TWI571479B - Copolymer, and method for preparing the same - Google Patents

Description

Copolymer, and preparation method thereof

This invention relates to a copolymer, and a process for the preparation of a monomer for forming the copolymer.

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. Therefore, the industry is attempting to produce a 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.

The invention discloses a copolymer which is a reaction product of a first monomer and a second monomer, wherein the first monomer has the structure represented by the formula (I)

Wherein, Y--NH ₂ or -CO ₂ H, m is a positive integer selected from 2-10; wherein when Y-CO ₂ H, the second monomer has formula (II), or formula (III) The structure shown; and, when Y is NH ₂ , the second monomer has the structure shown in formula (IV)

HO ₂ CA-CO ₂ H Formula (IV)

Wherein, the X system is independently -NH ₂ or -OH; the A system , ,or n is a positive integer chosen from 2-10; and l is a positive integer chosen from 1-5.

According to another embodiment of the present invention, the present invention provides a method for preparing a monomer, comprising: subjecting a compound having a structure represented by the formula (VIII) to a compound having a structure represented by the formula (IX) by a melting process, And performing an acidification reaction to obtain a monomer having a structure represented by the formula (I).

Wherein M is Na or K; m is a positive integer selected from 2-10; i is a positive integer selected from 1-3; Y is -CO ₂ H; and Z is H or -OH.

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, there is provided a copolymer comprising a product obtained by reacting a first monomer with a second monomer, wherein the first monomer has a structure represented by formula (I)

Wherein Y may be -NH ₂ or -CO ₂ H, and m may be selected from a positive integer of 2-10.

According to an embodiment of the present invention, when the Y system is -CO ₂ H, the second monomer may have a structure represented by formula (II) or formula (III); and, when Y is NH ₂ , the second monomer Can have the structure shown in formula (IV)

HO ₂ CA-CO ₂ H Formula (IV)

Wherein X can be independently -NH ₂ or -OH; A can be , ,or ;n can be chosen from a positive integer of 2-10; and l can be chosen from a positive integer of 1-5.

According to an embodiment of the invention, the first monomer may be Where m is a positive integer selected from 2-10. In addition, when the first monomer is When the second single system H ₂ NA-NH ₂ , wherein the A system , ,or And, n is a positive integer chosen from 2-10. For example, the second monomer can be

According to other embodiments of the present invention, when the first monomer is The second monomer can be, for example

According to some embodiments of the invention, the first monomer may be Where m is a positive integer selected from 2-10. When the first monomer is The second monomer can be, for example ,or

According to some embodiments of the present invention, the copolymer of the present invention may have a repeating unit of the structure shown by formula (V)

Among them, the A system , ,or m is a positive integer chosen from 2-10; and n is a positive integer chosen from 2-10.

According to some embodiments of the present invention, the copolymer of the present invention may have a repeating unit of the structure shown in formula (VI)

Wherein m is a positive integer selected from 2-10; and l is a positive integer selected from 1-5.

According to some embodiments of the present invention, the copolymer of the present invention may have a repeating unit of the structure represented by formula (VII)

Among them, the A system , ,or m is a positive integer chosen from 2-10; and n is a positive integer chosen from 2-10.

According to an embodiment of the invention, the copolymer of the present invention has a melting point temperature of between about 200 ° C and 270 ° C, such as between 240 ° C and 265 ° C.

The present invention also provides a process for preparing a monomer for forming the above copolymer, wherein the method comprises: melting a compound having a structure represented by the formula (VIII) with a compound having a structure represented by the formula (IX) Process or a solution process. Next, the obtained product is subjected to an acidification reaction to obtain a monomer having the structure represented by the formula (I).

Wherein, M is Na or K; m is a positive integer selected from 2-10; i is a positive integer selected from 0 or 1-3; Y is -CO ₂ H; and Z is H or -OH . Wherein, the temperature of the melting process is between 190 ° C and 210 ° C, and the temperature of the solution process is between 85 ° C and 95 ° C.

According to some embodiments of the present invention, the acidification reaction of the product obtained by the melt process or the solution process may comprise the steps of: mixing the product obtained through the melt process with water to obtain a mixture, and titrating with an aqueous solution of inorganic acid. The mixture is brought to a pH of between 5 and 7, for example between 5.6 and 6.4. Further, after the acidification reaction, the water of the mixture is removed and filtered. After washing the obtained solid product and drying, a monomer having a structure represented by the formula (I) can be obtained.

According to an embodiment of the present invention, the compound having the structure represented by the formula (VIII) may be And the compound having the structure represented by the formula (IX) may be ,or

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.

Monomer preparation with structure of formula (I)

Preparation Example 1 : Preparation of N,N'-bis(carboxypentyl)terephthalamide (BCTM) from dimethyl terephthalate and sodium 6-aminocaproate

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 after repeated 5 steps of washing and filtration, the washed solid was dried in an oven at 80 ° C to obtain N,N'-Bis(carboxypentyl)terephthalamide (BCTM). The reaction formula of the above reaction is as follows:

N,N'-bis(carboxypentyl)terephthalamide was measured by differential scanning calorimeter, and its melting temperature (Tm) was found to be 204 ° C (highest peak); and nuclear magnetic resonance spectroscopy was used. And infrared spectroscopy analysis of N, N'-bis(carboxypentyl)terephthalamide, the obtained spectral information is as follows: ¹ H NMR (D ₂ SO ₄ , ppm): 8.53 (4H, phenyl-1,4- ), 4.26 (4H, aromatic-CON-CH ₂ -, ACA), 3.52 (4H, aliphatic-CH ₂ -CO ₂ -, ACA), 1.88-2.37 (12H, aliphatic, ACA).

IR (cm ^-1 ): 3308 (NH); 3300-2930 (broad, OH); 2858; 1725 (carbonyl of CO ₂ H); 1640 (amide); 1570-1350; 1300-800.

According to the information fusion of nuclear magnetic resonance spectroscopy, the obtained compound BCTM has its group versus The molar ratio is 1:2.

Preparation Example 2 : Preparation of N,N'-bis(carboxypentyl)terephthalamide (BCTM)- by bis(2-hydroxyethyl)terephthalate and sodium 6-aminocaproate Solution method).

3.84 g (0.005 mole) of bis-hydroxylethyl terephthalate (BHET), 2.32 g (0.015 mole) of dried sodium 6-aminocaproate (ACA-Na) ), and 20 ml of ethylene glycol (EG), placed in a reaction bottle. Next, under nitrogen, slowly raise the reaction flask to 85-90 ° C, carry out the reaction for 14 hours, then cool to room temperature, add 20 ml of distilled water, and then completely dissolve into a solution, then slowly drop into the aqueous sulfuric acid solution (0.1 M). Neutralization was carried out to bring the pH to 6.0. Then, it was allowed to stand at room temperature for 20 hours, and a solid precipitated and precipitated. The solid was placed in a glass bottle, washed and filtered with 3 times by weight of distilled water, and after repeated 4 steps of washing and filtration, the washed solid was dried in an oven at 80 ° C to obtain N, N'-double. (carboxy, pentyl) terephthalamide (BCTM). The reaction formula of the above reaction is as follows:

The N,N'-bis(carboxypentyl)terephthalamide obtained in Preparation Example 2 was measured by a differential scanning calorimeter, and the melting temperature (Tm) thereof was found to be 204 ° C (the highest peak); And N,N'-bis(carboxypentyl)terephthalamide obtained in Preparation Example 2 was analyzed by nuclear magnetic resonance spectroscopy and infrared spectroscopy to obtain the same spectrum as in Preparation Example 1.

Preparation Example 3: Preparation of N,N'-bis(carboxypentyl)terephthalamide (BCTM)- by bis(2-hydroxyethyl)terephthalate and sodium 6-aminohexanoate Melting method).

3.84 g (0.005 mole) of bis-hydroxylethyl terephthalate (BHET), 2.32 g (0.015 mole) of dried sodium 6-aminocaproate (ACA-Na) ) placed in a reaction bottle. Next, the reaction flask was slowly heated to 195-200 ° C under nitrogen, and after reacting for 14 hours, it was cooled to room temperature, 20 ml of distilled water was added, and after completely dissolved into a solution, a sulfuric acid aqueous solution (0.1 M) was slowly added dropwise. Neutralization was carried out to bring the pH to 6.0. Then, it was allowed to stand at room temperature for 20 hours, and a solid precipitated and precipitated. The solid was placed in a glass bottle, washed and filtered with 3 times the weight of distilled water, weighing After the cleaning and filtration steps were repeated four times, the washed solid was dried in an oven at 80 ° C, and analyzed by nuclear magnetic resonance spectroscopy and infrared spectroscopy to show that N,N'-bis(carboxypentyl)-paraben was obtained. Indoleamine (the same spectrum as in Preparation Example 1) also contained about 30% by-product.

A method for synthesizing N,N'-bis(carboxypentyl)terephthalamide is 6-aminohexanoic acid (ACA) and terephthalic acid with chloride. Terephthaloyl chloride (TCL) is reacted in solution in the presence of hexamethylenediamine (HMDA), pyridine, and N-methylethylpyrrolidone (NMP). After purification, the same spectrum as in Preparation Example 1 was obtained. (The reaction formula is as follows:

However, terephthaloyl chloride (TCL), which is the starting material of the reaction, is a non-environmental ruthenium chloride compound, thus forming a N,N'-bis(carboxypentyl) pair with p-xylylene chloride. The preparation method of phthalicin is an environmentally friendly process.

Comparative Preparation Example 1:

0.97 g (0.005 mole) of dimethyl terephthalate (DMT), 1.69 g (0.015 mole) of 6-aminohexanoic acid (ACA), and 20 ml of ethylene glycol (ethylene glycol, EG), placed in a reaction bottle. Next, the reaction flask was slowly heated to 85 to 90 ° C under nitrogen, and after reacting for 14 hours, it was cooled to room temperature, 20 ml of distilled water was added thereto, and a sulfuric acid aqueous solution (0.1 M) was gradually added dropwise thereto to neutralize it. The pH reached 6.0. Then, it was allowed to stand at room temperature for 20 hours, and a solid precipitated and precipitated. The solid was placed in a glass bottle, washed and filtered with 3 times by weight of distilled water, and after repeated four steps of washing and filtration, the washed solid was dried in an oven at 80 °C. Since 6-aminocaproic acid undergoes self-polymerization, the obtained polymer reacts with dimethyl terephthalate, so the above reaction only gives a chaotic product, and N,N'-bis(carboxypentyl)-p-benzoic acid cannot be obtained. Formamide (BCTM).

Preparation 4 : Preparation of N,N'-bis(6-aminohexane)terephthalamide (BATM)

A reaction flask was taken, and 0.97 g (0.005 mole) of dimethyl terephthalate (DMT), 3.06 g (0.02 mole) of hexamethylenediamine (HMDA), and 20 ml of ethylene glycol ( Ethylene glycol, EG). The temperature was slowly raised to 85 to 90 ° C under nitrogen for 14 hours. After standing at room temperature for 20 hours, a solid precipitated and precipitated. The solid was placed in a glass bottle, washed and filtered with 3 times by weight of distilled water, and after repeated four steps of washing and filtration, the washed solid was dried in an oven at 80 °C. After drying, N,N'-bis(6-aminohexane)terephthalamide (BATM) solid was obtained. N,N'-bis(6-aminohexane)-p-xylyleneamine was measured by differential scanning calorimeter, and its melting temperature (Tm) was found to be 211 ° C (highest peak); and nuclear magnetic resonance was used. Resonance and Infrared Spectroscopy Analysis of N,N'-bis(6-Aminohexane)-p-dimethylguanamine, the obtained spectral information is as follows: ¹ H NMR (D ₂ SO ₄ , ppm): 8.52 (4H, phenyl- 1,4-), 4.26 (4H, aromatic-CON-CH ₂ -, HMDA), 3.91 (4H, aliphatic-CH ₂ -NH ₂ , HMDA), 1.88-2.37 (16H, aliphatic, HMDA).

IR (cm ^-1 ): 3308-3294 (NH); 2927; 2858; 1643 (amide); 1570-1350; 1300-800.

The group of compounds BATM can be known from the information fusion of nuclear magnetic resonance spectroscopy. versus The molar ratio is 1:2.

Preparation of copolymer

Example 1: Preparation of BCTM-co-HMDA copolymer

A reaction flask was taken, and 14.2 g (0.036 mole) of N,N'-bis(carboxypentyl)-p-xylguanamine (BCTM), 4.2 g (0.036 mole) of hexamethylenediamine (HMDA), and 60 g were added. 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. Next, 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 found to have a melting temperature (Tm) of 261 ° C (highest peak), a glass transition temperature (Tg) of 75 ° C, and a relative viscosity (RV). ) is 1.45. The relative viscosity (RV) of the copolymer was analyzed under the condition that 0.25 g of the nylon copolymer was placed in an analysis glass bottle, concentrated sulfuric acid (97 wt% concentration) was added to prepare a 50 ml solution, and then at 25 ° C, Perform a relative viscosity (RV) analysis. The BCTM-co-HMDA copolymer was analyzed by nuclear magnetic resonance spectroscopy and infrared spectroscopy. The obtained spectral information was as follows: ¹ H NMR (D ₂ SO ₄ , ppm): 8.53 (4H, phenyl, BCTM), 4.26 (4H, aromatic-CON) -CH ₂ -, ACA), 4.00 (4H, aliphatic-CON-CH ₂ -, HMDA), 3.18 (4H, aliphatic-CH ₂ -CON-, ACA), 1.87-2.34 (20H, aliphatic, ACA and HMDA) .

¹³ C NMR (D ₂ SO ₄ , ppm): 178 and 172 (amide), 131 (aromatic), 44-43, 33, 27-24.

IR (cm ^-1 ): 3304 (NH); 2930; 2858; 1630 (broad, amide); 1570-1350; 1300-800.

It can be known from the information fusion of nuclear magnetic resonance spectroscopy that the BCTM-co-HMDA copolymer has its group , ,versus The molar ratio is 1:1:2.

Repeat the steps described in Example 1, perform the first verification experiment and the second verification experiment, and measure the BCTM-co obtained by the first verification experiment and the second verification experiment by differential scanning calorimeter. The melting temperature (Tm) of the -HMDA copolymer was 262 ° C and 261 ° C (the highest peak); and, the glass transition temperature of the BCTM-co-HMDA copolymer obtained in the first verification experiment and the second verification experiment was measured. (Tg), 74-75 ° C. Further, the BCTM-co-HMDA copolymer obtained by the first verification experiment and the second verification experiment by the nuclear magnetic resonance spectrum showed the same spectral information as the BCTM-co-HMDA of Example 1. The chemical composition of the BCTM-co-HMDA copolymer of the present invention and the reproducibility of its physical properties are shown to be good.

Example 2 : Preparation of BCTM-co-TMDA copolymer

The BCTM-co-HMDA copolymer was synthesized as described in Example 1, except that 4.2 g of hexamethylenediamine (HMDA) was substituted with 3.18 g of tetramethylene diamine (TMDA) to obtain The repeating unit of the copolymer BCTM-co-TMDA.

The BCTM-co-TMDA copolymer was measured by a differential scanning calorimeter and found to have a melting temperature (Tm) of 263 ° C (highest peak), a glass transition temperature (Tg) of 76 ° C, and a relative viscosity (RV). ) is 1.52. The BCTM-co-TMDA copolymer was analyzed by nuclear magnetic resonance spectroscopy and infrared spectroscopy. The obtained spectral information was as follows: ¹ H NMR (D ₂ SO ₄ , ppm): 8.53 (4H, phenyl, BCTM), 4.26 (4H, aromatic-CON) -CH ₂ -, ACA), 4.00 (4H, aliphatic-CON-CH ₂ -, TMDA), 3.18 (4H, aliphatic-CH ₂ -CON-, ACA), 1.87-2.34 (16H, aliphatic, ACA and TMDA) .

¹³ C NMR (D ₂ SO ₄ , ppm): 178 and 173 (amide), 131 (aromatic), 44-43, 33, 27-24.

IR (cm ^-1 ): 3304 (NH); 2930; 2858; 1630 (broad, amide); 1570-1350; 1300-800.

According to the information fusion of nuclear magnetic resonance spectroscopy, the BCTM-co-TMDA copolymer has its group , ,versus The molar ratio is 1:1:2.

Example 3: Preparation of BCTM-co-EDA copolymer

The BCTM-co-HMDA copolymer was synthesized as described in Example 1, except that 4.2 g of hexamethylenediamine (HMDA) was substituted with 2.17 g of ethylene daimine (EDA) to obtain The repeating unit of the copolymer BCTM-co-EDA.

The BCTM-co-EDA copolymer was analyzed by nuclear magnetic resonance spectroscopy and infrared spectroscopy. The obtained spectral information was as follows: ¹ H NMR (D ₂ SO ₄ , ppm): 8.53 (4H, phenyl, BCTM), 4.26 (4H, aromatic-CON) -CH ₂ -, ACA), 4.10 (4H, aliphatic-CON-CH ₂ -, EDA), 3.18 (4H, aliphatic-CH ₂ -CON-, ACA), 1.87-2.34 (12H, aliphatic, ACA).

¹³ C NMR (D ₂ SO ₄ , ppm): 178 and 173 (amide), 131 (aromatic), 44-43, 33, 27-24.

IR (cm ^-1 ): 3309 (NH); 2930; 2855; 1630 (broad, amide); 1570-1350; 1300-800.

It can be known from the information fusion of nuclear magnetic resonance spectroscopy that the BCTM-co-EDA copolymer has its group , ,versus The molar ratio is 1:1:2.

Example 4: Preparation of BCTM-co-PDA copolymer

The synthesis of BCTM-co-HMDA was carried out as described in Example 1, except that 4.2 g of hexamethylenediamine (HMDA) was substituted with 3.91 g of para-phenylenediamine (PDA) to obtain repeating units. Copolymer BCTM-co-PDA.

The BCTM-co-PDA copolymer was measured by a differential scanning calorimeter, and it was found that the melting temperature (Tm) was 321 ° C (broad, the highest peak), and the glass transition temperature (Tg) was 110 ° C. The BCTM-co-PDA copolymer was analyzed by nuclear magnetic resonance spectroscopy and infrared spectroscopy. The obtained spectral information was as follows: ¹ H NMR (D ₂ SO ₄ , ppm): 8.53 (4H, phenyl, BCTM), 7.11 (4H, phenyl, PDA) ), 4.26 (4H, aromatic-CON-CH ₂ -, ACA), 3.18 (4H, aliphatic-CH ₂ -CON-, ACA), 1.87-2.34 (= 12H, aliphatic, ACA).

IR (cm ^-1 ): 3309-3270 (NH); 2920; 2861; 1645 (broad, amide); 1590-1350; 1300-800.

According to the information fusion of nuclear magnetic resonance spectroscopy, the BCTM-co-PDA copolymer has its group , ,versus The molar ratio is 1:1: 1.8-1.9.

Example 5: Preparation of BCTM-co-BHET copolymer

The synthesis of BCTM-co-HMDA copolymer was carried out as described in Example 1, except that 4.2 g of hexamethylenediamine (HMDA) was tetramerized with 31.38 g of bis(2-hydroxyethyl)terephthalate. Bis-hydroxylethyl terephthalate tetramer (chemical structure is ), BHET tetramer) substituted, obtained with The repeating unit of the copolymer BCTM-co-BHET.

The BCTM-co-BHET copolymer was measured by a differential scanning calorimeter, and its melting temperature (Tm) was found to be 247 ° C (highest peak).

Example 6: Preparation of BATM-co-AA copolymer

A reaction flask was taken, and 12.98 g (0.036 mole) of N,N'-bis(6-aminohexyl)terephthalamide, BATM, and 5.29 g (0.036 mole) of adipic acid were added under a nitrogen atmosphere. Adipic acid, AA), and 60g water. Next, the temperature of the reaction flask was raised to 85 ° C. After the solids were completely dissolved, it showed that BATM and AA were sufficiently uniformly mixed. At this time, the water was removed by distillation under reduced pressure, and the solid product remaining in the reaction flask was slowly heated to Maintain at 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, get Repeat unit copolymer BATM-co-AA.

The BATM-co-AA copolymer was measured by a differential scanning calorimeter and found to have a melting temperature (Tm) of 301 ° C (highest peak), a glass transition temperature (Tg) of 78 ° C, and a relative viscosity (RV). ) is 1.52. The BATM-co-AA copolymer was analyzed by nuclear magnetic resonance spectroscopy and infrared spectroscopy. The obtained spectral information was as follows: ¹ H NMR (D ₂ SO ₄ , ppm): 8.53 (4H, phenyl, BATM), 4.26 (4H, aromatic-CON -CH ₂ -, HMDA), 4.00 (4H, aliphatic-CON-CH ₂ -, HMDA), 3.18 (4H, aliphatic-CH ₂ -CON-, AA), 1.86-2.36 (20H, aliphatic, HMDA and AA) .

¹³ C NMR (D ₂ SO ₄ , ppm): 177 and 172 (amide), 131 (aromatic), 44-43, 32, 28-24.

IR (cm ^-1 ): 3302 (NH); 2930; 2855; 1630 (broad, amide); 1570-1350; 1300-800.

It can be known from the information fusion of nuclear magnetic resonance spectroscopy that the BCTM-co-HMDA copolymer has its group , ,versus The molar ratio is 1:1:2.

Example 7: Preparation of BATM-co-IPA copolymer

Take a reaction flask and add 12.98g (0.036mole) of N,N'-bis(6-aminohexyl)terephthalamide, BATM, 6.02g (0.036mole) of isophthalic acid (IPA). ), and 60g of water. Next, the temperature of the reaction flask was raised to 85 ° C. After the solid was dissolved, the water was removed by distillation under reduced pressure, and the solid product remaining in 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, get Repeat unit copolymer BATM-co-IPA.

The BATM-co-IPA copolymer was measured by a differential scanning calorimeter without a significant melting point temperature (Tm), a glass transition temperature (Tg) of 115 ° C, and a relative viscosity (RV) of 1.41. The BATM-co-IPA copolymer was analyzed by nuclear magnetic resonance spectroscopy and infrared spectroscopy. The obtained spectral information was as follows: ¹ H NMR (D ₂ SO ₄ , ppm): 9.02 (1H, phenyl, IPA), 8.53 (4H, phenyl, BATM) ), 8.45 (2H, phenyl, IPA), 7.96 (1H, phenyl, IPA), 4.26 (4H, aromatic-CON-CH ₂ -, HMDA), 4.00 (4H, aliphatic-CON-CH ₂ -, HMDA), 1.86-2.36 (8H, aliphatic, HMDA).

¹³ C NMR (D ₂ SO ₄ , ppm): 177 and 175 (amide), 140, 132, 129 (aromatic), 44-43, 28-24.

IR (cm ^-1 ): 3305-3300 (NH); 2930; 2878; 1676 (broad, amide); 1570-800.

According to the information fusion of nuclear magnetic resonance spectroscopy, the BATM-co-IPA copolymer has its group , ,versus The molar ratio is 1:1:2.

Comparative Example 1:

Hexanediamine (HMDA), terephthalic acid, TPA), and caprolactam (CPL) (molar ratio: 1:1:2) were subjected to melt copolymerization to obtain a copolymer (1).

The copolymer (1) was measured by a differential scanning calorimeter, and it was found that the melting temperature (Tm) had two distinct peaks of 183 ° C and 213 ° C (broad), respectively, and a relative viscosity of 2.0. The copolymer (1) was analyzed by nuclear magnetic resonance spectroscopy and infrared spectroscopy. The obtained spectral information was as follows: ¹ H NMR: δ 8.53 (4H, phenyl), 4.26 (4H, aromatic-CON-CH ₂ ), 4.00 (4H, aliphatic-CON-CH ₂ ), 3.18 (4H, aliphatic-CH ₂ -CON), 1.87-2.34 (aliphatic, CPL and HMDA).

¹³ C NMR (D ₂ SO ₄ , ppm): 178 and 172 (amide), 131 (aromatic), 44-43, 33, 27-24.

IR (cm ^-1 ): 3304 (NH); 2930; 2861; 1630 (broad, amide); 1570-800.

From the analysis of the information integration of nuclear magnetic resonance spectroscopy, because the spectral absorption peaks of CPL and HMDA are very similar, and the absorption peaks of the aliphatic overlap are mostly overlapped, only the ratio of aromatic to aliphatic is calculated, and the copolymerization is calculated by calculation. Compound (1) aromatic group Aliphatic group versus The molar ratio is 1.00: 2.97.

Comparative Example 2:

The procedure described in Comparative Example 1 was repeated, and a verification experiment was carried out to obtain a polymer (2). The melting temperature (Tm) of the polymer (2) was measured by a differential scanning calorimeter to be 190-220 ° C (wide peak). The copolymer (2) was analyzed by nuclear magnetic resonance spectroscopy and infrared spectroscopy, and the obtained spectral information was as follows: ¹ H NMR: δ 8.53 (4H, phenyl), 4.26 (4H, aromatic-CON-CH ₂ ), 4.00 (4H, aliphatic -CON-CH ₂ ), 3.18 (4H, aliphatic-CH ₂ -CON), 1.87-2.34 (aliphatic, CPL and HMDA).

¹³ C NMR (D ₂ SO ₄ , ppm): δ 178 and 172 (amide), 131 (aromatic), 44-43, 33, 27-24.

IR (cm ^-1 ): 3304 (NH); 2930; 2861; 1630 (broad, amide); 1570-800.

Calculate the ratio of aromatic to aliphatic, and calculate the aromatic group of copolymer (2) Aliphatic group versus The molar ratio is 1.00: 2.98.

Comparative Example 3:

The procedure described in Comparative Example 1 was repeated, and a verification experiment was carried out to obtain a polymer (3). The melting temperature (Tm) of the polymer (3) was measured by a differential scanning calorimeter to be 185 ° C, 192 ° C, and 218 ° C. The copolymer (3) was analyzed by nuclear magnetic resonance spectroscopy and infrared spectroscopy, and the obtained spectral information was as follows: ¹ H NMR: δ 8.53 (4H, phenyl), 4.26 (4H, aromatic-CON-CH ₂ ), 4.00 (4H, aliphatic -CON-CH ₂ ), 3.18 (4H, aliphatic-CH ₂ -CON), 1.87-2.34 (aliphatic, CPL and HMDA).

¹³ C NMR (D ₂ SO ₄ , ppm): 178 and 172 (amide), 131 (aromatic), 44-43, 33, 27-24.

IR (cm ^-1 ): 3304 (NH); 2930; 2861; 1630 (broad, amide); 1570-800.

Calculate the ratio of aromatic to aliphatic, and calculate the aromatic group of the copolymer (3) Aliphatic group versus The molar ratio is 1.00: 2.98.

Comparative Example 4:

According to the general method for synthesizing nylon 6 described in the literature (Rwei, SP et al., Thermochimica Acta, 555, 37-45, 2013), 0.8 kg of caprolactam (CPL), 0.16 kg of water, 0.06 kg of acetic acid, the temperature was raised to 180 ° C and maintained for 2 hours. The temperature was then brought to 220 ° C and maintained for 2 hours. Next, the temperature was gradually raised from 220 ° C to 260 ° C over 2 hours and continued for 6 hours. After cooling, the material was cut and pelletized to obtain a nylon 6 polymer.

Next, the hot water extractable amount experiment was carried out on Example 1 and its verification experiments 1 and 2, and Comparative Example 1-4, and the results are shown in Table 1. The step of the hot water extractable amount experiment comprises: placing the test object in a reaction bottle (the weight of the test object is W0), and adding 15 times the weight of the test object. Next, after heating under reflux for 10 hours, the aqueous solution was removed, and the remaining solid was dried and weighed (when the weight was W1), and the amount of hot water extractable ((W0-W1) / W0 x 100 wt%) was calculated.

Table 1

Remarks: CPL representative Group, TPA representative Group, HMDA representative Group, AA representative Group.

As can be seen from the results of Table 1, Comparative Examples 1-3 can be directly used as a reactive monomer by hexamethylenediamine (HMDA), terephthalic acid (TPA), and caprolactam (CPL). In the copolymerization reaction, even if Comparative Examples 1-3 were carried out in the same manner, the obtained copolymers (1) to (3) had a structure (repeating group ratio) and physical properties (for example, melting temperature and glass transition temperature). Differences. This is because the comparative examples 1-3 use the conventional polymerization method, and the polymerization reaction between the three monomers of HMDA, TPA and CPL has many different arrangement and combination, so the copolymer product is arranged by various groups with different molecular weights and different groups. A disordered copolymer composed of a combined structure. In addition, the compatibility between aromatic terephthalic acid and fat hexamethylene diamine and caprolactam is low, and the difference in reactivity between the two types of terminal functional groups is large, resulting in terephthalic acid in the main chain. The sequence distribution within is not uniformly dispersed. Therefore, the obtained copolymer has a poor regular structure, and the chemical structure and physical properties are not reproducible, so that it is difficult to obtain a stable chemical structure and physical properties of the copolymer. On the contrary, it can be seen from the first embodiment of the present invention and its verification experiment that there is almost no difference in the ratio of the amount of each monomer before the reaction to the content of each monomer derivative in the copolymer after the reaction, because of the structure of the formula (I). The monomer can be distributed in the sequence of the molecular structure uniformity of the backbone of the copolymer, which would otherwise cause a predominantly random distribution in the backbone molecule. And caprolactam (or / and diamine) is first reacted to obtain a comonomer of formula (I) containing two monomers of TPA and caprolactam (or diamine), such as formula (I) The comonomer is then subjected to alternate polymerization with the monomer of formula (II) to obtain a cross-linked copolymer. In addition, this method can also improve the mutual compatibility between the monomer having the formula (I) and the monomer having the formula (II), and the difference in reactivity between the terminal functional groups of both. Therefore, the method of the present invention can improve the symmetry of the copolymer, high sequence distribution, and physical properties such as high melting point with respect to known techniques of a random copolymer. This can improve The uniformity sequence distribution within the backbone of the copolymer results in a product that is close to an alternative copolymer. If applied to plastic or spinning processes, it can reduce product variability, improve stability and reduce yarn breakage.

In addition, the copolymer obtained in Example 1 and its verification experiment has a significant melting temperature and glass transition temperature compared to the currently commercially available nylon 6, or the copolymers described in Comparative Examples 1-4. improve. Moreover, the glass transition temperature of the copolymer obtained in Example 1 and its verification experiment was increased by about 20-30 ° C compared to the commercially available nylon 6 and nylon 66, and the melting point temperature was even close to that of nylon 66. Further, the copolymer obtained in Example 1 and its verification experiment had a hot water extractable amount (wt%) lower than that of the nylon 6 or the copolymer described in Comparative Examples 1-3.

Therefore, it is understood from Table 1 that the copolymer of the present invention is substantially superior in properties to the commercial nylon 6. Compared with nylon 66, the copolymer of the present invention The group content can be greater than 49 mole%, and the Tm and Tg are also close to or better than nylon 66, thus having the opportunity to replace the nylon 66 application market. Further, in the first embodiment of the present invention and the verification experiment 1-2, the copolymer of the present invention has extremely high reproducibility (i.e., high stability in chemical structure and physical properties), and is very suitable for commercialization (stability is commercialized). The most important conditional parameter is that the copolymer produced in each batch has the same properties).

From the experimental results of the above-mentioned Examples 1-7 and Comparative Examples 1-4 of the present invention, it has been found that since the present invention, terephthalic acid (TPA) is substituted with a monomer having a structure of the formula (I), and a diamine or an anthracene. The amine monomer reacts to form a copolymer, which allows The groups are uniformly distributed in the main chain of the copolymer to give an alternating copolymer (as described in Example 1). a copolymer of repeating units which form a main chain in the order of [-CPL-TPA-CPL-HMDA-] (CPL stands for Group, TPA representative Group, and HMDA representative Group), has a high melting point, softening point, heat resistance, mechanical strength, and low hot water extractable amount.

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 (9)

A method for preparing a copolymer comprising reacting a first monomer with a second monomer, wherein the first monomer has a structure represented by formula (I) Wherein, Y--NH ₂ or -CO ₂ H, m is a positive integer selected from 2-10; wherein when Y-CO ₂ H, the second monomer has formula (II), or formula (III) The structure shown; and, when Y is NH ₂ , the second monomer has the structure of formula (IV) XAX (II) HO ₂ CA-CO ₂ H Formula (IV) wherein X is independently -NH ₂ or -OH; A , ,or n is a positive integer chosen from 2-10; and l is a positive integer chosen from 1-5. The method for preparing a copolymer according to claim 1, wherein the first single system Where m is a positive integer selected from 2-10. The method for preparing a copolymer according to claim 2, wherein the second single system H ₂ NA-NH ₂ , wherein the A system , ,or And, n is a positive integer chosen from 2-10. The method for preparing a copolymer according to claim 3, wherein the second single system , , The method for preparing a copolymer according to claim 2, wherein the second single system , ,or The method for preparing a copolymer according to claim 1, wherein the first single system Where m is a positive integer selected from 2-10. The method for preparing a copolymer according to claim 6, wherein the second single system ,or . a copolymer having a repeating unit of the formula shown in formula (V), formula (VI), or formula (VII) , where A is , ,or m is a positive integer selected from 2-10; n is a positive integer selected from 2-10; and l is a positive integer selected from 1-5. The copolymer of claim 8 wherein the copolymer has a melting temperature between 220 ° C and 270 ° C.