TWI558739B - Diamine-dicarboxylic acid salt, copolymer, and method for preparing the same - Google Patents

Description

Diamine dicarboxylate, copolymer and preparation method thereof

The present invention relates to a bisamine dicarboxylate, a copolymer and a process for the preparation thereof.

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. In addition, the melting point of nylon 6 modified product can not be higher than its cracking point, otherwise it is not easy to carry out subsequent processing.

According to an embodiment of the present invention, the present invention discloses a copolymer and a method of preparing the same. The copolymer is a reaction product of a composition comprising a first monomer and a second monomer, wherein the first monomer has a structure represented by formula (I) Wherein n is independently selected from a positive integer of 2-6; and the second monomer has a structure represented by formula (II) Among them, A is -(CH ₂ ) _m -, ,or m is a positive integer selected from 2-12, and R ¹ is H, a C _1-8 alkyl group, or a C _1-6 alkanol group.

According to another embodiment of the present invention, the present invention provides a bisamine dicarboxylate which is a compound having the structure represented by the formula (VI): Among them, D ²⁺ Or a combination of the above, i is independently selected from a positive integer of 2-6, n is independently selected from a positive integer of 2-6, and A is -(CH ₂ ) _m -, ,or And m is a positive integer selected from 2-12.

According to another embodiment of the present invention, the present invention provides a method for preparing a copolymer for forming the copolymer of claim 1, comprising: forming a composition into a diamine dicarboxylate; and The amine dicarboxylate is subjected to a heating reaction to obtain the copolymer, wherein the composition comprises a first monomer and a second monomer, wherein the first monomer has a structure represented by the formula (I) Wherein n is independently selected from a positive integer of 2-6; and the second monomer has a structure represented by formula (II) Among them, A is -(CH ₂ ) _m -, ,or m is a positive integer selected from 2-12, and R ¹ is H, a C _1-8 alkyl group, or a C _1-6 alkanol group.

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

According to an embodiment of the present invention, the present invention provides a copolymer which is a reaction product of a composition. The composition may comprise a first monomer and a second monomer, wherein the molar ratio of the first monomer to the second monomer may be between 1.2:1 and 1:1.2, for example 1: 1. Wherein, the first monomer may have the structure represented by formula (I) Wherein n is independently selected from a positive integer of 2-6; and the second monomer may have a structure represented by formula (II) Among them, A is -(CH ₂ ) _m -, ,or m is a positive integer selected from 2-12, and R ¹ is H, a C _1-8 alkyl group, or a C _1-6 alkanol group.

For example, the first monomer can be ,or And the second monomer can be ,or

According to an embodiment of the present invention, the copolymer may have a repeating unit of the structure shown in formula (IV) Wherein n is independently selected from a positive integer of 2-6, such as 2, 3, 4, 5, or 6, and A is -(CH ₂ ) _m -, ,or And m is a positive integer selected from 2-12, such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12.

According to an embodiment of the present invention, in order to adjust the structural rigidity and melting point value of the obtained copolymer, the composition further comprises a third monomer, wherein the third monomer has the structure represented by formula (III) Wherein i is independently selected from a positive integer of 2-6, such as 2, 3, 4, 5, or 6. According to an embodiment of the invention, the molar ratio of the first monomer to the third monomer may be between 1:9 and 9:1. In addition, increasing the molar ratio of the first monomer to the third monomer can lower the melting point of the obtained copolymer, or avoid the melting point of the copolymer being higher than the cracking temperature thereof, and it is easier to carry out the subsequent processing. Furthermore, the ratio of the molar number of the first monomer and the third monomer to the molar number of the second monomer may be between 1:1.2 and 1.2:1. The above copolymer may have a repeating unit of the structure represented by formula (IV) and formula (V) Wherein, i is independently selected from a positive integer of 2-6, n is a positive integer selected from 2-6, and A is -(CH ₂ ) _m -, ,or And m is a positive integer selected from 2-12.

According to an embodiment of the present invention, the present invention provides a bisamine dicarboxylate which is a compound having the structure represented by the formula (VI): Among them, D ²⁺ Or a combination of the above, i is independently selected from a positive integer of 2-6, and n is a positive integer independently selected from 2-6, for example, 2, 3, 4, 5, or 6, and A is -(CH ₂ ) _m -, ,or And m is a positive integer selected from 2-12, such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12.

According to an embodiment of the invention, the D ²⁺ can be and And versus The equivalent ratio may be from 1:99 to 99:1, such as from 1:9 to 9:1, or from 1:5 to 5:1.

According to an embodiment of the present invention, there is provided a method of producing a copolymer for forming the above copolymer. The preparation method comprises: reacting the composition at 60-120 ° C for 6-16 hours to form a diamine dicarboxylate; and subjecting the bisamine dicarboxylate to a heating reaction (for example, a melting process or a The solution process, for example, is carried out at 180-260 ° C for 4-16 hours, and the copolymer is obtained after drying. In one embodiment, the heating reaction is temperature-increased from a starting temperature (for example, 180 ° C), and is heated at a temperature of 5-20 ° C at intervals (for example, 30 minutes to 2 hours) to complete the reaction, and the reaction temperature is not More than 260 ° C. The foregoing composition comprises a first monomer and a second monomer, wherein the first monomer has the structure represented by formula (I) Wherein n is independently selected from a positive integer of 2-6; and the second monomer has a structure represented by formula (II) Among them, A is -(CH ₂ ) _m -, ,or m is a positive integer selected from 2-12, and R ¹ is H, a C _1-8 alkyl group, or a C _1-6 alkanol group. Furthermore, the composition may further comprise a third monomer, wherein the third monomer has the structure represented by formula (III) Among them, i is a positive integer selected independently from 2-6.

The preparation of the monomer, bisamine dicarboxylate, and copolymer of the present invention will be described below by way of the following examples and comparative examples to further clarify the technical features of the present invention.

Preparation of the first monomer

Preparation Example 1 : Preparation of Compound 1 by EDA and DMI

A reaction flask was provided, and 36 g of ethylene daimine (EDA), 19.4 g of dimethyl isophthalate (DMI), and 100 ml of ethylene glycol (EG) were added. Next, the reaction flask was slowly warmed to 90 ° C under nitrogen. After reacting for 24 hours, it was cooled to room temperature and filtered. Next, the solid was collected, and the obtained solid was washed with water and methanol, and the washed solid was dried in an oven at 80 ° C to obtain Compound 1. The reaction formula of the above reaction is as follows:

Nuclear Magnetic Resonance (NMR) spectroscopic analysis of Compound 1 gave the following results: ¹ HNMR (D ₂ SO ₄ , ppm) = 8.7 (1H, s); 8.5 (2H, s); 8.4 (1H, s) ;4.4-4.3 (4H, m); 4.0 (4H, m).

Preparation 2 : Preparation of Compound 1 by EDA and BHEI

A reaction flask was provided, and 6 g of ethylene daimine (EDA), 2.54 g of bis-hydroxylethyl isophthalate (BHEI), and 20 ml of ethylene glycol were added. (ethylene glycol, EG). Next, 0.06 g of sodium acetate was added to the reaction flask. Next, the reaction flask was slowly warmed to 110 ° C under nitrogen. After reacting for 24 hours, it was cooled to room temperature and filtered. Next, the solid was collected, and the obtained solid was washed with water and methanol, and the washed solid was dried in an oven at 80 ° C to obtain Compound 1. The reaction formula of the above reaction is as follows:

The compound 1 was subjected to nuclear magnetic resonance (NMR) spectral analysis, and the results were the same as in Preparation 1.

Preparation 3 : Preparation of Compound 2 with BDA and DMI

A reaction flask was provided, adding 22.6 g of 1,4-butylene diamine (BDA), 5 g of dimethyl isophthalate (DMI), and 100 ml of ethylene glycol (EG). ). Next, the reaction flask was slowly warmed to 90 ° C under nitrogen. After reacting for 24 hours, it was cooled to room temperature and filtered. Next, the solid was collected, and the obtained solid was washed with water and methanol, and the washed solid was dried in an oven at 80 ° C to obtain Compound 2. The reaction formula of the above reaction is as follows:

Nuclear Magnetic Resonance (NMR) spectroscopic analysis of Compound 2 gave the following results: ¹ HNMR (D ₂ SO ₄ , ppm) = 8.7 (1H, s); 8.5 (2H, s); 8.4 (1H, s) ; 4.4-4.3 (4H, m); 4.0 (4H, m); 2.5-2.4 (8H, m).

Preparation 4 : Preparation of Compound 3 with EDA and DMT

A reaction flask was provided, and 36 g of ethylene daimine (EDA), 19.4 g of dimethyl teraphthalate (DMT), and 100 ml of ethylene glycol (EG) were added. Next, the reaction flask was slowly warmed to 90 ° C under nitrogen. After reacting for 24 hours, it was cooled to room temperature and filtered. Next, the solid was collected, and the obtained solid was washed with water and methanol, and the washed solid was dried in an oven at 80 ° C to obtain Compound 3. The reaction formula of the above reaction is as follows:

Preparation of bisamine dicarboxylate

Example 1

0.25 g of the compound obtained in Preparation Example 1, 0.146 g of adipic acid (AApic), and 5 ml of water were placed in a reaction flask. Next, the reaction flask was heated to 90 ° C and reacted for 8 hours. Then, it was cooled to room temperature, and filtered, and the obtained solid was washed with water and methanol. The washed solid was dried in an oven at 80 ° C to obtain a bisamine dicarboxylate 1. The reaction formula of the above reaction is as follows:

The nuclear magnetic resonance (NMR) spectrum of the diamine biscarboxylate 1 was measured and the results were as follows: ¹ H NMR (D ₂ SO ₄ , ppm) = 8.7 (1H, s); 8.5 (2H, s); 8.4 ( 1H, s); 4.4-4.3 (4H, m); 4.2-4.1 (4H, m); 3.3-3.2 (4H, m); 2.1-1.9 (4H, m).

Example 2

0.50 g of the compound obtained in Preparation Example 1, 0.41 g of sebacic acid (SA), and 5 ml of water were placed in a reaction flask. Next, the reaction flask was heated to 90 ° C and reacted for 8 hours. Then, it was cooled to room temperature, and filtered, and the obtained solid was washed with water and methanol. The washed solid was dried in an oven at 80 ° C to obtain a bisamine dicarboxylate 2. The reaction formula of the above reaction is as follows:

The nuclear magnetic resonance (NMR) spectrum of the diamine dicarboxylate 2 was measured and the results were as follows: ¹ H NMR (D ₂ SO ₄ , ppm) = 8.7 (1H, s); 8.5 (2H, s); 8.4 ( 1H, s); 4.4-4.3 (4H, m); 4.2-4.1 (4H, m); 3.3-3.2 (4H, m); 2.1-2.0 (4H, m); 1.8-1.7 (8H, m).

Example 3

5 g of the compound obtained in Preparation Example 2, 2.4 g of adipic acid (AApic), and 10 ml of water were placed in a reaction flask. Next, the reaction flask was heated to 90 ° C and reacted for 8 hours. Then, it was cooled to room temperature, and filtered, and the obtained solid was washed with water and methanol. The washed solid was dried in an oven at 80 ° C to obtain a bisamine dicarboxylate 3. The reaction formula of the above reaction is as follows:

The nuclear magnetic resonance (NMR) spectrum of the diamine biscarboxylate 3 was measured and the results were as follows: ¹ H NMR (D ₂ SO ₄ , ppm) = 8.7 (1H, s); 8.5 (2H, s); 8.4 ( 1H, s); 4.4-4.3 (4H, m); 4.2-4.0 (4H, m); 3.3-3.2 (4H, m); 2.4-2.2 (4H, m); 2.1-2.0 (4H, m).

Example 4

0.5 g of the compound obtained in Preparation Example 1, 2.0 g of the compound 3 obtained in Preparation Example 4, 1.46 g of adipic acid (AA), and 150 ml of water were placed in a reaction flask. Next, the reaction flask was heated to 90 ° C and reacted for 8 hours. Then, it was cooled to room temperature, and filtered, and the obtained solid was washed with water and methanol. The washed solid is dried in an oven at 80 ° C to obtain a bisamine dicarboxylate 4 ( Cation and The molar ratio of the cation is 1:4). The reaction formula of the above reaction is as follows:

The nuclear magnetic resonance (NMR) spectra of the diamine dicarboxylate 4 were measured and the results were as follows: ¹ H NMR (D ₂ SO ₄ , ppm) = 8.7 (1H, s, meta-aromatic); 8.5 (2H, s, meta-aromatic); 8.4 (1H, s, meta-aromatic); 8.5 (16H, s, para-aromatic); 4.4-4.3 (20H, m); 4.2-4.1 (20H, m); 3.3-3.2 (20H, m); 2.1-1.9 (20H, m).

Example 5

2.0 g of the compound obtained in Preparation Example 1, 0.5 g of the compound 3 obtained in Preparation Example 4, 1.46 g of adipic acid (AA), and 150 ml of water were placed in a reaction flask. Next, the reaction flask was heated to 90 ° C and reacted for 8 hours. Then, it was cooled to room temperature, and filtered, and the obtained solid was washed with water and methanol. The washed solid was dried in an oven at 80 ° C to obtain a bisamine dicarboxylate salt 5 ( Cation and The molar ratio of cations is 4:1). The reaction formula of the above reaction is as follows:

The nuclear magnetic resonance (NMR) spectrum of the diamine dicarboxylate 5 was measured and the results were as follows: ¹ H NMR (D ₂ SO ₄ , ppm) = 8.7 (4H, s, meta-aromatic); 8.5 (8H, s, meta-aromatic); 8.4 (4H, s, meta-aromatic); 8.5 (4H, s, para-aromatic); 4.4-4.3 (20H, m); 4.2-4.0 (20H, m); 3.3-3.2 (20H, m); 2.1-1.9 (20H, m).

Comparative Example 1

0.25 g of Compound 3 obtained in Preparation Example 4, 0.146 g of adipic acid (AA), and 5 ml of water were placed in a reaction flask. Next, the reaction flask was heated to 90 ° C and reacted for 8 hours. Then, it was cooled to room temperature, and filtered, and the obtained solid was washed with water and methanol. The washed solid was dried in an oven at 80 ° C to obtain a bisamine dicarboxylate 6. The reaction formula of the above reaction is as follows:

The nuclear magnetic resonance (NMR) spectrum of the diamine biscarboxylate 6 was measured and the results were as follows: ¹ H NMR (D ₂ SO ₄ , ppm) = 8.5 (4H, s); 4.4-4.3 (4H, m); 4.2-4.1 (4H, m); 3.3-3.2 (4H, m); 2.1-2.0 (4H, m).

Preparation of copolymer

Example 6

0.4 g of the bisamine dicarboxylate 1 obtained in Example 1 was placed in a reaction flask and connected to a rotary heating device. After evacuating for 5 minutes, nitrogen gas was added, and the above procedure was repeated three times. Next, the heating reaction was carried out under nitrogen, and the heating reaction conditions were heating at 180 ° C for 1 hour, heating at 200 ° C for 1 hour, heating at 220 ° C for 1 hour, heating at 240 ° C for 1 hour, and at 250 ° C. Heat for 1 hour. Finally, the obtained product was dried at 80 ° C for 24 hours. After cooling, copolymer 1 is obtained (having Repeat unit), yield 93%.

The copolymer 1 was measured by a differential scanning calorimeter and found to have a melting temperature (Tm) of 251 ° C (highest peak), a glass transition temperature (Tg) of between about 91 ° C and 92 ° C, and a relative viscosity. (RV) is 2.4. The relative viscosity (RV) of the copolymer was analyzed by placing 0.25 g of the nylon copolymer in an analytical glass bottle, adding concentrated sulfuric acid (97 wt% concentration) to a 50 ml solution, and then performing relative reaction at 25 ° C. Analysis of viscosity (RV). The copolymer 1 was analyzed by nuclear magnetic resonance spectroscopy and infrared spectroscopy, and the obtained spectral information was as follows: ¹ H NMR (D ₂ SO ₄ , ppm) = 8.7 (1H, s); 8.5 (2H, s); 8.4 (1H, s); 4.3 (4H, m); 4.0-3.9 (4H, m); 2.4-2.3 (4H, m); 2.1-2.0 (4H, m).

Example 7

0.4 g of the bisamine dicarboxylate salt 2 obtained in Example 2 was placed in a reaction flask and connected to a rotary heating device. After evacuating for 5 minutes, nitrogen gas was added, and the above procedure was repeated three times. Next, the heating reaction was carried out under nitrogen, and the heating reaction conditions were heating at 180 ° C for 1 hour, heating at 200 ° C for 1 hour, heating at 220 ° C for 1 hour, heating at 240 ° C for 1 hour, and at 250 ° C. Heat for 1 hour. Finally, the obtained product was dried at 80 ° C for 24 hours. After cooling, copolymer 2 is obtained (having Repeat unit), yield 93%.

The copolymer 2 was measured by a differential scanning calorimeter and found to have a melting temperature (Tm) of 220 ° C (highest peak), a glass transition temperature (Tg) of between about 91 ° C and 92 ° C, and a relative viscosity. (RV) is 1.6. The copolymer 2 was analyzed by nuclear magnetic resonance spectroscopy and infrared spectroscopy, and the obtained spectral information was as follows: ¹ H NMR (D ₂ SO ₄ , ppm) = 8.7 (1H, s); 8.5 (2H, s); 8.4 (1H, s); 4.4-4.3 (4H, m); 4.1-3.9 (4H, m); 3.3-3.2 (4H, m); 2.3-2.2 (4H, m); 1.8-1.7 (8H, m).

Example 8

0.4 g of the bisamine dicarboxylate 3 obtained in Example 3 was placed in a reaction flask and connected to a rotary heating device. After evacuating for 5 minutes, nitrogen gas was added, and the above procedure was repeated three times. Next, the heating reaction was carried out under nitrogen, and the heating reaction conditions were heating at 180 ° C for 1 hour, heating at 200 ° C for 1 hour, heating at 220 ° C for 1 hour, heating at 240 ° C for 1 hour, and at 250 ° C. Heat for 1 hour. Finally, the obtained product was dried at 80 ° C for 24 hours. After cooling, the copolymer 3 is obtained (having Repeat unit), yield 91%.

The copolymer 3 was measured by a differential scanning calorimeter and found to have a melting temperature (Tm) of 230 ° C (highest peak), a glass transition temperature (Tg) of between about 87 ° C and 88 ° C, and a relative viscosity. (RV) is 2.1. The copolymer 3 was analyzed by nuclear magnetic resonance spectroscopy and infrared spectroscopy, and the obtained spectral information was as follows: ¹ H NMR (D ₂ SO ₄ , ppm) = 8.7 (1H, s); 8.5 (2H, s); 8.4 (1H, s); 4.3 (4H, m); 4.0-3.9 (4H, m); 3.3-3.2 (4H, m); 2.4-2.3 (4H, m); 2.1-2.0 (4H, m).

Example 9

2 g of the bisamine dicarboxylate salt 4 obtained in Example 4 was placed in a reaction flask and connected to a rotary heating device. After evacuating for 5 minutes, nitrogen gas was added, and the above procedure was repeated three times. Next, the heating reaction was carried out under nitrogen, and the heating reaction conditions were heating at 180 ° C for 1 hour, heating at 200 ° C for 1 hour, heating at 220 ° C for 1 hour, heating at 240 ° C for 1 hour, and at 250 ° C. Heat for 1 hour. Finally, the obtained product was dried at 80 ° C for 24 hours. After cooling, the copolymer 4 is obtained (having and Repeat unit), yield 94%.

The copolymer 4 was measured by a differential scanning calorimeter and found to have a melting temperature (Tm) of 271-279 ° C (highest peak), a glass transition temperature (Tg) of between about 89 ° C and 92 ° C, and The relative viscosity (RV) was 2.3. The copolymer 4 was analyzed by nuclear magnetic resonance spectroscopy and infrared spectroscopy, and the obtained spectral information was as follows: ¹ H NMR (D ₂ SO ₄ , ppm) = 8.7 (1H, s, meta-aromatic); 8.5 (2H, s, meta-aromatic) ); 8.4 (1H, s, meta-aromatic); 8.5 (16H, s, para-aromatic); 4.4-4.3 (20H, m); 4.0-3.9 (20H, m); 3.3-3.2 (20H, m) ;2.1-1.9 (20H, m).

Example 10

2 g of the bisamine dicarboxylate 5 obtained in Example 5 was placed in a reaction flask and connected to a rotary heating device. After evacuating for 5 minutes, nitrogen gas was added, and the above procedure was repeated three times. Next, the heating reaction was carried out under nitrogen, and the heating reaction conditions were heating at 180 ° C for 1 hour, heating at 200 ° C for 1 hour, heating at 220 ° C for 1 hour, heating at 240 ° C for 1 hour, and at 250 ° C. Heat for 1 hour. Finally, the obtained product was dried at 80 ° C for 24 hours. After cooling, the copolymer 5 is obtained (having and Repeat unit), yield 92%.

The copolymer 5 was measured by a differential scanning calorimeter, and it was found that its melting temperature (Tm) was 208-221 ° C (highest peak), glass transition temperature (Tg) was between about 88 ° C and 92 ° C, and The relative viscosity (RV) is 1.4. The copolymer 5 was analyzed by nuclear magnetic resonance spectroscopy and infrared spectroscopy, and the obtained spectral information was as follows: ¹ H NMR (D ₂ SO ₄ , ppm) = 8.7 (4H, s, meta-aromatic); 8.5 (8H, s, meta-aromatic) ); 8.4 (4H, s, meta-aromatic); 8.5 (4H, s, para-aromatic); 4.4-4.3 (20H, m); 4.0-3.9 (20H, m); 3.3-3.2 (20H, m) ;2.1-1.9 (20H, m).

Comparative Example 2

0.4 g of the bisamine dicarboxylate 6 obtained in Comparative Example 1 was placed in a reaction flask and connected to a rotary heating device. After evacuating for 5 minutes, nitrogen gas was added, and the above procedure was repeated three times. Next, the heating reaction was carried out under nitrogen, and the heating reaction conditions were heating at 180 ° C for 1 hour, heating at 200 ° C for 1 hour, heating at 220 ° C for 1 hour, heating at 240 ° C for 1 hour, and at 250 ° C. Heat for 1 hour. Finally, the obtained product was dried at 80 ° C for 24 hours. After cooling, the copolymer 6 is obtained (having Repeat unit), yield 94%.

The copolymer 6 was measured by a differential scanning calorimeter, and it was found that its melting temperature was higher than the cracking temperature, so that the melting point was covered by the cracking temperature. The glass transition temperature (Tg) is between about 91 ° C and 93 ° C and the relative viscosity (RV) is 2.4. The copolymer 6 was analyzed by nuclear magnetic resonance spectroscopy and infrared spectroscopy, and the obtained spectral information was as follows: ¹ H NMR (D ₂ SO ₄ , ppm) = 8.5 (4H, s); 4.4-4.3 (4H, m); 4.2-4.1 (4H m); 3.3-3.2 (4H, m); 2.1-2.0 (4H, m).

Comparative Example 3

According to the synthesis method of a general nylon copolymer described in the literature (Rwei, SP et al., Thermochimica Acta, 555, 37-45, 2013), ethylenediamine (EDA), dimethyl isophthalate ( The dimethyl isophthalate, DMI), and adipic acid (AA) (molar ratio: 1:1:2) were subjected to melt copolymerization to obtain a copolymer 7.

The copolymer 7 was measured by a differential scanning calorimeter, and it was found that its melting temperature (Tm) had a plurality of distinct peaks, ranging from 196 ° C to 240 ° C, and a relative viscosity (R.V.) of 2.1.

As can be seen from Table 1, since the copolymer 6 (Comparative Example 2) uses relatively rigid dimethyl phthalate (DMT) as a reaction starting material (and no isophthalic acid is added) Methyl ester), thus compared to copolymer 1 of the present application (Example 6, using dimethyl isophthalate (DMI) as the starting material for the reaction), resulting in a product melting point above its pyrolysis temperature , the subsequent processing can not be carried out. Copolymer 7 (Comparative Example 3) is a commonly used random polymerization process (copolymerization using three monomers of EDA, DMI, AA), which causes a lot of confusion in the copolymer. The formation of a polymer block, such that the sequence distribution of each monomer component in the copolymer is poor, resulting in poor crystallinity, thereby reducing the melting point, strength, physical stability and the like of the copolymerized product. In contrast, copolymers 1-3 (Examples 6-8), which first synthesize EDA (or BDA) and DMI into diamine monomers, which are then co-linked with dicarboxylic acid monomers (AA or SA). The polymerization reaction can obtain an alternative polymer with optimal sequence distribution, and improve the symmetry, high sequence distribution, and high melting point physical properties of the copolymer. In addition, since a phenyl compound having a disubstituted functional group is used as a reactive monomer, the copolymer can be reduced. The problem is that the melting point of the copolymer is higher than the cracking temperature (>280 ° C), and the problem that the copolymer obtained by using the para-phenyl compound having a disubstituted functional group as a starting material cannot be processed is solved. On the other hand, the present application can also be used to adjust the melting point of the obtained copolymer by adding a phenyl compound as a reactive monomer between the disubstituted functional groups and a para-phenyl compound of the disubstituted functional group. It is known from the copolymers 4-5 (Examples 9-10) of the present application that increasing the molar ratio of the phenyl compound of the disubstituted functional group to the para-phenyl compound of the disubstituted functional group can reduce the copolymerization obtained. The melting point of the substance, to avoid the melting point of the copolymer is higher than its cracking temperature.

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 (12)

a copolymer, which is a reaction product of a composition, the composition comprising a first monomer and a second monomer, wherein the molar ratio of the first monomer to the second monomer is between 1.2:1 Between 1:1.2, wherein the first monomer has the structure represented by formula (I) Wherein n is independently selected from a positive integer of 2-6; and the second monomer has a structure represented by formula (II) Among them, A is -(CH ₂ ) _m -, ,or m is a positive integer selected from 2-12, and R ¹ is H, a C _1-8 alkyl group, or a C _1-6 alkanol group. The copolymer of claim 1, wherein the first single system ,or . The copolymer of claim 1, wherein the second single system , , ,or . The copolymer of claim 1, wherein the copolymer has a repeating unit of the structure represented by formula (IV) Wherein n is independently selected from a positive integer of 2-6, and A is -(CH ₂ ) _m -, ,or And m is a positive integer selected from 2-12. The copolymer of claim 1, wherein the composition further comprises a third monomer, wherein the third monomer has the structure represented by formula (III) Among them, i is a positive integer selected independently from 2-6. The copolymer of claim 5, wherein the first monomer and the third monomer have a molar ratio of from 1:9 to 9:1. The copolymer of claim 5, wherein the third single system ,or . The copolymer according to claim 5, wherein the copolymer has a repeating unit of the structure represented by formula (IV) and formula (V) Wherein, i is independently selected from a positive integer of 2-6, n is independently selected from a positive integer of 2-6, and A is -(CH ₂ ) _m -, ,or And m is a positive integer selected from 2-12. A bisamine dicarboxylate salt which is a compound having the structure of formula (VI): Among them, D ²⁺ , Or a combination of the above, i is independently selected from a positive integer of 2-6, n is independently selected from a positive integer of 2-6, and A is -(CH ₂ ) _m -, ,or And m is a positive integer selected from 2-12. The diamine dicarboxylate salt according to claim 9, wherein the D ²⁺ system and And versus The equivalent ratio is 1:9 to 9:1. A method for preparing a copolymer for forming the copolymer of claim 1, comprising: forming a composition into a diamine dicarboxylate; and subjecting the bisamine dicarboxylate to a heating reaction to obtain the copolymer a copolymer, wherein the composition comprises a first monomer and a second monomer, wherein a molar ratio of the first monomer to the second monomer is between 1.2:1 and 1:1.2, wherein The first monomer has the structure represented by the formula (I) Wherein n is independently selected from a positive integer of 2-6; and the second monomer has a structure represented by formula (II) Among them, A is -(CH ₂ ) _m -, ,or m is a positive integer selected from 2-12, and R ¹ is H, a C _1-8 alkyl group, or a C _1-6 alkanol group. The method for preparing a copolymer according to claim 11, wherein the composition further comprises a third monomer, wherein the third monomer has a structure represented by formula (III) Among them, i is a positive integer selected independently from 2-6.