TWI841925B - A copolymer amide resin, fiber and preparation method and application thereof - Google Patents

Abstract

The present invention provides a copolymer amide resin, fiber, and a preparation method and application thereof. The copolymer amide resin includes the following segments: segment A): -NH(CH ₂ ) ₅ NH CO(CH ₂ ) ₄ CO-, and segment B): -NH(CH ₂ ) ₆ NH CO(CH ₂ ) ₄ CO-; wherein the molar ratio of segment A) to segment B) is (95:5)-(5:95), and the terminal amino group content of the copolymer amide resin is 30-80 mmol/kg. The copolymer amide resin of the present invention has the advantages of moderate viscosity, moisture content and terminal amino group content, low oligomer content, large molecular weight and narrow molecular weight distribution, and can meet the use requirements in the spinning field. The spun fibers have excellent comprehensive properties.

Description

A copolymer amide resin, fiber and preparation method and application thereof

The present invention belongs to the field of polyamide material technology, and relates to a copolymerized polyamide resin, fiber, and its preparation method and application.

Copolyamide is a polyamide product obtained by polymerization of two or more polyamide monomers. By selecting appropriate copolymer monomers or polymers, the polyamide can be copolymerized and modified, and its melting point, crystallinity, solubility and transparency can be greatly changed while changing its ratio and structure, thereby preparing copolymeramide with a series of special properties such as softness, good transparency, low softening point, and easy solubility.

The copolymer structure prepared by copolymeramide is different according to the different polymerization processes. Its modification process can be divided into: block copolymerization, random copolymerization, alternating copolymerization and graft copolymerization. The research on copolymeramide was started early abroad. Catlin et al. studied three series of copolymeramides, PA66/6, PA66/610 and PA66/610/6, and analyzed and tested the melting point, water absorption, softening point and solubility of the copolymer products. The results showed that when the mass ratio of PA66:PA6 was 40:60, the melting point of the copolymer was the lowest, which was 154-156°C. Copolyamide 6/66 has unique copolymer amide properties such as low melting point, low crystallinity, and good transparency. It also has excellent properties such as good toughness, wear resistance, self-lubricating properties, and good chemical stability. It is widely used in films, fibers, and engineering plastics.

Li Pengzhou et al. pointed out in the development and application of copolymerized nylon 66/6 that the copolymerization effect is best when the caprolactam content is 2%-5% (mass ratio), the yarn full tube rate is increased from the original 63.9% to 81.2% after copolymerization, the superior product rate is increased from 63% to more than 85%, and the unit consumption is reduced from 1.08 to 1.05. The caprolactam content added is low, which is of little significance for reducing the production cost of nylon 66.

Luo Yuhang studied the preparation and performance of copolymer amide 6/66. Using caprolactam (CPL), nylon 66 salt (AH-salt), and terephthalic acid (PTA) as raw materials, and using two polymerization processes, namely, normal pressure polymerization and prepolymerization followed by polycondensation, a series of copolymer amide 6/66 was prepared by changing the copolymer monomer formula and process conditions. The nylon 66 salt content was 15-20%, and the prepared copolymer amide 6/66 had a melting point of 188.7-195°C, a relative viscosity of 3.08-3.65, a weight average molecular weight of 22884-28407, and a molecular weight distribution of 2.16-3.4. The copolymer amide 6/66 had a low melting point and a large molecular weight distribution.

Ma Haiyan studied the post-stretching properties of large diameter PA6/PA66 copolymer monofilaments. Using PA6/PA66 copolymer as raw material, large diameter monofilaments were spun. The copolymer PA6/PA66=60:40 was used, with a characteristic viscosity of 0.68dL/g, a molecular weight of 24000, and a melting point of 180℃. The viscosity and melting point of the PA6/PA66 copolymer were relatively low.

Patent No. CN 108250433 A discloses a PA6-56 copolymer material and a preparation method thereof, wherein the PA6-56 copolymer material is prepared by blending and polymerizing liquid caprolactam and an aqueous solution of pentamethylenediamine adipate salt; the molar ratio of the liquid caprolactam to the aqueous solution of pentamethylenediamine adipate salt is 7:3 to 9:1. The method comprises: mixing liquid caprolactam, an aqueous solution of pentamethylenediamine adipate salt and other reaction raw materials in proportion, stirring in a reactor under inert gas protection conditions, and performing a polycondensation reaction at 150-300°C to obtain the PA6-56 copolymer material. The patent application mainly uses PA6 monomer caprolactam as the main material, and PA56 monomer pentamethylenediamine adipate salt as the copolymer to produce PA6-56 copolymer material, with an equilibrium moisture absorption rate of 5.23-5.45%. The water absorption rate of the PA6-56 copolymer material is relatively high.

Patent No. CN106519219 A discloses a continuous polymerization process of PA6-5X copolymer and PA6-5X copolymer. In the PA6-5X copolymer, the mass percentage of PA5X salt can reach up to 60%, the melting point of the copolymer is between 165℃-219℃, and the relative viscosity is between 2.4-3.6. The PA6-5X copolymer is prepared by three-stage continuous polymerization, which is characterized by using a combination of solid nylon 5X salt and nylon 5X salt aqueous solution to mix caprolactam and 5X salt evenly before the reaction, and obtain a highly random copolymer after polymerization. The preparation method is used to prepare PA6-5X copolymer. The PA6-56 copolymer material has a low melting point.

Currently, there are few reports on PA56-66 copolymers. PA6-56 copolymers have a low melting point and a narrow application field. However, there are few reports on the application of PA56-66 copolymers, especially in the textile field.

The first object of the present invention is to provide a copolymeric amide resin having the characteristics of moderate viscosity and terminal amino group content, low oligomer content, large molecular weight and narrow molecular weight distribution.

To achieve the above object, the solution of the present invention is: a copolymeramide resin, the copolymeramide comprising the following segments: segment A): -NH(CH ₂ ) ₅ NH CO(CH ₂ ) ₄ CO-, and segment B): -NH(CH ₂ ) ₆ NH CO(CH ₂ ) ₄ CO-; wherein the molar ratio of segment A) to segment B) is (95:5)-(5:95), and the terminal amino group content of the copolymeramide resin is 30-80 mmol/kg, further 35-75 mmol/kg, further 40-60 mmol/kg.

Furthermore, the molar ratio of the chain segment A) to the chain segment B) is (95:5)-(20:80), further (95:5)-(35:65), further (95:5)-(50:50), and further (95:5)-(65:35). According to some embodiments of the present invention, appropriately increasing the content of the chain segment A) can improve the performance of the copolymerized amide resin and the textile product.

Furthermore, the total mass of the chain segment A) and the chain segment B) accounts for more than 90% of the mass of the copolymer amide resin, further more than 93%, further more than 95%, further more than 98%.

Furthermore, the relative viscosity of the copolymer amide resin is 2.4-3.7, further 2.5-3.5, and further 2.65-3.0.

Furthermore, the terminal amino group content of the copolymer amide resin is further 45~52.5mmol/kg.

1.0wt%，進一步為

0.8wt%，更進一步為

0.6wt%。 Further, the oligomer content of the copolymer amide is

1.0wt%, further

0.8wt%, further

0.6wt%.

6.5，進一步為

6，更進一步為

4。 Further, the yellowness index of the copolymer amide resin is

6.5, further

6. Further

4.

Furthermore, the number average molecular weight of the copolymer amide resin is 1.5*10 ⁴ -4.0*10 ⁴ g/mol, further 1.8*10 ⁴ -3.5*10 ⁴ g/mol, and further 2.2*10 ⁴ -3.0*10 ⁴ g/mol.

The molecular weight distribution of the copolymer amide resin is 1.4-2.5, further 1.6-2.4, and further 1.8-2.3.

The copolymer amide resin is a PA56/66 copolymer, and the monomers include 1,5-pentanediamine, hexamethylenediamine, and adipic acid.

According to some embodiments of the present invention, the copolymer amide resin contains additives, and the additives include any one or a combination of two or more of a capping agent, a catalyst, a flame retardant, an antioxidant, an ultraviolet absorber, an infrared absorber, a crystallization nucleating agent, a fluorescent brightener, and an antistatic agent.

The end-capping agent includes any one or a combination of two or more of aliphatic carboxylic acids of C2 to C16 and aromatic carboxylic acids of C7 to C9.

Furthermore, the C7-C9 aromatic carboxylic acid includes any one or a combination of two or more of terephthalic acid, isophthalic acid, phthalic acid, and benzoic acid.

Furthermore, the end-capping agent is a combination of aliphatic carboxylic acids of C2~C16 and aromatic carboxylic acids of C7~C9, and the mass ratio of aliphatic carboxylic acids of C2~C16 to aromatic carboxylic acids of C7~C9 is (8-1):1, and further (5-1):1.

Furthermore, the end-capping agent is a combination of decanedicarboxylic acid and terephthalic acid, and the mass ratio of the decanedicarboxylic acid to terephthalic acid is (8-1):1, and further is (5-1):1.

Furthermore, the end-capping agent is a combination of decanedioic acid and benzoic acid, and the mass ratio of the decanedioic acid to benzoic acid is (8-1):1, and further (5-1):1.

The content of the end-capping agent is 300-10000ppm, and further 800-7000ppm, of the total weight of 1,5-pentanediamine, hexamethylenediamine, and adipic acid monomers. The use of a suitable end-capping agent can regulate the polymerization process.

Furthermore, the antioxidant includes any one of sodium hypophosphite, sodium hypophosphite acetate, calcium hypophosphite, phosphorous acid, antioxidant 1010, antioxidant 1097, or a combination of two or more thereof; the content of the antioxidant accounts for 5-300ppm of the total weight of 1,5-pentanediamine, hexamethylenediamine, and adipic acid monomers, and further 10-200ppm.

The second purpose of the present invention is to provide a method for preparing a copolymer amide resin to obtain a copolymer amide resin with excellent performance and capable of meeting the requirements for use in the spinning field.

The preparation method comprises the following steps:

1) Mix the polyamide 56 salt solution with the polyamide 66 salt solution to obtain a mixed salt solution; or under nitrogen conditions, mix 1,5-pentanediamine, hexamethylenediamine, and adipic acid with water in a certain molar ratio to obtain a mixed salt solution directly.

2) The mixed salt solution is heated and concentrated, and prepolymerization is first performed to raise the internal pressure of the reaction system to 0.3-2.45MPa, exhaust and maintain the pressure, and then the pressure is reduced to reduce the internal pressure of the reaction system to a surface pressure of 0-0.3MPa, and then final polycondensation is performed under vacuum conditions, wherein the vacuum is evacuated to a vacuum degree of -(0.01~0.08)MPa to obtain a copolymeramide melt, and finally pelletized and dried to obtain a copolymeramide resin.

Unless otherwise stated or clearly contradictory, the pressures mentioned in this invention are gauge pressures.

The preparation method of the polyamide 56 salt solution can be conventional in the art. Furthermore, under nitrogen conditions, 1,5-pentanediamine, adipic acid and water are uniformly mixed to obtain the polyamide 56 salt solution; further, the molar ratio of 1,5-pentanediamine and adipic acid is (1-1.1):1.

The preparation method of the polyamide 66 salt solution can be conventional in the art. Further, under nitrogen conditions, hexamethylenediamine, adipic acid and water are uniformly mixed to obtain the polyamide 66 salt solution; further, the molar ratio of hexamethylenediamine and adipic acid is (1-1.1):1.

Furthermore, in step 1), the concentration of the polyamide 56 salt solution is 30-90wt.%, further 60-75wt.%; the percentage is the mass percentage of the polyamide salt in the polyamide salt solution.

Furthermore, in step 1), the concentration of the polyamide 66 salt aqueous solution is 20~70wt.%, further 50~60wt.%; the percentage is the mass percentage of the polyamide 66 salt in the polyamide 66 salt aqueous solution.

Furthermore, in step 1), in the mixed salt solution, the molar ratio of polyamide 56 salt in the polyamide 56 salt solution to polyamide 66 salt in the polyamide 66 salt solution is (95:5)-(20:80), further (95:5)-(35:65), further (95:5)-(50:50), further (95:5)-(65:35).

Furthermore, in step 2), the temperature of the reaction system is 220-260°C when the pressure maintenance is completed; the temperature of the reaction system is 240-280°C after the pressure reduction is completed; and the temperature of the reaction system is 260-290°C after the vacuuming.

Furthermore, the drying equipment in step 2) is a vacuum drum dryer or a continuous dehumidifying heat nitrogen dryer, the drying temperature is 80~120℃, further 90~115℃; the drying time is 8~25h, further 13~20h.

Furthermore, the method may also include step a) before step 1), mixing pentamethylenediamine, adipic acid and water evenly under nitrogen conditions to prepare a polyamide 56 salt solution. The polyamide 56 salt solution has the above-mentioned limitations.

Furthermore, the method may also include step b) before step 1), in which hexamethylenediamine, adipic acid and water are mixed evenly under nitrogen conditions to prepare a polyamide 66 salt solution. The polyamide 66 salt solution has the above-mentioned limitations.

The polyamide 56 salt solution and/or the polyamide 66 salt solution may include additives, or additives may be added at any stage of step a), step b), step 1) and/or step 2), wherein the additives include any one or more of a capping agent, a catalyst, a flame retardant, an antioxidant, an ultraviolet absorber, an infrared absorber, a crystallization nucleating agent, a fluorescent brightener and an antistatic agent; further, the amount of the additive added accounts for 0-1wt% of the total weight of 1,5-pentanediamine, hexamethylenediamine, and adipic acid monomers.

Furthermore, the end-capping agent includes: any one or a combination of two or more of aliphatic carboxylic acids of C2 to C16 and aromatic carboxylic acids of C7 to C9.

The C2~C16 aliphatic carboxylic acid includes any one of acetic acid, adipic acid, deca-dicarboxylic acid, undeca-dicarboxylic acid, and dodeca-dicarboxylic acid, or a combination of two or more thereof.

The C7~C9 aromatic carboxylic acid includes any one or a combination of two or more of terephthalic acid, isophthalic acid, phthalic acid, and benzoic acid.

The end-capping agent is further a combination of aliphatic carboxylic acids of C2~C16 and aromatic carboxylic acids of C7~C9, and the mass ratio of aliphatic carboxylic acids of C2~C16 to aromatic carboxylic acids of C7~C9 is (8-1):1, and further (5-1):1.

Furthermore, the end-capping agent is a combination of decanedioic acid and terephthalic acid, and the mass ratio of the decanedioic acid to terephthalic acid is (8-1):1, and further is (5-1):1.

Furthermore, the end-capping agent is a combination of decanedioic acid and benzoic acid, and the mass ratio of the decanedioic acid to benzoic acid is (8-1):1, and further is (5-1):1.

The amount of the end-capping agent added is 300-10000ppm based on the total weight of 1,5-pentanediamine, hexamethylenediamine, and adipic acid monomers. Further, it is 800-7000ppm.

Furthermore, the antioxidant includes any one or a combination of two or more of sodium hypophosphite, sodium hypophosphite acetate, calcium hypophosphite, phosphorous acid, antioxidant 1010, and antioxidant 1097.

The amount of the antioxidant added is 5-300ppm of the total weight of 1,5-pentanediamine, hexamethylenediamine, and adipic acid monomers. Further, 10-200ppm.

The third object of the present invention is to provide a copolymer amide fiber with excellent comprehensive properties.

The copolymer amide fiber includes undrawn yarn (UDY), pre-oriented yarn (POY), highly oriented yarn (HOY), fully oriented yarn (FOY), fully drawn yarn (FDY), drawn false twisted yarn (DTY), continuous bulked deformed filament (BCF), staple fiber, industrial yarn, and monofilament, and further includes fully drawn yarn, continuous bulked deformed filament, industrial yarn, and monofilament.

25%，進一步為

23%，更進一步為

20%，更進一步為

15%；及/或所述共聚醯胺纖維的斷裂強度為

2.2cN/dtex，進一步為

3.5cN/dtex，進一步為

3.8cN/dtex，更進一步為

4.2cN/dtex，更進一步為

6cN/dtex；及/或所述共聚醯胺纖維的斷裂伸長率

55%，進一步為

50%，更進一步為

45%，更進一步為

40%；及/或所述共聚醯胺纖維的初始模量為

55cN/dtex，進一步為

53cN/dtex，更進一步為

50cN/dtex；及/或所述共聚醯胺纖維的熱捲曲率

35%，進一步為

40%，更進一步為

45%；及/或所述共聚醯胺纖維的回潮率為

5.0%，進一步為

4.8%，更進一步為

4.7%；及/或所述共聚醯胺纖維的染色均勻度(灰卡)為

3.5級，進一步為

4.0級，更進一步為

4.5級；及/或所述共聚醯胺纖維的皂洗牢度：褪色牢度為

3.5級，進一步為

4.0級，更進一步為

4.5級；及/或所述共聚醯胺纖維的沾色牢度為

3.5級，進一步為

4.0級，更進一步為

4.5級。 The copolymer amide fiber meets the following conditions: the boiling water shrinkage rate of the copolymer amide fiber

25%, further

23%, and further

20%, and further

15%; and/or the breaking strength of the copolymer amide fiber is

2.2cN/dtex, further

3.5cN/dtex, further

3.8cN/dtex, further

4.2cN/dtex, further

6cN/dtex; and/or the elongation at break of the copolymer amide fiber

55%, further

50%, and further

45%, and further

40%; and/or the initial modulus of the copolymer amide fiber is

55cN/dtex, further

53cN/dtex, further

50cN/dtex; and/or the thermal roll curvature of the copolymer amide fiber

35%, further

40%, and further

45%; and/or the moisture regain of the copolymer amide fiber is

5.0%, further

4.8%, and further

4.7%; and/or the dyeing uniformity (gray card) of the copolymer amide fiber is

3.5, further

Level 4.0, further

4.5; and/or the soap fastness of the copolymer amide fiber: fading fastness is

3.5, further

Level 4.0, further

4.5; and/or the color fastness of the copolymer amide fiber is

3.5, further

Level 4.0, further

Level 4.5.

Oligomers are defects in the mechanical properties test process. Reducing the oligomer content in copolymer amide is beneficial to improving the mechanical properties of polymer resin. In addition, the oligomer content in copolymer amide resin is low, and very few oligomer molecules are produced in the fiber preparation process. The fiber is more stable, has a high moisture regain, high fading fastness, high staining fastness, and improved mechanical properties.

If oligomers enter the spinning section with the slices, it will not only cause serious consequences to the spinning process, but also be a great waste of raw materials. Oligomers are mainly produced in the polymerization stage, and the degree of polymerization is generally 1~8. For example, monomers polymerize to form dimers and trimers, and oligomers can be extracted by hot water. A high content of oligomers will affect the molecular weight distribution of the slices, and in the melt spinning process, these oligomers will evaporate from the melt and become gas, increasing the bubbles in the polyamide melt. The evaporated gas will also deteriorate the spinning environment after solidification. In addition, oligomers are also easy to precipitate on the surface of the filament, affecting the performance of the fiber.

The fourth object of the present invention is to provide a method for preparing copolymer amide fiber.

The preparation method comprises the following steps: 1) heating the copolymeramide resin to a molten state to form a copolymeramide melt; 2) transporting the copolymeramide melt to a spinning box through a melt pipe, and injecting it into a spinning element after being accurately metered by a metering pump, and extruding it from a nozzle hole to obtain spun yarn, wherein a single body suction device is provided under the nozzle plate; and 3) post-treating the obtained spun yarn to obtain copolymeramide fiber, wherein the post-treatment comprises: cooling, and/or oiling, and/or stretching, and/or shaping.

Furthermore, the post-treatment of step 3) includes: cooling, oiling, stretching, shaping, and winding the extruded primary yarn to obtain the fully drawn copolymeramide yarn; further, the oiling rate is 0.4-1.2%, and further 0.45-1.1%.

Furthermore, the post-treatment of step 3) includes: heat preservation, cooling, oiling, pre-netting, multi-stage stretching, tension setting, relaxation setting, main netting, and winding of the obtained primary yarn to obtain the copolymerized amide industrial yarn.

Furthermore, the post-treatment of step 3) includes: cooling, oiling, stretching, shaping, bulking, cold drum cooling, main network, and winding the prepared primary yarn to obtain the copolymer amide continuous bulked filament.

Furthermore, the post-treatment of step 3) includes: subjecting the obtained primary yarn to water bath cooling, primary stretching, secondary stretching, heat setting, and winding to obtain the copolymerized amide monofilament.

The heating in step 1) is carried out by a screw, and the screw is a four-zone heating mode, wherein the temperature of zone 1 is 220-270°C, further 230-265°C; the temperature of zone 2 is 230-280°C, further 240-275°C; the temperature of zone 3 is 240-290°C, further 250-285°C; and the temperature of zone 4 is 250-300°C, further 260-295°C.

Step 2) The spinning box temperature is 260-300°C, further 270-295°C; the component pressure is 10-17MPa, further 12-15MPa.

Step 3) The cooling wind speed is 0.3-0.7m/s, further 0.4-0.6m/s; the wind temperature is 16-22℃, further 18-21℃; the wind humidity is 65-95%, further 70-90%.

Step 3) The stretching ratio is 1.3-5.5, further 1.5-4.8; the setting temperature is 140-210℃, further 150-180℃.

The post-processing described in step 3) includes winding processing, and the winding speed is 2200-5500m/min, and further 2500-5200m/min.

The fifth object of the present invention is to provide a copolymer amide fiber for use in knitted and woven fabrics, carpet yarns, blended yarns, monofilaments or industrial yarns.

Due to the adoption of the above scheme, the beneficial effects of the present invention are:

First, the raw material 1,5-pentanediamine used to produce the copolymer amide fiber of the present invention is made by biological methods and is a green material. It does not rely on petroleum resources and does not cause serious pollution to the environment. It can also reduce carbon dioxide emissions and the generation of greenhouse effects, and adapt to the trend of carbon neutrality development.

Second, the copolymer amide resin of the present invention has the advantages of moderate viscosity, moisture content and terminal amino group content, low oligomer content, large molecular weight and narrow molecular weight distribution, and can meet the requirements for use in the textile field.

Third, the copolymer amide fiber of the present invention has good mechanical properties, thermal shrinkage properties, softness and dyeing properties, and has excellent comprehensive performance.

The test method involved in the embodiment is as follows:

1) Relative viscosity: by the concentrated sulfuric acid method using an Oberleitner viscometer: accurately weigh 0.25±0.0002g of the dried polyamide slices, add 50mL of concentrated sulfuric acid (96wt%) to dissolve; measure and record the concentrated sulfuric acid flow time _t0 and the polyamide sample solution flow time t in a 25℃ constant temperature water bath. Relative viscosity calculation formula: relative viscosity = t/ _t0 ; t-solution flow time; _t0 -concentrated sulfuric acid flow time.

2) Oligomer content: Use water extraction method (weighing method): Accurately weigh about 8g of copolymer amide resin dried at 130℃ for 7 hours (actual mass is recorded as m ₁ ), place in a 500mL round-bottom flask, add 400g of water, heat and reflux at 97℃~100℃ in a heating jacket for 36h, decant the solution, dry the particles at 130℃ in a constant weight flask for 7 hours, then seal in an aluminum plastic bag, cool and weigh (mass is recorded as m ₂ ), and calculate its weight loss (m ₁ -m ₂ ). Oligomer content (%) = (m ₁ -m ₂ )/m ₁ *100%.

3) Number average molecular weight and molecular weight distribution: determined by gel permeation chromatography (GPC).

4) Breaking strength, elongation at break, initial modulus: refer to GB/T 14344-2008 Test method for tensile properties of chemical fibers; apply 0.05±0.005cN/dtex pre-tension, clamping distance 500mm, tensile speed 500mm/min. Modulus = breaking strength corresponding to elongation at break of 1% × 100.

5) Moisture regain: Put the washed fiber in a loose state into an oven for drying, and then place the dried fiber sample in the standard atmosphere specified in GB/T6529 for adjustment and balance. The sample after washing and moisturizing is subjected to moisture regain measurement. The moisture regain measurement method is carried out in accordance with GB/T6503, where the drying temperature of the oven is 105°C and the drying time is 1h.

6) Boiling water shrinkage: measured in accordance with GB/6505.

7) Dyeing uniformity (gray card)/grade: FZ/T 50008 Test method for dyeing uniformity of nylon filaments.

8) Soap fastness (fading fastness, staining fastness): measured in accordance with the national standard GB/T 3921.1-1997.

9) Hot roll curvature: Use the oven in the self-made length measuring device to carry out according to FZ/T 50030-2015.

10) Yellowness index: According to ASTMD1925, use the measuring instrument 3600D and the CLE lab color difference evaluation standard to measure the yellowness index of the sample.

Embodiment 1

The preparation method of the copolymerized amide resin comprises the following steps: 1) under nitrogen conditions, 1,5-pentanediamine, adipic acid, a capping agent, an antioxidant and water are uniformly mixed to obtain a 60wt.% polyamide 56 salt solution; wherein the molar ratio of 1,5-pentanediamine to adipic acid is (1-1.04):1; 2) under nitrogen conditions, hexamethylenediamine, adipic acid, a capping agent, an antioxidant and water are uniformly mixed to obtain a 60wt.% polyamide 66 salt solution; wherein the molar ratio of hexamethylenediamine to adipic acid is (1-1.0 6): 1; and 3) polyamide 56 salt solution and polyamide 66 salt solution are mixed in a molar ratio of 85:15 for polyamide 56 salt and polyamide 66 salt, heated and concentrated, and firstly prepolymerized to raise the internal pressure of the reaction system to 2.45Mpa, exhaust and maintain the pressure, and then reduce the pressure to reduce the internal pressure of the reaction system to a surface pressure of 0MPa, and then perform final polycondensation under vacuum conditions, wherein the vacuum is evacuated to a vacuum degree of -0.07MPa to obtain a copolymeramide melt, and finally pelletized and dried to obtain a copolymeramide resin.

In the step 2), the temperature of the reaction system is 260°C at the end of the pressure maintenance; the temperature of the reaction system is 265°C after the pressure reduction; the temperature after the vacuum is 273°C; in the step 3), the drying equipment is a continuous dehumidifying nitrogen dryer, the drying temperature is 90°C, and the drying time is 22h.

The total amount of each raw material is shown in Table 1.

Embodiment 2

The preparation method of the copolymerized amide resin comprises the following steps: 1) under nitrogen conditions, 1,5-pentanediamine, adipic acid, a capping agent, an antioxidant and water are uniformly mixed to obtain a 60wt.% polyamide 56 salt solution; wherein the molar ratio of 1,5-pentanediamine to adipic acid is (1-1.06):1; 2) under nitrogen conditions, hexamethylenediamine, adipic acid, a capping agent, an antioxidant and water are uniformly mixed to obtain a 60wt.% polyamide 66 salt solution; wherein the molar ratio of hexamethylenediamine to adipic acid is (1-1.06):1. ): 1; and 3) Mixing polyamide 56 salt solution and polyamide 66 salt solution in a molar ratio of 70:30 of polyamide 56 salt and polyamide 66 salt, heating and concentrating, firstly prepolymerizing, raising the internal pressure of the reaction system to 2.25MPa, exhausting and maintaining the pressure, then reducing the pressure to reduce the internal pressure of the reaction system to a surface pressure of 0MPa, and then performing final polycondensation under vacuum conditions, wherein the vacuum is evacuated to a vacuum degree of -0.08MPa, to obtain a copolymerized amide melt, and finally pelletizing and drying to obtain a copolymerized amide resin.

In the step 2), the temperature of the reaction system is 260°C at the end of the pressure maintenance; the temperature of the reaction system is 265°C after the pressure reduction; the temperature after the vacuum is 272°C; in the step 3), the drying equipment is a continuous dehumidifying nitrogen dryer, the drying temperature is 110°C, and the drying time is 12h.

The total amount of each raw material is shown in Table 1.

Example 3-A

The preparation method of the copolymerized amide resin comprises the following steps: 1) under nitrogen conditions, 1,5-pentanediamine, adipic acid, a capping agent, an antioxidant and water are uniformly mixed to obtain a 60wt.% polyamide 56 salt solution; wherein the molar ratio of 1,5-pentanediamine to adipic acid is (1-1.04):1; 2) under nitrogen conditions, hexamethylenediamine, adipic acid, a capping agent, an antioxidant and water are uniformly mixed to obtain a 60wt.% polyamide 66 salt solution; wherein the molar ratio of hexamethylenediamine to adipic acid is (1-1.0 5): 1; and 3) polyamide 56 salt solution and polyamide 66 salt solution are mixed in a molar ratio of polyamide 56 salt to polyamide 66 salt of 60:40, heated and concentrated, and firstly prepolymerized to raise the internal pressure of the reaction system to 2.2MPa, exhaust and maintain the pressure, and then reduce the pressure to reduce the internal pressure of the reaction system to a surface pressure of 0MPa, and then perform final polycondensation under vacuum conditions, wherein the vacuum is evacuated to a vacuum degree of -0.05MPa, to obtain a copolymerized amide melt, and finally pelletized and dried to obtain a copolymerized amide resin.

In the step 2), the temperature of the reaction system at the end of the pressure maintenance is 262°C; the temperature of the reaction system after the pressure reduction is 266°C; the temperature after the vacuum is 270°C; in the step 3), the drying equipment is a continuous dehumidifying nitrogen dryer, the drying temperature is 105°C, and the drying time is 16h.

The total amount of each raw material is shown in Table 1.

Embodiment 3-B to Embodiment 3-F

Embodiment 3-B to Embodiment 3-F are basically the same as Embodiment 3-A, the only difference is the amount of raw materials used, the amount of raw materials used is shown in Table 1.

Embodiment 4

The preparation method of the copolymerized amide resin comprises the following steps: 1) under nitrogen conditions, 1,5-pentanediamine, adipic acid, a capping agent, an antioxidant and water are uniformly mixed to obtain a 60wt.% polyamide 56 salt solution; wherein the molar ratio of 1,5-pentanediamine to adipic acid is (1-1.08):1; 2) under nitrogen conditions, hexamethylenediamine, adipic acid, a capping agent, an antioxidant and water are uniformly mixed to obtain a 60wt.% polyamide 66 salt solution; wherein the molar ratio of hexamethylenediamine to adipic acid is (1-1.0 7): 1; and 3) polyamide 56 salt solution and polyamide 66 salt solution are mixed in a molar ratio of polyamide 56 salt to polyamide 66 salt of 35:65, heated and concentrated, and firstly prepolymerized to raise the internal pressure of the reaction system to 2.3MPa, exhaust and maintain the pressure, and then reduce the pressure to reduce the internal pressure of the reaction system to a surface pressure of 0MPa, and then perform final polycondensation under vacuum conditions, wherein the vacuum is evacuated to a vacuum degree of -0.04MPa, to obtain a copolymerized amide melt, and finally pelletized and dried to obtain a copolymerized amide resin.

In the step 2), the temperature of the reaction system is 258°C when the pressure maintenance is completed; the temperature of the reaction system is 265°C after the pressure reduction is completed; the temperature after the vacuum is 275°C; in the step 3), the drying equipment is a continuous dehumidifying heat nitrogen dryer, the drying temperature is 95°C, and the drying time is 20h.

The total amount of each raw material is shown in Table 1.

Embodiment 5

The preparation method of the copolymerized amide resin comprises the following steps: 1) under nitrogen conditions, 1,5-pentanediamine, adipic acid, a capping agent, an antioxidant and water are uniformly mixed to obtain a 60wt.% polyamide 56 salt solution; wherein the molar ratio of 1,5-pentanediamine to adipic acid is (1-1.05):1; 2) under nitrogen conditions, hexamethylenediamine, adipic acid, a capping agent, an antioxidant and water are uniformly mixed to obtain a 60wt.% polyamide 66 salt solution; wherein the molar ratio of hexamethylenediamine to adipic acid is (1-1.0 8): 1; and 3) polyamide 56 salt solution and polyamide 66 salt solution are mixed in a molar ratio of polyamide 56 salt to polyamide 66 salt of 20:80, heated and concentrated, and firstly prepolymerized to raise the internal pressure of the reaction system to 2.4MPa, exhaust and maintain the pressure, and then reduce the pressure to reduce the internal pressure of the reaction system to a surface pressure of 0MPa, and then perform final polycondensation under vacuum conditions, wherein the vacuum is evacuated to a vacuum degree of -0.08MPa to obtain a copolymeramide melt, and finally pelletized and dried to obtain a copolymeramide resin.

In the step 2), the temperature of the reaction system is 258°C when the pressure maintenance is completed; the temperature of the reaction system is 265°C after the pressure reduction is completed; the temperature after the vacuum is 276°C; in the step 3), the drying equipment is a continuous dehumidifying nitrogen dryer, the drying temperature is 110°C, and the drying time is 16h.

The total amount of each raw material is shown in Table 1.

The relative viscosity, terminal amino group content, number average molecular weight, molecular weight distribution, oligomer content, and yellow index of the raw materials and prepared resins of Examples 1-5 are shown in Table 1.

Embodiments 6 to 15

The method for preparing the fully drawn copolymeramide yarn comprises the following steps: 1) heating the copolymeramide resin prepared in the above embodiment to a molten state to form a copolymeramide melt; 2) transporting the copolymeramide melt to a spinning box through a melt pipe, injecting it into a spinning element after being accurately metered by a metering pump, and extruding it from a nozzle hole, wherein a single body suction device is provided under the nozzle plate; and 3) cooling, oiling, stretching, shaping, and winding the extruded primary fiber to obtain the fully drawn copolymeramide yarn.

The heating in step 1) is carried out by a screw, and the screw is a four-zone heating mode, wherein the temperature of zone 1 is 260°C; the temperature of zone 2 is 270°C; the temperature of zone 3 is 280°C; and the temperature of zone 4 is 290°C.

The spinning box temperature is 290℃; the component pressure is 15MPa. The cooling wind speed is 0.42m/s; the wind temperature is 18℃; the wind humidity is 80%. The oiling rate is 1.1%. The stretching multiple is 1.65, and the setting temperature is 160℃. The winding speed is 4800m/min.

The performance indicators of the resin raw materials and copolymer amide fully drawn yarns used in Examples 6 to 15 are shown in Table 2.

Embodiments 16 to 19

The method for preparing copolymerized amide industrial yarn comprises the following steps: 1) the copolymerized amide resin prepared in the above embodiment is solid-phase thickened to 3.2, and heated to a molten state to form a copolymerized amide melt; 2) the copolymerized amide melt is transported to a spinning box through a melt pipeline, and after being accurately metered by a metering pump, it is injected into a spinning element and extruded from a nozzle hole, wherein a single body suction device is arranged under the nozzle plate; 3) the prepared primary yarn is subjected to heat preservation, cooling, oiling, pre-netting, multi-stage stretching, tension setting, relaxation setting, main netting, and winding to obtain the above-mentioned Copolyamide industrial yarn; the stretching process uses 5 pairs of hot rollers and is divided into four stages of stretching. The stretching process is as follows: the oiled primary yarn is first fed to the first pair of hot rollers, and the first stage pre-stretching is performed between the first pair of hot rollers and the second pair of hot rollers, and then the second stage main stretching is performed between the second pair of hot rollers and the third pair of hot rollers, and the third stage main stretching and tension heat setting are performed between the third pair of hot rollers and the fourth pair of hot rollers, and then the fourth stage secondary stretching and relaxation heat setting are performed between the fourth pair of hot rollers and the fifth pair of hot rollers, and finally winding is performed.

The heating in step 1) is carried out by a screw, and the screw is a four-zone heating mode, wherein the temperature of zone 1 is 265°C; the temperature of zone 2 is 275°C; the temperature of zone 3 is 285°C; and the temperature of zone 4 is 295°C.

The spinning box temperature is 293°C; the component pressure is 11MPa.

The cooling wind speed is 0.55m/s; the wind temperature is 20℃; and the wind humidity is 78%.

The oiling rate is 1.2%.

The total stretching ratio of the stretching is 5.2, the tension heat setting temperature is 215°C, the relaxation heat setting temperature is 120°C, and the winding speed is 2800m/min.

The performance indicators of the resin raw materials and copolymerized amide industrial yarns used in Examples 16 to 19 are shown in Table 3.

Embodiments 20 to 23

The method for preparing continuous expanded copolymer amide filaments comprises the following steps: 1) heating the copolymer amide resin prepared in the above embodiment to a molten state to form a copolymer amide melt; 2) transporting the copolymer amide melt to a spinning box through a melt pipe, injecting the copolymer amide melt into a spinning element after being accurately metered by a metering pump, and extruding the melt from a nozzle hole, wherein a monomer suction device is provided below the nozzle plate; and 3 ) The obtained primary yarn is cooled, oiled, stretched, shaped, deformed by an expander, cooled by a cold drum, main meshed, and wound to obtain the copolymeramide continuous expanded filament; the heating in step 1) is performed by a screw, and the screw is a four-zone heating mode, wherein the temperature of the first zone is 265°C; the temperature of the second zone is 270°C; the temperature of the third zone is 280°C; and the temperature of the fourth zone is 290°C.

The spinning box temperature is 285℃; the component pressure is 10MPa. The cooling wind speed is 0.5m/s; the wind temperature is 20℃; the wind humidity is 80%. The oiling rate is 1.1%. The expansion deformation temperature is 230℃. The winding speed during winding molding is 3000m/min.

The performance indicators of the resin raw materials and copolymerized amide continuous expanded filaments used in Examples 20 to 23 are shown in Table 4.

Embodiments 24 to 27

The method for preparing copolymerized amide monofilament comprises the following steps: 1) heating the copolymerized amide resin prepared in the above embodiment to a molten state to form a copolymerized amide melt; 2) transporting the copolymerized amide melt to a spinning box through a melt pipe, and injecting it into a spinning element after being accurately metered by a metering pump, and extruding it from a nozzle hole; 3) subjecting the obtained primary yarn to water bath cooling, primary stretching, secondary stretching, heat setting, and winding to obtain the copolymerized amide monofilament.

The heating in step 1) is carried out by a screw, and the screw is a four-zone heating mode, with the temperature of the first zone being 265°C; the temperature of the second zone being 275°C; the temperature of the third zone being 280°C; and the temperature of the fourth zone being 285°C.

The spinning box temperature is 285°C; the component pressure is 11MPa.

In step 3), the water bath cooling temperature is 30°C, the first-stage stretching ratio is 3.0, the second-stage stretching ratio is 1.5, the total stretching ratio is 4.5, the stretching temperature is 100°C, and the heat setting temperature is 220°C; The winding speed is 180m/min.

The performance indicators of the resin raw materials and copolymerized amide monofilaments used in Examples 24 to 27 are shown in Table 5.

The above is only the best implementation of the present invention. It should be pointed out that those with ordinary knowledge in the technical field to which the present invention belongs can make some improvements and modifications without departing from the concept of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims (19)

A copolymer amide resin is characterized in that the copolymer amide resin comprises the following chain segments: chain segment A): -NH(CH ₂ ) ₅ NH CO(CH ₂ ) ₄ CO-, and chain segment B): -NH(CH ₂ ) ₆ NH CO(CH ₂ ) ₄ CO-; wherein the molar ratio of the chain segment A) to the chain segment B) is (85:15)-(20:80), and the terminal amino group content of the copolymer amide resin is 30-80 mmol/kg; the copolymer amide resin contains additives, and the additives include a capping agent and an antioxidant, and any one or a combination of two or more of a catalyst, a flame retardant, an ultraviolet absorber, an infrared absorber, a crystallization nucleating agent, a fluorescent brightener and an antistatic agent that are optionally present; the capping agent is a combination of a C2-C16 aliphatic carboxylic acid and a C7-C9 aromatic carboxylic acid. The copolymer amide resin of claim 1 is characterized in that the molar ratio of the chain segment A) to the chain segment B) is (85:15)-(35:65); and/or the relative viscosity of the copolymer amide resin is 2.4-3.7; and/or the terminal amino group content of the copolymer amide resin is 45-52.5 mmol/kg; and/or the oligomer content of the copolymer amide is

1.0wt%; and/or, the yellowness index of the copolymer amide resin is

6.5; and/or, the number average molecular weight of the copolymer amide resin is 1.5*10 ⁴ -4.0*10 ⁴ g/mol; and/or, the molecular weight distribution of the copolymer amide resin is 1.4-2.5. The copolymer amide resin of claim 2 is characterized in that the relative viscosity of the copolymer amide resin is 2.65-3.0. The copolymeramide resin of claim 2 is characterized in that the number average molecular weight of the copolymeramide resin is 2.2*10 ⁴ -3.0*10 ⁴ g/mol. The copolymer amide resin of claim 2 is characterized in that the molecular weight distribution of the copolymer amide resin is 1.8-2.3. The copolymer amide resin of claim 2 is characterized in that the raw materials for preparing the copolymer amide resin include 1,5-pentanediamine, hexamethylenediamine, and adipic acid monomers, and the amount of the additive added is less than 1wt% of the total weight of the 1,5-pentanediamine, hexamethylenediamine, and adipic acid monomers; and/or the C7-C9 aromatic carboxylic acid includes any one or a combination of two or more of terephthalic acid, isophthalic acid, phthalic acid, and benzoic acid; and/or the C2-C16 aliphatic carboxylic acid includes any one or two or more of acetic acid, adipic acid, deca-dicarboxylic acid, undecane-dicarboxylic acid, and dodeca-dicarboxylic acid. and/or, the end-capping agent is a combination of deca-dicarboxylic acid and terephthalic acid; and/or, the end-capping agent is a combination of deca-dicarboxylic acid and benzoic acid; and/or, the content of the end-capping agent accounts for 300-10000ppm of the total weight of 1,5-pentanediamine, hexamethylenediamine, and adipic acid monomers; and/or, the antioxidant includes any one of sodium hypophosphite, calcium hypophosphite, phosphorous acid, antioxidant 1010, and antioxidant 1097, or a combination of two or more thereof; and/or, the content of the antioxidant accounts for 5-300ppm of the total weight of 1,5-pentanediamine, hexamethylenediamine, and adipic acid monomers. The copolymer amide resin of claim 6 is characterized in that the end-capping agent is a combination of decanedioic acid and terephthalic acid. The copolymer amide resin of claim 6 is characterized in that the end-capping agent is a combination of deca-dicarboxylic acid and benzoic acid. A method for preparing a copolymerized amide resin is characterized in that it comprises the following steps: 1) mixing a polyamide 56 salt solution with a polyamide 66 salt solution to obtain a mixed salt solution; or, under nitrogen conditions, uniformly mixing 1,5-pentanediamine, hexamethylenediamine, adipic acid and water in a certain molar ratio to directly obtain a mixed salt solution, in which the polyamide 56 salt solution is mixed with water; The molar ratio of the polyamide 56 salt in the polyamide 56 salt solution to the polyamide 66 salt in the polyamide 66 salt solution is (85:15)-(20:80); 2) the mixed salt solution is heated and concentrated, and firstly prepolymerized to raise the internal pressure of the reaction system to 0.3-2.45MPa, exhaust and maintain the pressure, and then reduce the pressure to reduce the internal pressure of the reaction system to the surface The polyamide 56 salt solution and/or the polyamide 66 salt solution contain additives, or at any stage of step 1) and/or step 2) Adding additives in the first stage; the additives include end-capping agents and antioxidants, and any one or a combination of two or more of the optional catalysts, flame retardants, ultraviolet absorbers, infrared absorbers, crystallization nucleating agents, fluorescent brighteners and antistatic agents; The end-capping agent is a combination of aliphatic carboxylic acids of C2~C16 and aromatic carboxylic acids of C7~C9. The method for preparing the copolymerized amide resin of claim 9 is characterized in that, in step 1), the concentration of the polyamide 56 salt solution is 30-90 wt.%; and/or, in step 1), the concentration of the polyamide 66 salt aqueous solution is 20-70 wt.%; and/or, in step 1), in the mixed salt solution, the molar ratio of the polyamide 56 salt in the polyamide 56 salt solution to the polyamide 66 salt in the polyamide 66 salt solution is (85:15)-(35:65); and/or, in step 2), The temperature of the reaction system at the end of the pressure maintenance is 220-260°C; and/or, in step 2), the temperature of the reaction system after the pressure reduction is 240-280°C; and/or, in step 2), the temperature after vacuuming is 260-290°C; and/or, in step 2), the drying equipment is a vacuum drum dryer or a continuous dehumidifying hot nitrogen dryer; and/or, in step 2), the drying temperature is 80~120°C; and/or, in step 2), the drying time is 8~25h. A copolymeramide fiber, characterized in that the copolymeramide fiber is made from a copolymeramide resin as described in any one of claims 1 to 8 or a copolymeramide resin obtained by a method as described in any one of claims 9 to 10, and the copolymeramide fiber includes undrawn yarn (UDY), pre-oriented yarn (POY), highly oriented yarn (HOY), fully oriented yarn (FOY), fully drawn yarn (FDY), drawn false twisted yarn (DTY), continuous bulked deformed filament (BCF), staple fiber, industrial yarn, and monofilament; and/or, the boiling water shrinkage of the copolymeramide fiber

25%; and/or the breaking strength of the copolymer amide fiber is

2.2 cN/dtex; and/or, the elongation at break of the copolymer amide fiber

55%; and/or, the initial modulus of the copolymer amide fiber is

55cN/dtex; and/or, the curvature of the thermal roll of the copolymer amide fiber

35%; and/or, the moisture regain of the copolymer amide fiber is

5.0%; and/or, the dyeing uniformity (gray card) of the copolymer amide fiber is

3.5; and/or, the soap fastness of the copolymer amide fiber: fading fastness is

3.5; and/or, the color fastness of the copolymer amide fiber is

Level 3.5. The copolymer amide fiber of claim 11, wherein the copolymer amide fiber has a boiling water shrinkage of

15%. The copolymer amide fiber of claim 11, wherein the copolymer amide fiber has a breaking strength of

6cN/dtex; and the elongation at break of the copolymer amide fiber

40%. The copolymer amide fiber of claim 11 is characterized in that the thermal curvature of the copolymer amide fiber is

45%. The copolymer amide fiber of claim 11 is characterized in that the moisture regain of the copolymer amide fiber is

4.7%. The copolymer amide fiber of claim 11 is characterized in that the dyeing uniformity (gray card) of the copolymer amide fiber is

Grade 4.5; the fading fastness of the copolymer amide fiber is

4.5, and the color fastness of the copolymer amide fiber is

Level 4.5. A method for preparing copolymerized amide fibers, characterized in that it comprises the following steps: 1) heating the copolymerized amide resin as described in any one of claims 1 to 8 or the copolymerized amide resin obtained by the method as described in any one of claims 9 to 10 to a molten state to form a copolymerized amide melt; 2) transporting the copolymerized amide melt to a spinning box through a melt pipe, injecting it into a spinning element after being accurately metered by a metering pump, and extruding it from a nozzle hole to obtain spun yarn, wherein a single body suction device is provided under the nozzle plate; and 3) post-treating the obtained spun yarn to obtain copolymerized amide fibers, wherein the post-treatment comprises: cooling, and/or oiling, and/or stretching, and/or shaping. The method for preparing copolymerized amide fiber of claim 17 is characterized in that the heating in step 1) is performed by a screw, and the screw is a four-zone heating mode, wherein the temperature of zone 1 is 220-270°C; the temperature of zone 2 is 230-280°C; the temperature of zone 3 is 240-290°C; and the temperature of zone 4 is 250-300°C; and/or, in step 2), the temperature of the spinning box is 260-300°C; and /or, step 2) the pressure of the spinning assembly is 10-17MPa; and/or, step 3) the cooling wind speed is 0.3-0.7m/s; the wind temperature is 16-22℃ and the wind humidity is 65-95%; and/or, step 3) the stretching ratio is 1.3-5.5; and/or, step 3) the shaping temperature is 140-210℃; and/or, The post-treatment described in step 3) includes winding treatment, the winding speed The speed is 2200-5500m/min; and/or, the post-treatment in step 3) includes: cooling, oiling, stretching, shaping, and winding the extruded spun yarn to obtain the fully drawn copolymeramide yarn; and/or, the post-treatment in step 3) includes: heat preservation, cooling, oiling, pre-netting, multi-stage stretching, tension shaping, relaxation shaping, main netting, and winding the prepared spun yarn to obtain the copolymer. amide industrial yarn; and/or, the post-treatment described in step 3) includes: cooling, oiling, stretching, shaping, bulking, cold drum cooling, main network, and winding the obtained spun yarn to obtain the copolymeramide continuous expanded filament; and/or, the post-treatment described in step 3) includes: water bath cooling, primary stretching, secondary stretching, heat setting, and winding molding the obtained spun yarn to obtain the copolymeramide monofilament. An application of a copolymer amide fiber as claimed in any one of claims 11 to 16 in the fields of knitted and woven fabrics, carpet yarns, blended yarns, monofilaments or industrial yarns.