22-201132679 2,3-dicarboxylic anhydride represented by the formula (V) and the diisocyanate compound represented by the above formula (VI). It is preferably from 20 to 500 parts by mass, more preferably from 30 to 30,000 parts by mass, most preferably from 5 to 2 parts by mass. When the amount used is less than 2 parts by mass, the raw material cannot be completely dissolved, and the reaction rate is slow. On the other hand, when it exceeds 500 parts by mass, there is no particular advantage in that only the yield of the imide compound per batch is lowered. (Reaction conditions for obtaining a polyamidoquinone imine having a mercaptoamine structure) Use of a dicarboxylic acid having a mercaptoamine structure represented by the above formula (I) and a diisocyanate compound represented by the formula (Π) The amount of moles of the isocyanate group is preferably from 0.7 to 2.0, more preferably from 0.8 to 1.7, still more preferably from 0.9 to 1.5, based on the molar number of the carboxyl group of the dicarboxylic acid having a methylene chloride structure. Good for 0.95~1.3. When it is less than 0.7 or more than 2.0, it is difficult to increase the molecular weight of the obtained polyamidoximine, and there is a tendency that mechanical properties, heat resistance, and the like are lowered. The reaction temperature is preferably from 80 to 2 〇 0 ° C, more preferably from 90 to 190 ° C, most preferably from 100 to 180 ° C. The reaction time can be appropriately selected depending on the size of the batch and the reaction conditions employed. A solvent can be used for the reaction of the dicarboxylic acid having a mercaptoamine structure represented by the formula (1) with the diisocyanate compound represented by the formula (II). The solvent which can be used is not particularly limited as long as it is a compound which can be used as a raw material (a dicarboxylic acid having a mercaptoamine structure of the formula (I) and a diisocyanate compound represented by the formula (II)). Specific examples of the solvent which can be suitably used may be N-methylpyrrolidone, hydrazine, hydrazine, -dimethylacetamide, N,N'-dimethylformamide, 1,3-dimethyl

S -23- 201132679 base-3,4,5,6-tetrahydro-2(1 fluorene)-pyrimidinone and other nitrogen-containing solvents; diethylene glycol dimethyl ether, diethylene glycol diethyl ether , an ether solvent such as trimethyl ether or triethylene glycol diethyl ether; - methyl hydrazine, diethyl hydrazine, dimethyl hydrazine, cyclobutyl solvent; γ-butyrolactone, acetic acid lysis An ester solvent such as a ketone; a ketone solvent such as cyclohexanone or methyl ethyl ketone; The amount of the solvent to be used is preferably from 20 to 500 parts by mass, more preferably from 3 to 500 parts by mass, based on 100 parts by mass of the diisocyanate represented by the formula (I) and the diisocyanate represented by the formula (II). , parts, preferably 50 to 200 parts by mass. When the amount is less than 20 masses, the material does not dissolve completely, and the reaction rate tends to be slow. When the amount is exceeded, only the yield of each batch of polyamidoquinone is particularly advantageous. Further, the reaction liquid obtained by the above method containing a ruthenium imine having a mercaptoamine structure becomes a polymer solution, so that the polyamidoguanide can be heated by heating at normal pressure or under normal pressure. <2> Polyamidoquinone imine having a mercaptoamine structure The number average molecular weight of the imine having a mercaptoamine structure obtained by the production method of the present invention is preferably from 2,000 to 250,000 3,000 to 220,000. When the number average molecular weight is less than 2,000, there is a tendency to decrease, and when it exceeds 250,000, there is a tendency to dissolve the solvent. When the total amount of the sulfur-containing sulfoximine frame such as ethylene glycol dioxime obtained by the production method of the present invention is -300 mass parts, the original 500 mass drop is obtained, and the polyacetamide decompression environment is not provided. The polyamines are better in heat resistance and the like. Polyamine 醯-24- 201132679 The imine has a structure represented by the following formula (νιι). [Chemistry 9]

(ντί) Further, in the above formula (VII), the R1 system is the same as the above formula (〇, the above formula (III), and the above formula (IV). The R2 group in the above formula (VII) is as described above. R2 in the diisocyanate compound represented by the formula (II) is the same. Further, in the above formula (VII), n is U00. The number average molecular weight of the polyamidoquinone having a sub-an amine structure is within the above range 'The production may be carried out by the production method of the present application. The 'number average molecular weight is measured using a gel permeation chromatography (hereinafter abbreviated as GPC)' under the following conditions and calculated using a standard polystyrene calibration curve. Device: manufactured by Hitachi, Ltd., L6000 type column: manufactured by Showa Denko (share), Shodex KD-806Mxl root dissolving solution 'N-methyl_2_卩比略院嗣l.Oml/min Detector: UV (280 nm) EXAMPLES Hereinafter, the present invention will be described in detail by way of examples. However, the scope of the present invention is not limited by the following examples. <Synthesis of a bis-indolamine compound represented by the formula (III) &gt; -25- 201132679 (Synthesis Example 1) [Di-indoleamine compound (NDi-丨) Synthesis] [Chemical 10]

Into a one-liter flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a cooling tube, 196.8 g of norbornene-2,3-dicarboxylic anhydride and 100.8 g of hexamethylene diisocyanate (anhydride/isohydroester) were fed. (Equivalent ratio) = ι·〇〇/ι·〇〇) and N-methylpyrrolidone 297.6 g, heated in an oil bath. After the temperature was raised to 120 ° C and the reaction was carried out for 3 hours, the solvent N-methylpyrrolidone was distilled off under reduced pressure to obtain a bis phthalamide compound 240g. The obtained diammonium compound was analyzed by liquid chromatography to have a purity of 100%. Further, the FT-IR spectrum of NDI-1 was measured to confirm the absorption of the quinone imine characteristic in the vicinity of 1 780 CHT1. &lt;Synthesis of a dicarboxylic acid derivative having a mercaptoamine structure represented by the general formula (IV)&gt; (Synthesis Example 2) [Synthesis of a dicarboxylic acid derivative having a mercaptoamine structure] [Chemical 11]

In a pressurized reaction apparatus made of stainless steel having an internal volume of 500 ml, a mixture of 25.25 mmol of [Ru(CO)3C12]2 as a ruthenium compound and 0.25 mmol of a cobalt compound as a cobalt compound (CO) 8, 5mmol as a catalyst system of the halogen--26-201132679 compound salt of trioctylmethylammonium chloride, 20mmol of triethylamine as a basic compound, and 5mmol of p-cresol as a phenol compound After adding 100 mmol of the bis-indolamine compound (NDI-1) obtained in Synthesis Example 1, and 50 ml of methyl formate, the reaction vessel was purged with nitrogen gas at 0. 5 MP a and maintained at 120 ° C for 8 hours. Subsequently, the reaction apparatus was cooled to room temperature, pressure was released, and a part of the residual organic phase was taken and analyzed using a gas chromatograph. According to the analysis results, the methyl dicarboxylate having a methylene chloride structure formed by the reaction was 93.0 mmol (yield 9 3.0% based on methyl dicarboxylate having a methylene chloride structure). The resulting dicarboxylic acid methyl ester having a methylene chloride structure was isolated by distillation under reduced pressure. &lt;Synthesis of a dicarboxylic acid having a mercaptoamine structure represented by the general formula (I)&gt; (Synthesis Example 3) [Synthesis of a dicarboxylic acid having a mercaptoamine structure] [Chemical 12]

Into a 1 liter pear-shaped flask equipped with a cooling tube, 30 g of a dicarboxylic acid methyl ester having a mercaptoamine structure and 200 g of methanol obtained in Synthesis Example 2 were poured into a homogeneous solution, and then a 10% sodium hydroxide solution was fed and placed. The mixture was heated under reflux for 6 hours in a 100 ° C oil bath. Then, methanol was distilled off until the amount of the reaction liquid became 140 g, and 48 ml of 36% hydrochloric acid was added thereto to adjust the pH to 1, and a white powder was precipitated. The white powder was filtered, washed with water and dried to obtain 28 g of a dicarboxylic acid having a methylene chloride structure. &lt;Synthesis of polyamidoquinone imine having a mercaptoamine structure&gt; S: -27- 201132679 (Example 1) [Synthesis of polyamidoquinone imine (PA1·1) having a mercaptoamine structure] In a 500 ml flask equipped with a stirrer, a thermometer, a nitrogen gas introduction tube, and a cooling tube, 90.00 g (0.180 mol) of a dicarboxylic acid having a mercaptoamine structure obtained in Synthesis Example 3, and a hexamethylene diisocyanate 30.84 g (0.184) were added. Mohr) (dicarboxylic acid / diisocyanate (mole ratio) = 1.00 / 1.02) and &gt; 1-methylpyrrolidone 181.278, after raising the temperature to 1201, the reaction was carried out for 5 hours to obtain a number average molecular weight of 80,000. Polyamine amidoxime (PA 1-1) in the guanamine structure. The obtained polyamidoximine (PAI-1) having a mercaptoamine structure was coated on a Teflon (registered trademark) substrate, heated at 250 ° C, and the organic solvent was dried to form a film having a film thickness of 3 Ομηι. . The glass transition temperature (Tg) and the thermal decomposition onset temperature (5% mass reduction temperature, Td5) of the coating film were measured under the following conditions. The results are shown in Table 1. (1) Glass transition temperature (Tg) Measured by a thermomechanical analyzer (manufactured by Seiko Electronics Co., Ltd., Model 5200 TMA). Measurement mode: Extended measurement spacing: l〇mm Load: 1 〇g Heating rate '· 5 °C/min Ambient: Air (2) Thermal decomposition onset temperature (5% mass reduction temperature, Td5) -28- 201132679 A thermobalance (manufactured by Seiko Electronics Co., Ltd., Model 5200 TG-DTA) was measured. Heating rate: 5 ° C / min Atmosphere: Air, measured by the V_5 type 70 UV/VIS spectrometer manufactured by Japan Spectrophotometer, the wavelength of the polyamidoquinone imine (PAI-1) having the methylene chloride structure Light transmission rate. The evaluation results are summarized in Table 1. (Example 2) [Synthesis of Polyamidoamine Iine (P A1-2) having a melamine structure] In a 50 ml flask equipped with a stirrer, a thermometer, a nitrogen gas introduction tube, and a cooling tube, Synthesis Example 3 was placed. The obtained dicarboxylic acid having a mercapto structure of 80.00 g (0.160 mol), 4,4'-cyclohexylmethane diisocyanate 42.76 g (0.163 mol) (dicarboxylic acid / diisocyanate (mole ratio) = 1,00/1.02) and N-methylpyrrolidone 184.14g, after heating to 12〇t, reacting for 5 hours to obtain a polyamidoquinone imine (PAI-) having a molecular weight average molecular weight of 88,00. 2). The properties of the obtained polyamidamine imine (PAI-2) having a methylene chloride structure were evaluated in the same manner as in Example 1. The results are summarized in Table 1. (Example 3) [Synthesis of polyamidoquinone imine (pAI_3) having a melamine structure] In a 500 ml flask equipped with a stirrer, a thermometer, a nitrogen gas introduction tube, and a cooling tube, the synthesis example 3 was obtained. 2-9g (0.160 moles), 4,4'-cyclohexylmethane diisocyanate 40.80g (0.163 moles) (dicarboxylic acid / diisocyanate (mole ratio) = 1.00/1.02) and 181.20 g of N-methylpyrrolidone were heated to l2〇r, and reacted for 5 hours to obtain a polyamidoquinone imine (PAI-3) having a molecular weight average molecular weight of 78,000. The properties of the obtained polyamidamine imine (PAI-3) having a methylene chloride structure were evaluated in the same manner as in Example 1. The results are summarized in Table 1. (Comparative Example 1) 264.00 g (0.50 mol) and hexamethylenediamine 58.00 having a mercapto structure obtained in Synthesis Example 3 were fed into a 500 ml flask equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a cooling tube. g (0.50 mol) (dicarboxylic anhydride / diamine (mole ratio) = 1. 〇〇 / 1 · 〇〇), reacted at 1 60 ° C for 2 hours, at 1 90 ° C for 3 hours, at The reaction was carried out at 240 ° C for 5 hours to obtain a polyamidoquinone imine (PAI-4) having a molecular weight average molecular weight of 5,500. The properties of the obtained polyamidamine imine (PAI-4) having a methylene chloride structure were evaluated in the same manner as in Example 1. The results are shown in Table 1. (Comparative Example 2) 211.20 g (〇.40 mol) of a dicarboxylic acid having a mercaptoamine structure obtained in Synthesis Example 3 was fed into a 500 ml flask equipped with a stirrer, a thermometer, a nitrogen gas introduction tube, and a cooling tube. 4,4'-Diaminodicyclohexylmethane 84.0 08 (0.40 mol) (dicarboxylic anhydride/diamine (mole ratio) = 1.0 0/1.00), reacted at 160 ° C for 2 hours at 190 ° C The reaction was carried out for 3 hours at 240 ° C for -30 to 201132679 for 5 hours to obtain a polyamidoquinone imine (PAI-5) having a molecular weight average molecular weight of 4,600. The properties of the obtained polyamidoximine (PAI-5) were evaluated in the same manner as in Example 1. The results are summarized in Table 1. [Table 1] Item Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 160ΐ: /21ι 160^/2h Synthesis conditions 120*C/5h 120t:/5h 120t:/5h 190t:/3K 190t:/ 3h 240t:/5h 2Λ〇Χ:/ΒΗ Number average molecular weight 80,000 88,000 78, 000 5,500 4, 600 Glass transfer temperature re) 210 215 218 180 168 Film thermal decomposition starting temperature 420 437 428 315 307 Characteristic light 400nra 100 100 80 100 100 Transmittance 500 nm 100 100 95 100 100 (%) 600 nm 100 100 100 100 100 As can be seen from Table 1, Examples 1 to 3 can be manufactured at a lower temperature and a shorter time at 120 ° C for 5 hours. Polyammonium imine. On the other hand, in Comparative Example 1 and Comparative Example 2, even when the reaction was carried out at 160 ° C for 2 hours, the reaction was carried out at 190 t for 3 hours, and the reaction was carried out at 240 t for 5 hours, the number average molecular weight was still not sufficiently large, and the number average molecular weight was found to be small. When the degree of polyamine of Examples 1 to 3 is increased, a reaction at a higher temperature for a longer period of time is required. [Industrial Applicability] According to the production method of the present invention, a polyamidoquinone imine having a mercaptoamine structure excellent in heat resistance and transparency can be obtained. Further, the obtained polyamidoximine having a melamine structure can be used as an optical material such as an optical fiber or an optical lens, and can be used as a display-related material or a medical material. -31 -

Claims (1)

201132679 VII. Patent Application No. K - A method for producing a polyamidoximine having a Nadiimide structure, characterized in that a diterpenoid having a ruthenium structure represented by the following formula (I) , [Chemical 1] (However, R1 is a divalent organic group selected from an aliphatic group, an alicyclic group and an aromatic group), and is reacted with a diisocyanate compound represented by the following formula (II), OCN-R2- NCO (II) (wherein, R2 is a divalent organic group selected from an aliphatic group, an alicyclic group, and an aromatic group). 2. A process for producing a polyamidoquinone imine having a mercaptoamine structure, wherein the dihydrous acid derivative having a mercaptoamine structure represented by the above formula (I) is contained in the following (1) to (1) 2) The method of the step is obtained; (1) Step: a diiminamide compound represented by the following formula (III), -32-201132679 [Chemical 2] (ITT) (However, in the formula, R1 is a divalent organic group selected from an aliphatic group, an alicyclic group, and an aromatic group), and a catalyst containing a phthalic acid compound, a cobalt compound, and a halide salt The reaction is carried out in the presence of a system to obtain a dicarboxylic acid derivative having a mercaptoamine structure represented by the following formula (IV), [Chemical 3] (However, R1 is a monovalent organic group selected from an aliphatic group, an alicyclic group, and an aromatic group, and R1 2 is independently an alkyl group having a carbon number), (2) a step. The dicarboxylic acid derivative represented by the above formula (IV) is hydrolyzed to obtain a dicarboxylic acid having a mercaptoamine structure represented by the above formula (1). The bismuth compounding system of the first or second type having the amide structure represented by the above formula (ΙΠ) is exo-formulated, (al) step: the following formula is used: (V) Table 5 - norbornene - 33 - 1 · Method of manufacture of the second polyamidoximine as claimed in the patent application, 201132679 Reaction with a diisocyanate compound represented by the following formula (VI), OCN - R1 - NC Ο (VI) (however, R1 is a divalent organic compound selected from an aliphatic group, an alicyclic group and an aromatic group) The bis-indenamine compound represented by the above formula (III) is obtained. 4. The method for producing a polyamidamine having a melamine structure according to the second or third aspect of the patent application, wherein the nail compound is intramolecularly having a carbonyl ligand and a halogen ligand Things. 5. The process for producing a polyamidoquinone imine having a ruthenium amine structure according to any one of claims 2 to 4, wherein the aforementioned halide salt is a quaternary ammonium salt. The method for producing a polyamidoquinone imine having a mercaptoamine structure according to any one of claims 2 to 5, wherein the catalyst system further contains a basic compound. 7. The process for producing a polyamidamine imine having a methylene chloride structure according to claim 6, wherein the basic compound is a tertiary amine. 8. The method of producing a polyamidoquinone imine having an amnesty structure according to any one of claims 2 to 7, wherein the catalyst system further comprises a phenol compound. The method for producing a polyamidoquinone imine having a mercaptoamine structure according to any one of claims 2 to 8, wherein the catalyst system further contains an organic halogen compound. S -35- 201132679 Four designated representative maps: (1) The representative representative of the case is: No (2) The symbol of the representative figure is a simple description: No 201132679 5. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: formula (I) -4-