TWI580667B - Method for preparing a diamine-dicarboxylic acid salt - Google Patents

Description

Preparation method of bisamine dicarboxylate

This invention relates to a process for the preparation of a bisamine dicarboxylate.

At present, nylon 6 (nylon 6) fiber has been widely used in daily life, such as clothing, home furnishings, or other fields. However, compared to nylon 66 (nylon 66), nylon 6 has a lower melting point, softening point, heat resistance, and mechanical strength than nylon 66. These unfavorable physical properties have long limited the development of nylon 6 downstream applications. The industry is attempting to produce differentiated nylon 6 by chemical synthesis, which increases the added value of nylon 6. However, in the current upgrading technology of nylon 6, it is still impossible to obtain a nylon 6 product having a high uniformity sequence distribution and a high melting point physical property. Therefore, the development of a novel polymer fiber or its precursor, which can improve the above-mentioned conventional technology, is urgently needed in the industry.

According to an embodiment of the present invention, the present invention discloses a method for preparing a bisamine dicarboxylate, comprising: providing a first solution, wherein the first solution comprises a compound having the structure represented by formula (I) and having formula (II) Reaction product of the compound of the structure shown

Wherein M is Na or K; m is an integer from 2 to 10; i is an integer from 1 to 5; j is an integer of 0 or 1-5; and, k is 0 or 1; a second solution is provided, wherein The second solution comprises a reaction product of a compound having the structure of the formula (III) and a mineral acid

Wherein n is an integer from 2 to 10; and the first solution is reacted with the second solution to obtain the bisamine dicarboxylate.

According to other embodiments of the present invention, there is provided a bisamine dicarboxylate salt which is a compound having the structure of formula (IV):

Wherein m is an integer of 2 to 10 and n is an integer of 2 to 10.

The above and other objects, features, and advantages of the present invention will become more apparent and understood.

The preparation method of the bisamine dicarboxylate salt of the invention is a mechanism of exchange reaction between organic/inorganic salts, and the dicarboxylate salt in the solution is directly mixed with the bisamine salt. The salt exchange reaction is carried out to form a diamine dicarboxylate and precipitate. Therefore, the preparation of the bisamine dicarboxylate salt of the present invention can prepare the diamine dicarboxylate salt in one pot, improve the yield of the diamine dicarboxylate salt and reduce the reaction complexity.

According to an embodiment of the present invention, the present invention provides a method for preparing a bisamine dicarboxylate, comprising: providing a first solution, wherein the first solution comprises a compound having the structure of the formula (I) and having the formula (II) Reaction product of a compound showing structure

Wherein M is Na or K; m is an integer from 2 to 10; i is an integer from 1 to 5; j is an integer of 0 or 1-5; and, k is 0 or 1; a second solution is provided, wherein The second solution comprises a reaction product of a compound having the structure of the formula (III) with a monoacid (for example, a mineral acid)

Wherein n is an integer of 2 to 10; and the acid is sulfuric acid, phosphoric acid, hydrochloric acid, hydrobromic acid, or hydroiodic acid; and the first solution is reacted with the second solution to obtain the diamine double Carboxyl salt.

According to an embodiment of the present invention, the compound having the structure represented by the formula (I) may be ,or a compound having the structure represented by formula (II) may be ,or Further, according to an embodiment of the present invention, the compound having the structure represented by the formula (II) may be ,or And a compound having the structure represented by formula (III) may be ,or

According to an embodiment of the present invention, the method for preparing the first solution may include placing a compound having the structure represented by the formula (I), a compound having the structure represented by the formula (II), and a solvent in a reaction bottle, and The reaction is carried out at 50 to 120 ° C for 6 to 24 hours under nitrogen (for example, at 85 to 110 ° C for 12 to 20 hours). In addition, the preparation method of the second solution may include dropping an aqueous acid solution (for example, an aqueous solution of sulfuric acid, an aqueous solution of phosphoric acid, an aqueous solution of hydrochloric acid, an aqueous solution of hydrobromic acid or an aqueous solution of hydroiodic acid) into the formula (III) under cooling in an ice water bath. An aqueous solution of the compound of the structure shown. Further, the first solution and the second solution may be reacted at 40 to 100 ° C (for example, a two-stage heating method), and the reaction time may be from 10 minutes to several hours to obtain the bisamine dicarboxylate. For example, the first solution and the second solution can be reacted at 70 to 90 ° C for 0.5 to 1.0 hours.

According to other embodiments of the present invention, there is provided a bisamine dicarboxylate salt which is a compound having the structure of formula (IV):

Wherein m is an integer of 2 to 10 and n is an integer of 2 to 10.

The preparation of the monomers and polymers of the present invention will be described below by way of the following examples to further clarify the technical features of the present invention.

Preparation of the first solution

Preparation Example 1 :

A reaction vial was provided, 1 equivalent of 6-aminohexanoic acid (ACA), and 1 equivalent of sodium hydroxide (NaOH) were added, and an appropriate amount of water was added as a solvent. After reacting for two hours, the reaction flask was heated to remove water to obtain a solid mixture. Next, the obtained solid mixture was placed in an oven and dried at 90 ° C for 12 hours to obtain a 6-aminohexanoic acid sodium salt (ACA-Na) solid. The reaction formula of the above reaction is as follows:

Next, 0.97 g (0.005 mole) of dimethyl terephthalate (DMT), 1.53 g (0.01 mole) of dried sodium 6-aminocaproate (ACA-Na), and 20 ml of ethylene Alcohol (ethylene glycol, EG), placed in a reaction bottle. Next, the reaction flask was slowly warmed to 85 to 90 ° C under nitrogen. After reacting for 12 hours, it was cooled to room temperature to obtain N,N'-bis(carboxypentyl)terephthalamide sodium salt (BCTM-Na). The first solution. The reaction formula of the above reaction is as follows:

Component Analysis: A portion of the first solution was taken and added dropwise to ethyl acetate to give a solid precipitate. After drying, the solid magnetic resonance (Nuclear Magnetic Resonance, NMR) and infrared (Infrared Spectrometry, IR) spectra were analyzed. The results were as follows: ¹ H NMR (D ₂ O, ppm): 7.1 (4H, phenyl-1,4- ), 3.3 (4H, aromatic-CON-CH ₂ -, ACA-Na), 2.1 (4H, aliphatic-CH ₂ -CO ₂ ^- , ACA-Na), 1.3-1.2 (12H, aliphatic, ACA).

IR (cm ^-1 ): 3308 (NH); 3300-2930 (broad, OH); 2858; 1700 (carbonyl of CO ₂ -); 1640 (amide); 1570-1350; 1300-800.

Preparation Example 2:

Next, 3.84 g (0.005 mole) of bis(2-hydroxyethyl)terephthalate (BHET), 1.53 g (0.01 mole) of dried sodium 6-aminocaproate Salt (ACA-Na), and 20 ml of ethylene glycol (EG) were placed in a reaction vial. Next, the reaction flask was slowly warmed to 85 to 90 ° C under nitrogen. After reacting for 12 hours, it was cooled to room temperature to obtain N,N'-bis(carboxypentyl)terephthalamide sodium salt (BCTM-Na). The first solution. The reaction formula of the above reaction is as follows:

Component Analysis: A portion of the first solution was taken and added dropwise to ethyl acetate to give a solid precipitate. After drying, the solid was subjected to nuclear magnetic resonance (NMR) and infrared (Infrared Spectrometry, IR) spectral analysis, and the results were the same as in Preparation 1.

Preparation of the second solution

Preparation Example 3:

1.16 g of hexamethylene daimine (HMDA) was dissolved in 5 g of H ₂ O and cooled in an ice water bath. Next, an aqueous solution of 0.98 g of sulfuric acid (dissolved in 10 g of water) was slowly added dropwise to the above hexamethylenediamine solution to obtain a second solution (having a hexamethylenediamine-sulfate ion compound). The reaction formula of the above reaction is as follows:

Preparation Example 4:

0.88 g of tetramethylene diamine was dissolved in 5 g of H ₂ O and cooled in an ice water bath. Next, 0.98 g of an aqueous solution of sulfuric acid (dissolved in 10 g of water) was slowly dropped into the above hexamethylenediamine solution to obtain a second solution (having a butanediamine-sulfate ion compound). The reaction formula of the above reaction is as follows:

Preparation of bisamine dicarboxylate

Example 1

The first solution obtained in Preparation Example 1 (containing 1 equivalent of BCTM-Na) was slowly added to the second solution obtained in Preparation Example 3 (containing 1 equivalent of hexamethylenediamine-sulfate ion compound). After complete addition, the resulting mixture was heated to 50 ° C for half an hour. Then, the temperature was raised to 90 ° C for 1 hour. After the reaction, the mixture was cooled to room temperature and added to an acetone solvent (the ratio of the solution to acetone was 1:10) to give a white precipitate. After filtration, the solid was washed with ethanol or water at least 3 times, and the obtained solid was dried to give the diamine dicarboxylate salt (I) in a total yield of 80.3%. The reaction formula of the above reaction is as follows:

The obtained bisamine dicarboxylate (I) was measured by Differential Scanning Calorimetry (DSC) to have a melting point (Tm) of = 204 °C. Next, the nuclear magnetic resonance (NMR) spectrum of the bisamine dicarboxylate (I) was measured, and the results were as follows: ¹ H NMR (D ₂ O, ppm): 7.1 (4H, benzene ring); 3.3 (4H, Aromatic amide is linked to CH ₂ ); 2.8 (4H, CH ₂ next to aliphatic amid); 2.1 (CH ₂ next to carbonyl); 1.4 to 1.2 ppm (CH ₂ on the aliphatic chain).

Example 2

The first solution obtained in Preparation Example 1 (containing 1 equivalent of BCTM-Na) was slowly added to the second solution obtained in Preparation Example 4 (containing 1 equivalent of butanediamine-sulfate ion compound). After complete addition, the resulting mixture was heated to 50 ° C for half an hour. Then, the temperature was raised to 90 ° C for 1 hour. After the reaction, the mixture was cooled to room temperature and added to an acetone solvent (the ratio of the solution to acetone was 1:10) to give a white precipitate. After filtration, the solid was washed with ethanol or water at least 3 times, and the obtained solid was dried to give a bisamine dicarboxylate salt (II) in a total yield of 80%. The reaction formula of the above reaction is as follows:

The nuclear magnetic resonance (NMR) spectra of the bisamine dicarboxylate (II) were measured and the results were as follows: ¹ HNMR (D ₂ O, ppm) = 7.1 (4H, benzene ring); 3.3 (4H, next to aromatic amide Linked to CH ₂ ); 2.8 (4H, CH ₂ next to aliphatic amid); 2.1 (CH ₂ next to carbonyl); 1.4 to 1.2 ppm (CH ₂ on the aliphatic chain).

Comparative Example 1:

A reaction vial was provided, 1 equivalent of 6-aminohexanoic acid (ACA), and 1 equivalent of sodium hydroxide (NaOH) were added, and an appropriate amount of water was added as a solvent. After reacting for two hours, the reaction flask was heated to remove water to obtain a solid mixture. Next, the obtained solid mixture was placed in an oven and dried at 90 ° C for 12 hours to obtain a 6-Aminohexanoic acid sodium salt (ACA-Na) solid. Next, 0.97 g (0.005 mole) of dimethyl terephthalate (DMT), 2.32 g (0.015 mole) of dried sodium 6-aminocaproate (ACA-Na), and 20 ml of ethylene Alcohol (ethylene glycol, EG), placed in a reaction bottle. Next, the reaction flask was slowly warmed to 85 to 90 ° C under nitrogen. After reacting for 14 hours, it was cooled to room temperature, and 20 ml of distilled water was added. After the solid was dissolved, it was slowly dropped into an aqueous sulfuric acid solution (0.1 M) to neutralize it to have a pH of 6.0. Then, it was allowed to stand at room temperature for 20 hours, and solids were observed to precipitate and precipitate. Next, the solid was collected, and the solid was placed in a glass bottle, washed and filtered with 3 times by weight of distilled water, and this washing and filtration step was repeated 5 times to remove a large amount of by-product sodium sulfate. Next, the washed solid was dried in an oven at 80 ° C to obtain N,N'-bis(carboxypentyl)terephthalamide (BCTM) in a yield of 62wt%. The reaction formula of the above reaction is as follows:

Next, a reaction flask was taken, and 14.2 g (0.036 mole) of N,N'-bis(carboxypentyl)terephthalamide (BCTM) and 4.2 g (o.036 mole) of hexamethylenediamine (HMDA) were added. And 60g of water. Next, the temperature of the reaction flask was raised to 85 ° C. After all the solids were dissolved, it was shown that BCTM and HMDA were sufficiently uniformly mixed. At this time, the water was removed by vacuum distillation to retain the solid product in the reaction flask. After filtration, the solid was washed with ethanol or water at least 3 times, and the obtained solid was dried to give a bisamine dicarboxylate salt (I) in a yield of 99% by weight (so the total yield of the bisamine dicarboxylate (I) was 61.3. %). The reaction formula of the above reaction is as follows:

The obtained bisamine dicarboxylate (I) was measured by Differential Scanning Calorimetry (DSC) to have a melting point (Tm) of =204 °C. Next, measuring the nuclear magnetic resonance of the diamine dicarboxylate (I) (Nuclear Magnetic Resonance, NMR) spectra were obtained in the same manner as in Example 1. When the monomer N,N'-bis(carboxypentyl)terephthalamide (BCTM) was synthesized in the first step of Comparative Example 1, a large amount of sodium sulfate was produced simultaneously (1 mol of CPL produced 1/2 mol). Sodium sulphate), the precipitate in the aqueous solution is a mixed colloid of BCTM and sodium sulfate. After the first washing and filtration with water, N,N'-bis(carboxypentyl)-p-benzene can be obtained with a small amount of small particles. A mixed colloid of methotrexate (BCTM) and sodium sulfate, which requires 4 times of repeated water washing and filtration to separate and purify N, N'-bis(carboxypentyl)terephthalamide (BCTM). . This process is difficult to filter, time-consuming and energy-consuming, and has high yield loss.

It can be seen from Comparative Example 1 that the bisamine dicarboxylate salt is prepared by using a separate two-stage process, so the process steps are complicated and the obtained bisamine dicarboxylate salt is lower (less than 62%); The preparation of the bisamine dicarboxylate salt can be carried out in a one-pot process, thereby greatly simplifying the process steps, and the resulting bisamine dicarboxylate has a higher yield (higher than 80%). In addition, since Comparative Example 1 was subjected to the second stage process, it was necessary to first purify the obtained N,N'-bis(carboxypentyl)terephthalamide (BC, BCTM). ) to avoid a large amount of by-products from subsequent reactions. Moreover, in order to purify N,N'-bis(carboxypentyl)terephthalamide (BCTM), it is necessary to wash and filter the obtained mixed colloid with a large amount of water (and repeat 4 times or more), and then separate and purify it. N,N'-bis(carboxypentyl)terephthalamide (BCTM); in view of the preparation method of the bisamine dicarboxylate of the present invention, since a one-pot process is used, The reaction intermediate needs to be purified.

Further, the bisamine dicarboxylate obtained by the method for producing a bisamine dicarboxylate according to the present application may be further subjected to a polymerization reaction (for example, heat polymerization or melt polymerization) to obtain a copolymer.

Example 3: Copolymer

The diamine dicarboxylate salt obtained in the examples was placed in a reaction flask, and the reaction flask was slowly heated to 150 ° C for 1 hour. Next, the reaction flask was warmed to 180 ° C and maintained for 2 hours. Next, the reaction flask was further heated to 200 ° C and maintained for 2 hours. Next, the reaction flask was warmed to 220 ° C and maintained for 2 hours. Finally, the reaction flask was warmed to 250 ° C and maintained for 4 hours. After cooling, BCTM-co-HMDA copolymer (light brownish white solid) was obtained (with Repeat unit).

The BCTM-co-HMDA copolymer was measured by a differential scanning calorimeter, and the melting temperature (Tm) was found to be 261 ° C (the highest peak), the glass transition temperature (Tg) was 75 ° C, and the relative viscosity (RV) was measured. It is 1.45, and the amount of hot water quenching drops to 0.5-2.1 wt%. The aromatic terephthalic acid and the aliphatic hexamethylene diamine and caprolactam in the copolymer are sequentially distributed to the copolymer. Therefore, the obtained copolymer has a good regular structure, a chemical structure and a reproducibility of physical properties, and a stable chemical structure and physical properties of the copolymer can be obtained. If applied to a plastic or spinning process, the variability of the product can be reduced and the product can be improved. Stability and reduced yarn breakage.

The preparation method of the bisamine dicarboxylate salt of the invention is a mechanism of exchange reaction between organic/inorganic salts, and the dicarboxylate salt in the solution is directly subjected to salt exchange reaction with the bisamine salt to form a BCTM-HMDA salt and precipitated. The synthesis of Comparative Example 1 is a mechanism of acid/base reaction, N,N'-bis(carboxypentyl)-p-xylamine (BCTM, dicarboxylic acid) and hexamethylenediamine (HMDA, diamine) in solution. The acid/base reaction is carried out to form a BCTM-HMDA salt and precipitate. Based on the above, the reaction process of the present application has no problem of BCTM formation and isolation purification as described in Comparative Example 1.

Although the embodiments of the present invention and its advantages are disclosed above, it should be understood that those skilled in the art can make modifications, substitutions, and refinements without departing from the spirit and scope of the invention. In addition, the scope of the present invention is not limited to the processes, machines, manufacture, compositions, devices, methods, and steps in the specific embodiments described in the specification. Any one of ordinary skill in the art can. The processes, machines, fabrications, compositions, devices, methods, and procedures that are presently or in the future are understood to be used in accordance with the present invention as long as they can perform substantially the same function or achieve substantially the same results in the embodiments described herein. Accordingly, the scope of the invention includes the above-described processes, machines, manufactures, compositions, devices, methods, and steps. In addition, the scope of each of the claims constitutes an individual embodiment, and the scope of the invention also includes the combination of the scope of the application and the embodiments.

Claims (7)

A method for preparing a bisamine dicarboxylate comprising: providing a first solution, wherein the first solution comprises a reaction product of a compound having a structure represented by the formula (I) and a compound having a structure represented by the formula (II) Wherein M is Na or K; m is an integer from 2 to 10; i is an integer from 1 to 5; j is an integer of 0 or 1-5; and, k is 0 or 1; a second solution is provided, wherein The second solution comprises a reaction product of a compound having the structure of the formula (III) and a mineral acid Wherein n is an integer of 2 to 10; and the first solution is reacted with the second solution to obtain the bisamine dicarboxylate, wherein the bisamine dicarboxylate is a compound having the structure represented by formula (IV) : Wherein m is an integer of 2 to 10 and n is an integer of 2 to 10. The method for preparing a bisamine dicarboxylate salt according to claim 1, wherein the compound having the structure represented by the formula (I) The method for preparing a bisamine dicarboxylate salt according to claim 1, wherein the compound having the structure represented by the formula (II) The method for preparing a bisamine dicarboxylate salt according to claim 1, wherein the compound having the structure represented by the formula (II) The method for preparing a bisamine dicarboxylate salt according to claim 1, wherein the compound having the structure represented by formula (III) is a compound The method for producing a bisamine dicarboxylate salt according to claim 1, wherein the inorganic acid is sulfuric acid, phosphoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, or a combination thereof. A bisamine dicarboxylate salt which is a compound having the structure of formula (IV): Wherein m is an integer of 2 to 10 and n is an integer of 2 to 10.