TWI789520B - Composition and manufacturing method thereof - Google Patents

Abstract

A composition of the present invention includes an isomer mixture of a compound represented by the following formula (1). In the formula, R¹ , R² and R³ independently represent a hydrogen atom, aryl group, alkyl group having 1 to 8 carbon atom(s) or alkoxy group having 1 to 8 carbon atom(s); and X represents a group represented by the following formula (2), a group represented by the following formula (3) or a group represented by the following formula (4).

Description

Composition and its manufacturing method

The present invention relates to a composition and a manufacturing method thereof. This case claims priority on the basis of Japanese Patent Application No. 2018-105406 filed in Japan on May 31, 2018, and its contents are cited here.

4,4'-Methylenebissalxaldehyde can be used in a variety of applications because the formyl group it contains is highly reactive and can be modified through oxidation/reduction reactions. For example, a polyimine is obtained by reacting 4,4'-methylenebissial and diamine (Non-Patent Document 1). Polyimides using 4,4'-methylenebissial have excellent mechanical strength, heat resistance, and electrical properties, and are expected to be applied to various polymer industrial materials.

However, the solvent solubility of 4,4'-methylenebissial aldehyde is weak, so the workability is poor and modification is not easy. Moreover, when making polyimine, since even polar solvents such as N-methylpyrrolidone are insoluble, it is impossible to synthesize polyimine without using specific solvents such as m-cresol and the like that are toxic and irritating, and Even if it is synthesized, it is difficult to obtain a high molecular weight product with a weight average molecular weight of 20,000 or more.

prior art literature non-patent literature Non-Patent Document 1: Organic Synthetic Chemistry Vol. 41 No. 10 (1983) pp. 972-984

The problem to be solved by the invention The object of the present invention is to provide a composition which is very useful as a raw material of a polymer material and the like, and a method for producing the same.

means to solve problems The present invention has the following aspects. [1] A composition comprising a mixture of isomers of a compound represented by the following formula (1).

[chemical formula 1]

(In the formula, R ¹ , R ² and R ³ are each independently representing a hydrogen atom, an allyl group, an alkyl group with 1 to 8 carbon atoms or an alkoxy group with 1 to 8 carbon atoms, and X represents the following formula (2 ), the group represented by the following formula (3) or the group represented by the following formula (4).)

[chemical formula 2]

[2] The composition according to [1] above, wherein the ratio of the peak area of the isomer mixture to the total peak area measured by gel permeation chromatography is 80 area % or more. [3] A method for producing a composition, which is a method for producing the composition of [1] or [2] above, which comprises reacting a compound represented by the following formula (11) with a crosslinking agent in the presence of orthophosphoric acid, and The orthophosphoric acid is removed from the obtained reaction product, and the crosslinking agent is selected from the group consisting of formaldehyde, a compound represented by the following formula (13), and a compound represented by the following formula (14).

[chemical formula 3]

(In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom, an allyl group, an alkyl group with 1 to 8 carbon atoms or an alkoxy group with 1 to 8 carbon atoms, Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent an alkoxy group or a halogen atom having 1 to 4 carbon atoms.) [4] The method for producing the composition according to the aforementioned [3], which further removes at least a part of the untreated compound from the aforementioned reaction product. Reactant. [5] The method for producing the composition according to [4] above, wherein the reaction product from which at least a part of the unreacted substances have been removed is distilled, and the evaporated components are recovered.

Invention effect According to the present invention, it is possible to provide a composition which is very useful as a raw material of a polymer material and the like, and a method for producing the same.

[composition] The composition of the present invention (hereinafter also referred to as "the present composition") contains a mixture of isomers of the compound represented by the following formula (1) (hereinafter also referred to as "compound 1").

[chemical formula 4]

In formula (1), R ¹ , R ² and R ³ each independently represent a hydrogen atom, an allyl group, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms. Each of the alkyl group and the alkoxy group may be linear or branched. X represents a group represented by the following formula (2), a group represented by the following formula (3), or a group represented by the following formula (4).

[chemical formula 5]

The isomer mixture of compound 1 is composed of two or more isomers (structural isomers) in which R ¹ , R ² , R ³ and X in formula (1) are the same. As a mixture of isomers of compound 1, the present composition may contain only one kind, or may contain a mixture of two or more kinds of which R ¹ , R ² , R ³ and X are different in at least one. The isomer mixture of compound 1 typically includes two or more isomers with different X-bonding positions of the two benzene rings (benzene rings bonded with OH and CHO) in formula (1). Such isomers can be exemplified: compounds in which the X-bonding position of one benzene ring and the X-bonding position of the other benzene ring are p-positions relative to the OH-bonding position (hereinafter also referred to as "p,p'-materials) ”); a compound where the X-bonding position of one benzene ring is o-position relative to the OH-bonding position, and the X-bonding position of the other benzene ring is p-position relative to the OH-bonding position (hereinafter also referred to as “o,p -物”); a compound in which the X-bonding position of one benzene ring and the X-bonding position of the other benzene ring are o-positions relative to the OH-bonding position (hereinafter also referred to as “o,o’-thing”). For example, when X is a group (methylene group) shown in the aforementioned formula (2), the p,p'-material, o,p-material, o,o'-material are as follows formula (1a), the following formula ( 1b), shown in the following formula (1c).

[chemical formula 6]

Relative to the total molar amount of the isomer mixture, the isomer mixture preferably contains 50-90% of p,p'-, 10-50% of o,p-, 0-20% of o,o' - things. When the respective ratios of the p,p'-material, o,p-material, and o,o'-material are within the aforementioned ranges, the workability and the solvent solubility of the polyimide obtained by using this composition are more excellent. Containing 0% of o,o'-matter means not containing o,o'-matter. The isomer ratio (composition ratio) constituting the isomer mixture was measured by ¹³ C-NMR (nuclear magnetic resonance analysis). In addition, % of composition ratio is mole %.

When X is a group represented by the aforementioned formula (2), relative to the total molar amount of the isomer mixture, the isomer mixture preferably comprises 50-80% p,p'-, 15-40% o,p-materials, 1~10% of o,o'-materials, more preferably 55~75% of p,p'-materials, 20~35% of o,p-materials, 2~8% The o,o'-thing.

When X is a group represented by the aforementioned formula (3), relative to the total molar amount of the isomer mixture, the isomer mixture preferably comprises 50-85% p,p'-, 15-35% The o,p-substances preferably contain 55-80% of p,p'-substances and 20-30% of o,p-substances.

When X is a group represented by the aforementioned formula (4), relative to the total molar amount of the isomer mixture, the isomer mixture preferably comprises 60-90% p,p'-, 10-35% The o,p-substances preferably contain 65-85% of p,p'-substances and 15-30% of o,p-substances.

The content of the isomer mixture of compound 1 is based on the ratio of the peak area of the isomer mixture of compound 1 measured by gel permeation chromatography (GPC) to the total peak area, preferably more than 80 area%, 85 Area % or more is better, 90 area % or more is more preferable, 95 area % is more preferable, and area % or more is the best. The upper limit of the content of the isomer mixture of Compound 1 is not particularly limited, and may be 100 area %. The ratio of the peak area of the isomer mixture of compound 1 to the total peak area can be 80-100 area %, can be 85-100 area %, can be 90-100 area %, can be 95-100 area %, can be 99~100 area%. GPC measurement conditions are as described in Examples described later.

This composition may further contain other components other than the compound 1 isomer mixture. Examples of other components include unreacted raw materials (compound represented by formula (11) and crosslinking agent described later) used in the synthesis of the isomer mixture of Compound 1, and when synthesizing the isomer mixture of Compound 1. High molecular weight by-products, etc. As the high molecular weight substance, for example, three or more molecules of the compound represented by the formula (11) are bonded through X.

〔Manufacturing method of the composition〕 This composition can be manufactured by the following manufacturing method, for example. A method for producing a composition, in the presence of orthophosphoric acid, reacting the compound represented by the following formula (11) (hereinafter also referred to as "saloxals") and a crosslinking agent, and removing the aforementioned orthophosphoric acid from the obtained reaction product, Wherein the crosslinking agent is selected from formaldehyde, compounds represented by the following formula (13) (hereinafter also referred to as "xylenes") and compounds represented by the following formula (14) (hereinafter also referred to as "extended biphenyls") formed group.

[chemical formula 7]

In the formula (11), R ¹ , R ² and R ³ have the same meaning as above. In formulas (13) and (14), Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent an alkoxy group or a halogen atom having 1 to 4 carbon atoms. The alkoxy group may be linear or branched. Examples of the halogen atom include chlorine atom, bromine atom and the like.

As for the willoxals, salicaldehyde (another name: 2-hydroxybenzaldehyde) is preferable from the standpoint that the remaining raw materials after the reaction can be easily removed and recovered.

Xylenes can be exemplified by 4,4'-, 2,2'-, 2,4-of bis(alkoxymethyl)xylene, 4,4' of bis(halogenated methyl)xylene -things, 2,2'-things, 2,4-things, etc. Among them, the 4,4'-product of bis(alkoxymethyl)xylene is suitable from the viewpoint of relatively low cost and good reactivity with salicillals, that is, 4,4'-bis (Alkoxymethyl)xylene.

Extended biphenyls can be exemplified by 4,4'-, 2,2'-, 2,4-of bis(alkoxymethyl)biphenyl, 4,4-of bis(halogenated methyl)biphenyl '-things, 2,2'-things, 2,4-things, etc. Among them, the 4,4'-bis(alkoxymethyl)biphenyl is preferable from the viewpoint of relatively low cost and good reactivity with salicillaldehydes, that is, 4,4'-bis (Alkoxymethyl)biphenyl.

In the presence of orthophosphoric acid, if the willoxal is reacted with a cross-linking agent, two molecules of willal will be cross-linked by the cross-linking agent, and a mixture of isomers of compound 1 will be generated. If formaldehyde is used as a cross-linking agent, X in compound 1 will be the group represented by the aforementioned formula (2). If xylenes are used as the crosslinking agent, X in compound 1 will be the group represented by the aforementioned formula (3). If extended biphenyls are used as the crosslinking agent, X in compound 1 will be the group represented by the aforementioned formula (4). When one type of salicaldehyde is used and any one type of crosslinking agent selected from formaldehyde, xylene type, and biphenylene type is used, a composition containing one type of compound 1 isomer mixture is obtained. If R ¹ , R ² and R ³ have at least one of different willowals or two or more cross-linking agents among formaldehyde, xylenes and biphenyls, then a compound containing 2 A composition of more than one isomer mixture of compound 1. In addition, Y1 ^{and Y2} of the xylenes are dissociated during the reaction, so even if either of ^Y1 and ^Y2 or two or more different xylenes are used in combination, a compound 1 containing one compound 1 can be obtained. Composition of a mixture of isomers. The same applies to extended biphenyls.

Orthophosphoric acid functions as a catalyst in the reaction between salicillals and crosslinking agents. When orthophosphoric acid is used as a catalyst, compared with the case of using other acid catalysts, it is possible to suppress the reaction of the generated compound 1 with the crosslinking agent to by-produce high molecular weight substances. Since the cross-linking agent can be selectively reacted with the salicillals, the yield can be improved.

The reaction between willoxals and cross-linking agents can also be carried out in the presence of water. Water can be added to the reaction system alone, or it can be mixed with the crosslinking agent or orthophosphoric acid first, and then added to the reaction system in the form of crosslinking agent aqueous solution or orthophosphoric acid aqueous solution.

Formaldehyde-based aqueous solution or solid can be used. The concentration of formaldehyde in the aqueous solution may be, for example, 30 to 50% by mass (50% by mass, 37% by mass, etc.). The solid formaldehyde concentration can be, for example, 70-92% by mass (86% by mass, 92% by mass, etc.). Because the reaction speed is fast and the yield increases when the moisture is low, 92% by mass of formaldehyde is preferred.

The molar ratio of cross-linking agent to salicillals (cross-linking agent/saloxals) is preferably 0.05-0.80, more preferably 0.20-0.60. Therefore, the amount of the crosslinking agent is preferably 0.10 to 1.60 mol, more preferably 0.40 to 1.20 mol, based on 2 mol of salicaldehyde. If the ratio of the cross-linking agent to the salicillals is too low, the residual salicinals may increase and the yield may decrease. If the ratio of the crosslinking agent is too high, a large amount of high molecular weight substances may be by-produced and the yield of the isomer mixture of Compound 1 may decrease.

The amount of orthophosphoric acid is preferably 1.0 to 30.0% by mass, more preferably 5.0 to 15.0% by mass relative to the salicillals. If the amount of orthophosphoric acid is larger than the upper limit of this range, the formyl groups of salicillals may react and the target product may not be obtained. If the amount of orthophosphoric acid is less than the lower limit of this range, the reaction rate may be slowed down and the unreacted crosslinking agent may remain.

The temperature (reaction temperature) at which the willoxals and the crosslinking agent react is preferably 50 to 200°C, more preferably 90 to 180°C. When the reaction temperature is too low, the reaction may not proceed. If the reaction temperature is too high, there is a possibility that the formyl group of the salicillals will react and the target product may not be obtained. The time (reaction time) which makes salicillals and a crosslinking agent react can be 1-30 hours, for example.

By removing orthophosphoric acid from the reaction product obtained after reacting salicillals with the crosslinking agent, it is possible to suppress further reaction of the produced compounds 1 with each other, and decrease in the purity of the compound 1, etc. The method of removing orthophosphoric acid is, for example, a method of adding a base to the reaction product to neutralize orthophosphoric acid, and then washing the reaction product with water (removing orthophosphate). The base should just be able to neutralize orthophosphoric acid, and examples thereof include triethylamine, sodium hydroxide, potassium hydroxide, and the like. The reaction product after removing orthophosphoric acid can be used as this composition as it is.

After orthophosphoric acid is removed, at least a part of unreacted substances are removed from the reaction product if necessary. In this way, the content of the isomer mixture of compound 1 can be increased. A method of removing at least a part of unreacted substances may, for example, be a method of concentrating the reaction product. Salicaldehydes, formaldehyde, and xylenes are removed from the reaction product by volatilization when the reaction product is concentrated. Concentration can be performed using conventional methods. When the reaction product contains water, at least a part of water can also be removed from the reaction product by concentration (dehydration). A reaction product obtained by removing at least a part of unreacted substances can also be used as the present composition as it is.

After removing at least a part of unreacted substances as described above, it is preferable to further distill the reaction product and recover the evaporated components. Once the reaction product was distilled, the isomer mixture of Compound 1 was evaporated and distilled from the evaporator; on the other hand, the high molecular weight material was not evaporated and became the bottom component. Therefore, the isomer mixture of Compound 1 can be separated from high molecular weight substances by distillation to increase the content (purity) of the isomer mixture of Compound 1. The obtained evaporated components can be directly used as the present composition.

Examples of distillation methods include vacuum distillation, molecular distillation, and steam distillation. Among them, vacuum distillation is preferable from the viewpoint of obtaining high-purity compound 1, and among vacuum distillations, thin-film distillation is preferable from the viewpoint of obtaining compound 1 in high yield.

The distillation temperature (heating medium temperature) of thin film distillation is preferably 200~300°C, more preferably 210~270°C. If the distillation temperature is too low, the isomer mixture of compound 1 may not evaporate and the yield may decrease. If the distillation temperature is too high, even the impurity will be evaporated, and the content of the isomer mixture of Compound 1 in the evaporated fraction may decrease.

The vacuum degree of thin film distillation is preferably below 20mmHg, preferably below 10mmHg. If the degree of vacuum is too high, the mixture of isomers of compound 1 will not be distilled. The degree of vacuum may be 0 mmHg, but if the degree of vacuum is low, even impurities may be distilled and the content of the isomer mixture of Compound 1 in the evaporated fraction may decrease, so it is preferably 3 mmHg or more. The degree of vacuum can be 0~20mmHg or 3~10mmHg.

Since the present composition described above contains Compound 1 in the form of a mixture of multiple isomers, it has low crystallinity and excellent solvent solubility. Therefore, it is easy to prepare a solution for modification and other operations, and it has excellent workability.

Since this composition contains the compound 1 with abundant reactive formyl groups, it can be modified in various ways through oxidation and reduction reactions. Also, by utilizing the two formyl groups or two phenolic hydroxyl groups possessed by compound 1, polymer materials, dicoumarin compounds, bissalicylic acid, alkoxy compounds, etc. can be produced. For example, this composition or its modified product can be used as a monomer for forming polyimide, epoxy resin, polyester resin, polycarbonate resin, phenoxy resin, and the like. For example, polyimine is obtained by reacting this composition with diamine. The phenolic hydroxyl groups in this composition can be modified with epoxy to form epoxy compounds. The composition can be reacted with polycarboxylic acid to form polyester resin. The formyl group in this composition is oxidized to carboxyl group, which can form polyester resin with polyol compound.

Conventionally, polyimides using 4,4'-methylenebissial are insoluble in polar solvents such as N-methylpyrrolidone because of their high crystallinity. Therefore, polyimine cannot be synthesized without using a specific solvent with strong toxicity and irritation such as m-cresol, and even if it is synthesized, it is difficult to obtain a high molecular weight product with a weight average molecular weight of 20,000 or more. The polyimine obtained by using the composition has excellent solvent solubility, even in polar solvents such as N-methylpyrrolidone and the like, it can be fully dissolved. Therefore, by using this composition, it becomes possible to synthesize|combine the high molecular weight polyimide of 20000 or more weight average molecular weights, without using m-cresol etc., and using a polar solvent, for example. Therefore, this composition is very useful as a raw material of polyimide. In addition to polyimides, there are other resins (such as polyester resins, polycarbonate resins, phenoxy resins) that have problems due to crystallinity. These resins are also in the same situation as polyimine, and the problems caused by crystallinity can be solved by using this composition as a monomer.

Example Hereinafter, the present invention will be further described in detail using examples, but the present invention is not limited by the examples. In each of the following examples, "parts" means "parts by mass" unless otherwise specified. "Purity" means the ratio (area %) of the peak area of the isomer mixture of Compound 1 measured for the composition by GPC to the total peak area.

(Measuring method) The measuring methods of the purity, the composition ratio of the isomer mixture, and the monomer consumption rate in each example are as follows. <Purity, monomer consumption rate> GPC measurement was performed under the following measurement conditions. GPC measuring device: Tosoh Corporation make, HLC8120GPC. Pipe string: manufactured by Tosoh Corporation, TSKgel G3000H+G2000H+G2000H. <Composition ratio> It measured using the following NMR apparatus. NMR measurement device: ECZ500R ¹³ C measurement mode manufactured by JEOL RESONANCE. When X in the aforementioned formula (1) is a group represented by the aforementioned formula (2), the structures of the p,p'-material, o,p-material, and o,o'-material are as described above. When X in the aforementioned formula (1) is a group shown in the aforementioned formula (3) or (4), let the compound with the structure shown in the following formula (1d) be a p,p'-material, with the following formula (1e ) The compound with the structure shown in ) is an o,p-material, find the composition ratio.

[chemical formula 8]

(Example 1) <Synthesis of crude methylenebissalaldehyde through the reaction of 2-hydroxybenzaldehyde and formaldehyde; molar ratio 0.30> Put 2-hydroxybenzaldehyde in a 1L reaction vessel equipped with a thermometer, a stirrer, and a cooling tube 244.2 g (2.0 mol) of benzaldehyde, 19.6 g (0.60 mol) of 92% by mass formaldehyde, and 24.4 g of 85% by mass orthophosphoric acid aqueous solution were heated up to 100° C. and reacted for 2 hours. Next, after heating up to 140 degreeC, carrying out dehydration, reaction was performed for 3 hours. After cooling the reaction solution to 80° C., orthophosphoric acid was neutralized with triethylamine. Then, the neutralized reaction product was washed with water and concentrated to obtain crude methylenebissial-1. GPC was performed on the reaction product after neutralization, and the result was that the purity of methylenebissial was 75.4%, and the consumption rate of 2-hydroxybenzaldehyde monomer was 65.78%. The GPC chart at this time is shown in FIG. 1 . The composition ratio of the isomer mixture was determined by ¹³ C-NMR on the crude methylene bissalxaldehyde-1, and the result was that the aforementioned composition ratio was 69.58% of p,p'-methylene bissalxal, 69.58% of o,p-methylene Bissial 27.06%, o, o'-methylene bissal 3.36%.

<Distillation> The heating medium at 220°C was circulated through the thin-film still (heating conduction surface 0.068m ² , internal condenser conduction surface 0.019m ² , with glass-containing polytetrafluoroethylene (PTFE) scraper) through the heating sleeve, and The internal condenser circulates heated water at 150°C, and the rotation speed of the rotor is set at 350rpm, and it operates under a vacuum degree of 1~5mmHg. The thin-film distiller in this state continuously supplied the crude methylenebisisal-1 at 600g/hr for 1 hour, and continuously extracted the evaporated component and the bottom component to obtain the methylenebissaloxal as the evaporated component (distillate) Aldehyde-1. GPC was performed on methylene bissal-1, and the result was that the purity of methylene bissal was 99.45%. Also, the composition ratio of the isomer mixture was measured by ¹³ C-NMR. As a result, the above composition ratio was 68.48% of p,p'-methylene bissal, 28.36% of o,p-methylene bissal, and o, o'-methylenebissial 3.16%.

(Example 2) <Synthesis of crude methylenebissalaldehyde through the reaction of 2-hydroxybenzaldehyde and formaldehyde; molar ratio 0.40> Put 2-hydroxybenzaldehyde in a reaction vessel with a capacity of 1L equipped with a thermometer, a stirrer, and a cooling tube 244.2 g (2.0 mol) of benzaldehyde, 26.1 g (0.80 mol) of 92% by mass formaldehyde, and 24.4 g of 85% by mass orthophosphoric acid aqueous solution were heated up to 100° C. and reacted for 2 hours. Next, after heating up to 140 degreeC, carrying out dehydration, reaction was performed for 3 hours. After cooling the reaction solution to 80° C., orthophosphoric acid was neutralized with triethylamine. Then, the neutralized reaction product was washed with water and concentrated to obtain crude methylenebissial-2. GPC was performed on the neutralized reaction product, and the result was that the purity of methylenebissial was 72.39%, and the consumption rate of 2-hydroxybenzaldehyde monomer was 80.88%. The GPC chart at this time is shown in FIG. 2 . Using ¹³ C-NMR to measure the composition ratio of the isomer mixture of crude methylene bissalxal-2, the result is that the aforementioned composition ratio is 69.88% of p,p'-methylene bissalxal, o,p-methylene Bissial 26.52%, o,o'-methylene bissal 3.59%.

＜Distillation＞ Flow the heating medium at 220°C through the heating sleeve of the thin film still (heating conduction surface 0.068m ² , internal condenser conduction surface 0.019m ² , with glass-containing PTFE scraper), and 150°C through the internal condenser Then add warm water, set the rotation speed of the rotor to 350rpm, and operate under the vacuum degree of 1~5mmHg. The thin-film distiller in this state continuously supplies the crude methylenebisisal-2 at 600g/hr for 1 hour, continuously extracts the evaporated component and the bottom component, and obtains methylenebissaloxal as the evaporated component (distillate) Aldehyde-2. GPC was performed on methylene bissal-2, and the result was that the purity of methylene bissal was 99.41%. In addition, the composition ratio of the isomer mixture was measured by ¹³ C-NMR. As a result, the above composition ratio was 69.68% of p,p'-methylenebissal, 27.42% of o,p-methylenebissal, and o, o'-methylenebissial 2.90%.

(Example 3) <Synthesis of crude methylenebissalaldehyde through the reaction of 2-hydroxybenzaldehyde and formaldehyde; molar ratio 0.50> Put 2-hydroxybenzaldehyde in a reaction vessel with a capacity of 1 L equipped with a thermometer, a stirrer, and a cooling tube 244.2 g (2.0 mol) of benzaldehyde, 32.6 g (1.00 mol) of 92% by mass formaldehyde, and 24.4 g of 85% by mass orthophosphoric acid aqueous solution were heated up to 100° C. and reacted for 2 hours. Next, after heating up to 140 degreeC, carrying out dehydration, reaction was performed for 3 hours. After cooling the reaction solution to 80° C., orthophosphoric acid was neutralized with triethylamine. Then, the neutralized reaction product was washed with water and concentrated to obtain crude methylenebissial-3. GPC was performed on the neutralized reaction product, and the result was that the purity of methylenebissalaldehyde was 69.67%, and the consumption rate of 2-hydroxybenzaldehyde monomer was 89.30%. The GPC chart at this time is shown in FIG. 3 . The composition ratio of the isomer mixture was determined by ¹³ C-NMR on the crude methylene bissalxaldehyde-3, and the result was that the aforementioned composition ratio was 71.10% of p,p'-methylene bissalxal, 71.10% of o,p-methylene Bissial 25.16%, o,o'-methylene bissal 3.74%.

＜Distillation＞ Flow the heating medium at 220°C through the heating sleeve of the thin film still (heating conduction surface 0.068m ² , internal condenser conduction surface 0.019m ² , with glass-containing PTFE scraper), and 150°C through the internal condenser Then add warm water, set the rotation speed of the rotor to 350rpm, and operate under the vacuum degree of 1~5mmHg. The thin-film distiller in this state continuously supplies the crude methylenebisisal-2 at 600g/hr for 1 hour, continuously extracts the evaporated component and the bottom component, and obtains methylenebissaloxal as the evaporated component (distillate) Aldehyde-3. GPC was performed on methylene bissal-3, and the result was that the purity of methylene bissal was 99.39%. Also, the composition ratio of the isomer mixture was measured by ¹³ C-NMR. As a result, the above composition ratio was 71.08% of p,p'-methylenebissal, 25.11% of o,p-methylenebissal, o, o'-methylenebissal 3.81%.

(Example 4) <Synthesis of crude xylylbissalaldehyde through the reaction of 2-hydroxybenzaldehyde and p-xylylene dimethyl ether; molar ratio 0.40> 1L capacity in a thermometer, agitator, and cooling tube 244.2 g (2.0 mol) of 2-hydroxybenzaldehyde and 24.4 g of 85 mass % orthophosphoric acid aqueous solution were placed in the reaction container, and it heated up to 160 degreeC. Next, 132.8 g (0.8 mol) of p-xylylene dimethyl ether was added dropwise over 3 hours. Then remove the by-product methanol to the outside of the system. Then, the reaction was carried out for 2 hours while maintaining 160°C, and after confirming that the distillation of by-produced methanol was completed, it was cooled to 80°C. Orthophosphoric acid was then neutralized with triethylamine. Then the neutralized reaction product was washed with water and concentrated to obtain crude xylylbissal. GPC was performed on the neutralized reaction product, and the result was that the purity of xylylbissal was 82.37%, and the consumption rate of 2-hydroxybenzaldehyde monomer was 93.35%. The GPC chart at this time is shown in FIG. 4 . The composition ratio of the isomer mixture was determined by ¹³ C-NMR on crude xylyl bissalxaldehyde, and the result was that the aforementioned composition ratio was 73.43% of p,p'-xylyl bissalxaldehyde, o,p-xylyl bissaloxal Aldehyde 26.57%.

＜Distillation＞ Flow the heating medium at 265°C through the heating sleeve of the thin film still (heating conduction surface 0.068m ² , internal condenser conduction surface 0.019m ² , with glass-containing PTFE scraper), and 150°C through the internal condenser Then add warm water, set the rotation speed of the rotor to 350rpm, and operate under the vacuum degree of 1~5mmHg. The thin-film distiller in this state continuously supplied the crude xylylbisalxaldehyde at 600 g/hr for 1 hour, continuously extracted the evaporated component and the bottom component, and obtained xylylizedisalxaldehyde as the evaporated component (distillate). GPC was performed on p-xylylbissal, and the result was that the purity of xylylbissal was 99.81%. Also, the composition ratio of the isomer mixture was measured by ¹³ C-NMR. As a result, the composition ratio was 71.41% of p,p'-xylyldisal, and 28.59% of o,p-xylyldisal.

(Example 5) <Synthesis of extended biphenyl bissalaldehyde through the reaction of 2-hydroxybenzaldehyde and 4,4-bismethoxymethylbiphenyl; molar ratio 0.30> In a room equipped with a thermometer, a stirrer, and a cooling tube 244.2 g (2.0 moles) of 2-hydroxybenzaldehyde and 24.4 g of an 85% by mass orthophosphoric acid aqueous solution were placed in a reaction container with an inner capacity of 1 L, and the temperature was raised to 160°C. Next, 145.2 g (0.6 mol) of 4,4-bismethoxymethylbiphenyl was dripped over 3 hours. Then remove the by-product methanol to the outside of the system. Then, the reaction was carried out for 2 hours while maintaining 160°C, and after confirming that the distillation of by-produced methanol was completed, it was cooled to 80°C. Orthophosphoric acid was then neutralized with triethylamine. Then the neutralized reaction product was washed with water and concentrated to obtain biphenyl bissal. GPC was performed on the neutralized reaction product, and the result was that the purity of biphenyl bissalaldehyde was 91.39%, and the consumption rate of 2-hydroxybenzaldehyde monomer was 97.25%. The GPC chart at this time is shown in FIG. 5 . The composition ratio of the isomer mixture was measured by ¹³ C-NMR p-extended bissalxaldehyde, and the result was that the aforementioned composition ratio was 81.45% of p,p'-extended bissalxaldehyde, o,p-extended bissalxaldehyde Bissial 18.55%.

(Comparative Example 1) <Using the reaction of 2-hydroxybenzaldehyde and formaldehyde to synthesize crude methylene bissalaldehyde; reacting with p-toluenesulfonic acid; molar ratio 0.40> Reaction in a capacity of 1L equipped with a thermometer, agitator, and cooling tube 244.2 g (2.0 mol) of 2-hydroxybenzaldehyde, 32.6 g (1.00 mol) of 92% by mass formaldehyde, and 12.2 g of p-toluenesulfonic acid were placed in the container, and the reaction was carried out for 2 hours after heating up to 100° C. Next, after heating up to 120 degreeC, carrying out dehydration, reaction was performed for 3 hours. After cooling the reaction liquid to 80° C., p-toluenesulfonic acid was neutralized with triethylamine. Then, the neutralized reaction product was washed with water and concentrated to obtain crude methylenebissial. GPC was performed on the neutralized reaction product, and the result was that the purity of methylenebissalaldehyde was 49.55%, and the consumption rate of 2-hydroxybenzaldehyde monomer was 86.57%. The GPC chart at this time is shown in FIG. 6 . The composition ratio of the isomer mixture was determined by ¹³ C-NMR on crude methylene bissalxaldehyde, and the result was that the aforementioned composition ratio was p,p'-methylene bissalxaldehyde 71.10%, o,p-methylene bissalxaldehyde Aldehyde 25.16%, o,o'-methylenebissial 3.74%.

From the comparison of Fig. 2 and Fig. 6, it can be confirmed that compared with Example 2, which performed the same operation except for using orthophosphoric acid, Comparative Example 1 using p-toluenesulfonic acid as a catalyst produced more high-molecular-weight substances, and methylene The purity of double salicaldehyde is low.

(Comparative Example 2) <Synthesis of crude xylylbissalaldehyde through the reaction of 2-hydroxybenzaldehyde and p-xylylene dimethyl ether; reaction with p-toluenesulfonic acid; molar ratio 0.40> Equipped with a thermometer, a stirrer, 244.2 g (2.0 mol) of 2-hydroxybenzaldehyde and 12.2 g of p-toluenesulfonic acid were placed in a reaction vessel with a capacity of 1 L inside the cooling tube, and the temperature was raised to 160°C. Next, 132.8 g (0.8 mol) of p-xylylene dimethyl ether was added dropwise over 3 hours. Then remove the by-product methanol to the outside of the system. Then, the reaction was carried out for 2 hours while maintaining 160°C, and after confirming that the distillation of by-produced methanol was completed, it was cooled to 80°C. The p-toluenesulfonic acid was then neutralized with triethylamine. Then the neutralized reaction product was washed with water and concentrated to obtain crude xylylbissal. GPC was performed on the neutralized reaction product, and the result was that the purity of xylylbisal was 22.94%, and the consumption rate of 2-hydroxybenzaldehyde monomer was 86.79%. The GPC chart at this time is shown in FIG. 7 . The composition ratio of the isomer mixture was determined by ¹³ C-NMR on crude xylyl bissalxaldehyde, and the result was that the aforementioned composition ratio was 61.34% of p,p'-xylyl bissalxaldehyde, o,p-xylyl bissaloxal Aldehyde 38.66%.

From the comparison of Fig. 4 and Fig. 7, it can be confirmed that compared with Example 4, which performed the same operation except for using orthophosphoric acid, Comparative Example 2 using p-toluenesulfonic acid as a catalyst produced more high molecular weight substances, and xylylene The purity of double salicaldehyde is low.

(Comparative Example 3) <Synthesis of biphenyl bissalaldehyde via reaction of 2-hydroxybenzaldehyde and 4,4-bismethoxymethylbiphenyl; reaction with p-toluenesulfonic acid; molar ratio 0.30> in equipment 244.2 g (2.0 moles) of 2-hydroxybenzaldehyde and 12.2 g of p-toluenesulfonic acid were placed in a reaction vessel with a capacity of 1 L inside a thermometer, a stirrer, and a cooling tube, and the temperature was raised to 160°C. Next, 145.2 g (0.8 mol) of 4,4-bismethoxymethylbiphenyl was dripped over 3 hours. Then remove the by-product methanol to the outside of the system. Then, the reaction was carried out for 2 hours while maintaining 160°C, and after confirming that the distillation of by-produced methanol was completed, it was cooled to 80°C. The p-toluenesulfonic acid was then neutralized with triethylamine. Then the neutralized reaction product was washed with water and concentrated to obtain biphenyl bissal. GPC was performed on the neutralized reaction product, and the result was that the purity of biphenyl bissalaldehyde was 27.65%, and the consumption rate of 2-hydroxybenzaldehyde monomer was 87.50%. The GPC chart at this time is shown in FIG. 8 . The composition ratio of the isomer mixture was determined by ¹³ C-NMR p-extended biphenyl bis-salaldehyde, and the result was that the aforementioned composition ratio was 78.12% of p,p'-extended bis-salxaldehyde, o,p-extended bis-salxaldehyde Bissial 21.88%.

From a comparison of Fig. 5 and Fig. 8, it can be confirmed that compared with Example 5, which performed the same operation except for using orthophosphoric acid, Comparative Example 3 using p-toluenesulfonic acid as a catalyst produced more high-molecular-weight substances, and extended biphenyl The purity of base bis-salaldehyde is low.

(reference example A) ＜Reaction of Methylenebissial and Diamine-1＞ Put 256.0 g (1.0 moles) of methylene bis-sialaldehyde and 553.1 g of N-methyl-2-pyrrolidone obtained in Example 1 into a reaction vessel with a capacity of 2 L equipped with a thermometer, a stirrer, and a cooling pipe. The methylenebisisal was dissolved at room temperature. Next, 89.2 g (0.45 moles) of 4,4-diaminodiphenylmethane and 59.5 g (0.55 moles) of m-phenylenediamine were added at the same temperature, and reacted for 2 hours. Next, the temperature was raised to 70° C., and the reaction was carried out for 3 hours. Subsequently, the water produced by the reaction was removed under vacuum to obtain polyimide varnish A. The weight average molecular weight (Mw) of the polyimide measured by GPC was 42391, and the number average molecular weight (Mn) was 15195. Mw and Mn of polyimide are measured using the following GPC measuring device and column and converted to standard polystyrene values (the same applies below). GPC measuring device: HLC8120GPC manufactured by Tosoh Corporation. Pipe string: manufactured by Tosoh Corporation, TSKgel G3000H+G2000H+G2000H.

(reference example B) ＜Reaction of Methylenebissial and Diamine-2＞ Put 256.0 g (1.0 moles) of methylenebissalaldehyde and 991.4 g of N-methyl-2-pyrrolidone obtained in Example 1 into a reaction vessel with a capacity of 2 L equipped with a thermometer, a stirrer, and a cooling pipe. The methylenebisisal was dissolved at room temperature. Next, 89.2 g (0.45 moles) of 4,4-diaminodiphenylmethane and 115.7 g (0.55 moles) of 4,4-diaminodicyclohexylmethane were added at the same temperature and allowed to react for 2 hours . Next, the temperature was raised to 70° C., and the reaction was carried out for 3 hours. Subsequently, the water produced by the reaction was removed under vacuum to obtain polyimide varnish B. The Mw of the polyimide measured by GPC was 42391, and the Mn was 16286.

(reference example C) ＜Reaction of xylylbissal and diamine＞ In a reaction vessel with a capacity of 2L equipped with a thermometer, a stirrer, and a cooling pipe, 346.0 g (1.0 moles) of xylylbissalaldehyde and 674.8 g of N-methyl-2-pyrrolidone obtained in Example 4 were placed. The xylylbisal was dissolved at room temperature. Next, 89.2 g (0.45 moles) of 4,4-diaminodiphenylmethane and 59.5 g (0.55 moles) of m-phenylenediamine were added at the same temperature, and reacted for 2 hours. Next, the temperature was raised to 70° C., and the reaction was carried out for 3 hours. Subsequently, the water produced by the reaction was removed under vacuum to obtain polyimide varnish C. The Mw of the polyimide measured by GPC was 34836, and the Mn was 12251.

(reference example D) ＜Reaction of extended biphenyl bisisal with diamine＞ In a reaction vessel with a capacity of 2L equipped with a thermometer, a stirrer, and a cooling pipe, 422.0 g (1.0 moles) of biphenyl bissalaldehyde and 778.5 g of N-methyl-2-pyrrolidone obtained in Example 5 were placed. The diphenylbisal was dissolved at room temperature. Next, 89.2 g (0.45 moles) of 4,4-diaminodiphenylmethane and 59.5 g (0.55 moles) of m-phenylenediamine were added at the same temperature, and reacted for 2 hours. Next, the temperature was raised to 70° C., and the reaction was carried out for 3 hours. Subsequently, the water produced by the reaction was removed under vacuum to obtain polyimide varnish D. The Mw of the polyimide measured by GPC was 59208, and the Mn was 15683.

(Refer to Comparative Example E) ＜Reaction of 4,4-methylenebissialal with diamine＞ Put 256.0 g (1.0 mol) of 4,4-methylenebissalaldehyde and 553.1 g of N-methyl-2-pyrrolidone into a reaction vessel with a capacity of 2 L equipped with a thermometer, a stirrer, and a cooling tube. Dissolve 4,4-methylenebissalaldehyde at room temperature. Next, 89.2 g (0.45 moles) of 4,4-diaminodiphenylmethane and 59.5 g (0.55 moles) of m-phenylenediamine were added at the same temperature to react, but about 30 minutes after the start of the reaction Resin precipitated. The precipitate is insoluble in ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, alcoholic solvents such as methanol, ethanol, and butanol, and all polar solvents such as tetrahydrofuran, N-methyl-2-pyrrolidone, and γ-butyrolactone , unable to make polyimide varnish.

Industrial availability This composition contains Compound 1 in high purity and has excellent workability (operability), and is extremely useful as a raw material for high-functional polymers.

Fig. 1 is the GPC graph measured for the reaction product after neutralization in Example 1. Fig. 2 is the GPC graph measured for the reaction product after neutralization in Example 2. Fig. 3 is the GPC graph measured for the reaction product after neutralization in Example 3. Fig. 4 is a GPC graph measured in Example 4 for the reaction product after neutralization. Fig. 5 is a GPC graph measured in Example 5 for the reaction product after neutralization. FIG. 6 is a GPC graph measured for the reaction product after neutralization in Comparative Example 1. FIG. Fig. 7 is a GPC graph measured for the reaction product after neutralization in Comparative Example 2. Fig. 8 is a GPC graph measured for the reaction product after neutralization in Comparative Example 3.

Claims (4)

A composition comprising a mixture of isomers of a compound represented by the following formula (1):

(In the formula, R ¹ , R ² and R ³ are each independently representing a hydrogen atom, an allyl group, an alkyl group with 1 to 8 carbon atoms or an alkoxy group with 1 to 8 carbon atoms, and X represents the following formula (2 ), the group represented by the following formula (3) or the group represented by the following formula (4))

The ratio of the peak area of the aforementioned isomer mixture measured by gel permeation chromatography to the total peak area is more than 80 area %, and relative to the total molar amount of the aforementioned isomer mixture, in the aforementioned formula (1) Among the two benzene rings, the ratio of the compound with the X-bonding position of one benzene ring and the X-bonding position of the other benzene ring at the p-position relative to the OH-bonding position is 50-90 mole %; the aforementioned formula ( Among the two benzene rings in 1), the X-bonding position of one benzene ring is o-position relative to the OH-bonding position, and the ratio of the compound whose X-bonding position is p-position relative to the OH-bonding position of the other benzene ring It is 10~50 mole %; Among the two benzene rings in the aforementioned formula (1), the X-bonding position of one benzene ring and the X-bonding position of the other benzene ring are respectively at the o-position relative to the OH-bonding position The ratio of the compound is 0~20 mol%. A method for producing a composition comprising a mixture of isomers of a compound represented by the following formula (1):

(In the formula, R ¹ , R ² and R ³ are each independently representing a hydrogen atom, an allyl group, an alkyl group with 1 to 8 carbon atoms or an alkoxy group with 1 to 8 carbon atoms, and X represents the following formula (2 ), the group represented by the following formula (3) or the group represented by the following formula (4)),

The production method is to react the compound represented by the following formula (11) with a cross-linking agent in the presence of orthophosphoric acid, and remove the above-mentioned orthophosphoric acid from the reaction product obtained. The cross-linking agent is selected from formaldehyde, the following formula The group formed by the compound represented by (13) and the compound represented by the following formula (14):

(In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom, an allyl group, an alkyl group with 1 to 8 carbon atoms or an alkoxy group with 1 to 8 carbon atoms, Y ¹ , Y ² , ^Y3 and ^Y4 each independently represent an alkoxy group or a halogen atom with 1 to 4 carbon atoms). The method for producing a composition according to claim 2, which further removes at least a part of unreacted substances from the aforementioned reaction product. The method for producing the composition according to claim 3, which distills the reaction product after removing at least a part of the aforementioned unreacted substances, and recovers the evaporated components.

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