WO2023273306A1 - Copolyamide resin, fiber, preparation method therefor and application thereof - Google Patents

Abstract

Provided in the present invention are a copolyamide resin, a fiber, a preparation method therefor and an application thereof. The copolyamide resin comprises the following segments: segment A): -NH(CH2)5NH CO(CH2)4CO-, and segment B): -NH(CH2)6NH CO(CH2)4CO-; a mole fraction ratio of the segment A) to the segment B) is (95:5)-(5:95), and a terminal amino group content of the copolyamide resin is 30-80 mmol/kg. The copolyamide resin of the present invention has advantages such as moderate viscosity, moisture content and terminal amino group content, low oligomer content, high molecular weight and narrow molecular weight distribution, and can meet requirements for use in the spinning field. Fibers obtained by spinning have excellent overall properties.

Description

A kind of copolyamide resin, fiber and its preparation method and application technical field

The invention belongs to the technical field of polyamide materials, and relates to a copolyamide resin, a fiber and a preparation method and application thereof.

Background technique

Copolyamide is a polyamide product formed by the polymerization of two or more polyamide monomers. By selecting suitable comonomers or polymers, polyamide can be modified by copolymerization, and its melting point, crystallinity, solubility and transparency can be greatly changed while changing its proportion and structure. In this way, a copolyamide with a series of special properties such as softness, good transparency, low softening point and easy dissolution can be prepared.

According to the different polymerization process, the prepared copolymer structure of copolyamide is also different. Its modification process can be divided into: block copolymerization, random copolymerization, alternating copolymerization and graft copolymerization, etc. The research on copolyamide abroad is carried out earlier. Catlin et al. studied PA66/6, PA66/610, and PA66/610/6 three series of copolyamides, and analyzed and tested the melting point, water absorption, softening point and solubility of the copolymerized products. The results showed that in PA66: When the mass ratio of PA6 is 40:60, the melting point of the copolymer is the lowest, which is 154-156°C. Copolyamide 6/66 has unique copolyamide properties such as low melting point, low crystallinity, and good transparency. It also has excellent properties such as good toughness, wear resistance, self-lubrication, and good chemical stability. It is widely used in films, Fiber and engineering plastics.

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

Luo Yuhang studied the preparation and properties of copolyamide 6/66. Using caprolactam (CPL), nylon 66 salt (AH-salt) and terephthalic acid (PTA) as raw materials, two methods of normal pressure polymerization and prepolymerization followed by polycondensation were adopted. Polymerization process, prepared a series of copolyamide 6/66 by changing the comonomer formula and process conditions. The salt content of nylon 66 is 15-20%. The prepared copolyamide 6/66 has 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 copolyamide 6/66 /66 has a low melting point and a large molecular weight distribution.

Ma Haiyan studied the post-tensile properties of large-diameter PA6/PA66 copolymer monofilaments. Using PA6/PA66 copolymers as raw materials, large-diameter monofilaments were spun. The copolymer PA6/PA66=60:40 was used, and the intrinsic viscosity was 0.68dL. /g, molecular weight 24000, melting point 180°C, the viscosity and melting point of the PA6/PA66 copolymer are relatively low.

Patent No. CN 108250433 A discloses a PA6-56 copolymer material and its preparation method. The PA6-56 copolymer material is formed by blending and polymerizing liquid caprolactam and pentamethylenediamine adipate salt solution; the liquid caprolactam and adipic acid The molar ratio of pentamethylenediamine salt is 7:3 to 9:1. The method is as follows: mix liquid caprolactam, aqueous solution of pentamethylenediamine adipate and other reaction raw materials in proportion, stir in a reactor under inert gas protection conditions, and carry out polycondensation reaction at 150-300°C to obtain PA6- 56 Copolymeric materials. This patent application is based on PA6 monomer caprolactam, and PA56 monomer pentamethylenediamine adipate is copolymerized to obtain PA6-56 copolymer material. The equilibrium moisture absorption rate is 5.23-5.45%. The water absorption rate of the PA6-56 copolymer material is partial high.

Patent No. CN106519219 A discloses a continuous polymerization process of PA6-5X copolymer and PA6-5X copolymer. In PA6-5X copolymer, the mass percentage of PA5X salt can reach up to 60%, and the melting point of the copolymer is 165°C Between -219°C, the relative viscosity is between 2.4-3.6. Three-stage continuous polymerization is used to prepare PA6-5X copolymer, which is characterized by the combination of solid nylon 5X salt and nylon 5X salt solution, so that caprolactam and 5X salt are mixed evenly before the reaction, and highly random copolymerization is obtained after polymerization Material, the preparation method is used to prepare PA6-5X copolymer. The PA6-56 copolymer material has a relatively low melting point.

At present, there are few reports on PA56-66 copolymers. PA6-56 copolymer has a low melting point and narrow application fields. However, there are few reports on the application of PA56-66 copolymer fibers, especially in the textile field.

Contents of the invention

The first object of the present invention is to provide a copolyamide resin, which has the characteristics of moderate viscosity, moderate amino group content, low oligomer content, high molecular weight and narrow molecular weight distribution.

To achieve the above object, the solution of the present invention is:

A kind of copolyamide resin, described copolyamide comprises following segment:

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 mole fraction ratio of the segment A) to the segment B) is (95:5)-(5:95), and the amino-terminal content of the copolyamide resin is 30-80 mmol/kg, further 35 -75 mmol/kg, further 40-60 mmol/kg.

Further, 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), further (95:5)-(65:35). According to some embodiments of the present invention, appropriately increasing the content of the segment A) can improve the performance of the copolyamide resin and the spinning product.

Further, the total mass of the segment A) and the segment B) accounts for more than 90%, further more than 93%, further more than 95%, and further more than 98% of the mass of the copolyamide resin.

Further, the relative viscosity of the copolyamide resin is 2.4-3.7, further 2.5-3.5, and further 2.65-3.0.

Further, the terminal amino group content of the copolyamide resin is further 45-52.5 mmol/kg.

Further, the oligomer content of the copolyamide is ≤1.0wt%, further ≤0.8wt%, further ≤0.6wt%.

Further, the yellowness index of the copolyamide resin is ≤6.5, further ≤6, and further ≤4.

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

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

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

According to some embodiments of the present invention, the copolyamide resin contains additives, and the additives include end-capping agents, catalysts, flame retardants, antioxidants, ultraviolet absorbers, infrared absorbers, crystallization nucleating agents, fluorescent whitening agents Any one or a combination of two or more of antistatic agents.

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

Further, 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.

Further, the end-capping agent is a combination of C2-C16 aliphatic carboxylic acid and C7-C9 aromatic carboxylic acid, the quality of the C6-C9 aliphatic carboxylic acid and C7-C16 aromatic carboxylic acid The ratio is (8-1):1, and further is (5-1):1.

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

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

The content of the end-capping agent accounts for 300-10000 ppm of the total weight of 1,5-pentanediamine, hexamethylenediamine, and adipic acid monomers, and further ranges from 800-7000 ppm. The polymerization process can be regulated by using suitable end-capping agents.

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

The second object of the present invention is to provide a method for preparing a copolyamide resin, so as to obtain a copolyamide resin with excellent performance, which can meet the requirements of the spinning field.

Described preparation method comprises the 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 in a certain molar fraction with The water is mixed evenly, and the mixed salt solution is directly prepared.

2) heating and concentrating the mixed salt solution, first performing pre-polymerization, raising the pressure in the reaction system to 0.3-2.45MPa, exhausting and maintaining the pressure, and then reducing the pressure to reduce the pressure in the reaction system to a gauge pressure of 0-0.3MPa, Then carry out the final polycondensation under vacuum conditions, wherein the vacuum is drawn to a vacuum degree of - (0.01-0.08) MPa to obtain a copolyamide melt, which is finally pelletized and dried to obtain a copolyamide resin.

Unless otherwise stated or obviously contradicted, the pressures mentioned in the present invention are gauge pressures.

Wherein, the preparation method of the polyamide 56 salt solution can be conventional in the art, further, under nitrogen conditions, 1,5-pentanediamine, adipic acid and water are uniformly mixed to prepare the polyamide 56 salt solution ; Further, the molar ratio of 1,5-pentanediamine to 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 a polyamide 66 salt solution; further, the hexamethylene diamine The molar ratio of diamine to adipic acid is (1-1.1):1.

Further, 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.

Further, in step 1), the concentration of the polyamide 66 salt solution is 20-70wt.%, further 50-60wt.%. The percentage is the mass percentage of the polyamide 66 salt in the polyamide 66 salt solution.

Further, in step 1), in the mixed salt solution, the mole fraction ratio of the polyamide 56 salt in the polyamide 56 salt solution to the 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).

Further, in step 2), the temperature of the reaction system at the end of the pressure holding is 220-260° C.; the temperature of the reaction system after the depressurization is 240-280° C.; the temperature of the reaction system after vacuuming is 260-290°C.

Further, the drying treatment equipment in step 2) is a vacuum drum dryer or a continuous dehumidification heat nitrogen dryer, and the temperature of the drying treatment is 80-120°C, further 90-115°C; the drying treatment The time is 8-25 hours, further 13-20 hours.

Further, the method may also include step a) before step 1) under nitrogen condition, uniformly mixing pentamethylenediamine, adipic acid and water to prepare a polyamide 56 salt solution. The polyamide 56 salt solution has the above-mentioned definition.

Further, the method may also include step b) before step 1), uniformly mixing hexamethylenediamine, adipic acid and water under nitrogen conditions to prepare a polyamide 66 salt solution. The polyamide 66 salt solution has the above-mentioned limitations.

Additives may be included in the polyamide 56 salt solution and/or polyamide 66 salt solution, or add additives at any stage of step a), step b), step 1) and/or step 2), and the additives include Any one or more of end-capping agents, catalysts, flame retardants, antioxidants, ultraviolet absorbers, infrared absorbers, crystallization nucleating agents, fluorescent whitening agents and antistatic agents; further, the additives The added amount accounts for 0-1wt% of the total weight of 1,5-pentanediamine, hexamethylenediamine and adipic acid monomers.

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

The C2-C16 aliphatic carboxylic acid includes any one or a combination of two or more of acetic acid, adipic acid, decadioic acid, undecanedioic acid, and dodecanedioic acid.

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 C2-C16 aliphatic carboxylic acids and C7-C9 aromatic carboxylic acids, the mass ratio of the C6-C9 aliphatic carboxylic acids to C7-C16 aromatic carboxylic acids is (8-1):1, and further is (5-1):1.

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

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

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

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

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

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

The copolyamide 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 textured filament (BCF), staple fiber, industrial yarn, and monofilament, further fully drawn yarn, continuous bulked textured filament, industrial yarn, and monofilament.

Described copolyamide fiber satisfies the following conditions:

The boiling water shrinkage of the copolyamide fiber is ≤25%, further ≤23%, further ≤20%, further ≤15%; and/or

The breaking strength of the copolyamide fiber is ≥ 2.2 cN/dtex, further ≥ 3.5 cN/dtex, further ≥ 3.8 cN/dtex, further ≥ 4.2 cN/dtex, further ≥ 6 cN/dtex; and/or or

The elongation at break of the copolyamide fiber is ≤55%, further ≤50%, further ≤45%, further ≤40%; and/or

The initial modulus of the copolyamide fiber is ≤55cN/dtex, further ≤53cN/dtex, further ≤50cN/dtex; and/or

The thermal crimp rate of the copolyamide fiber is ≥ 35%, further ≥ 40%, further ≥ 45%; and/or

The moisture regain of the copolyamide fiber is ≤5.0%, further ≤4.8%, further ≤4.7%; and/or

The dyeing uniformity (gray card) of the copolyamide fiber is ≥ 3.5, further ≥ 4.0, further ≥ 4.5; and/or

The soaping fastness of the copolyamide fiber: the fading fastness is ≥3.5 grade, further ≥4.0 grade, further ≥4.5 grade; and/or

The staining fastness of the copolyamide fiber is grade ≥ 3.5, further grade ≥ 4.0, further grade ≥ 4.5.

Oligomers are defects in the process of mechanical property testing, and the content of oligomers in copolyamide is reduced, which is conducive to improving the mechanical properties of polymer resins. Moreover, the content of oligomers in the copolyamide resin is small, and few oligomer molecules are produced during the fiber preparation process, the fibers are more stable, the moisture regain is high, the fading fastness and staining fastness are high, and the mechanical properties are improved.

If the oligomer enters the spinning section with the chip, it will not only cause serious consequences to the spinning process, but also a great waste of raw materials. Oligomers are mainly produced in the polymerization stage, and the degree of polymerization is generally 1 to 8. For example, dimers and trimers are formed by polymerization between monomers, and oligomers can be extracted by hot water. A high oligomer content will affect the molecular weight distribution of the chips, and during the melt spinning process, these oligomers will evaporate from the melt and become gas, increasing the bubbles in the polyamide melt, and the evaporated gas will be After coagulation, it will also deteriorate the spinning environment. In addition, oligomers are also easy to precipitate on the surface of the silk, which affects the performance of the fiber.

The fourth object of the present invention is to provide a method for preparing copolyamide fibers.

Described preparation method comprises the steps:

1) heating the copolyamide resin to a molten state to form a copolyamide melt;

2) The copolyamide melt is transported into the spinning box through the melt pipeline, and after being accurately metered by the metering pump, it is injected into the spinning assembly, and extruded from the spinneret hole to obtain as-spun filaments, wherein the spinneret below the spinneret Provide unit suction; and

3) Post-processing the as-spun filaments to obtain copolyamide fibers. The post-processing includes: cooling, and/or oiling, and/or stretching, and/or setting.

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

Further, the post-processing of step 3) includes: heat preservation, cooling, oiling, pre-internetting, multi-stage stretching, tension setting, relaxation setting, main network, and winding of the prepared as-spun silk, to obtain the obtained Copolyamide industrial yarn described above.

Further, the post-processing of the step 3) includes: cooling, oiling, stretching, shaping, deformation of the expander, cooling of the cold drum, main network, and winding of the as-spun silk produced to obtain the copolyamide Continuous bulky filament.

Further, the post-processing of step 3) includes: cooling the as-spun yarn in a water bath, primary drawing, secondary drawing, heat setting, and winding forming to obtain the copolyamide monofilament.

The heating in step 1) is carried out with a screw, and the screw is in a four-zone heating mode, wherein the temperature in the first zone is 220-270°C, further 230-265°C; the temperature in the second zone is 230-280°C, further 240- 275°C; the temperature in the third zone is 240-290°C, further 250-285°C; and the temperature in the fourth zone is 250-300°C, further 260-295°C.

Step 2) The temperature of the spinning box is 260-300°C, further 270-295°C; the assembly 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; wind temperature is 16-22°C, further 18-21°C; wind humidity is 65-95%, further 70 -90%.

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

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

The fifth object of the present invention is to provide the application of a copolyamide fiber in the fields of knitted and woven fabrics, carpet yarns, blended yarns, monofilaments or industrial yarns.

Owing to adopting said scheme, the beneficial effect of the present invention is:

First, 1,5-pentanediamine, the raw material for the production of copolyamide fibers of the present invention, is made by biological methods, is a green material, does not depend on petroleum resources and does not cause serious pollution to the environment, and can reduce carbon dioxide emissions and reduce greenhouse gas emissions. Effect generation, adapting to the development trend of carbon neutrality.

Second, the copolyamide 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 of the spinning field.

Third, the copolyamide fiber of the present invention has good mechanical properties, thermal shrinkage properties, soft properties and dyeing properties, etc., and has excellent comprehensive properties.

The test method involved in the embodiment is as follows:

1) Relative viscosity: Ubbelohde viscometer concentrated sulfuric acid method: accurately weigh 0.25±0.0002g of dried polyamide slices, add 50mL concentrated sulfuric acid (96wt%) to dissolve; measure and record the concentrated sulfuric acid in a constant temperature water bath at 25°C Flow through time t ₀ and polyamide sample solution flow through time t. Relative viscosity calculation formula: relative viscosity = t/t ₀ ; t—solution flow time; t ₀ —concentrated sulfuric acid flow time.

2) Oligomer content: Water extraction method (weighing method): Accurately weigh about 8g of copolyamide resin dried at 130°C for 7 hours (the actual mass is denoted as m ₁ ), put it in a 500mL round bottom flask, add Heat 400g of water in a heating jacket at 97°C to 100°C for 36h, decant the solution, dry the particles at 130°C in a constant weight beaker for 7 hours, then plastic seal them in an aluminum-plastic bag and weigh them (mass is denoted as m ₂ ), calculate its weight loss (m ₁ -m ₂ ). Oligomer content (%)=(m ₁ -m ₂ )/m ₁ *100%.

3) Number average molecular weight, 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 pretension, clamping distance 500mm, tensile speed 500mm/ min. Modulus = breaking strength corresponding to 1% elongation at break × 100.

5) Moisture regain: put the washed fiber in a loose state into an oven for drying, and place the dried fiber sample in the standard atmosphere specified in GB/T6529 to adjust the balance. Wash the sample after humidity adjustment, and measure the moisture regain. The moisture regain measurement method is carried out according to GB/T6503, in which the drying temperature of the oven is 105°C, and the drying time is 1h.

6) Boiling water shrinkage: determined according to GB/6505.

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

8) Soaping fastness (fading fastness, staining fastness): determined according to the national standard GB/T 3921.1-1997.

9) Hot crimp rate: use the oven in the self-made length measuring device to carry out according to FZ/T 50030-2015.

10) Yellowness index: according to ASTM D1925, use a meter 3600D to measure the yellowness index of the sample using the CLE lab color difference evaluation standard.

Example 1

Copolyamide resin preparation method comprises the steps:

1) Under nitrogen, mix 1,5-pentanediamine, adipic acid, end-capping agent, antioxidant and water uniformly to prepare a 60wt.% polyamide 56 salt solution; wherein, 1,5-pentanediamine The molar ratio of diamine and adipic acid is (1-1.04): 1;

2) Under nitrogen conditions, mix hexamethylenediamine, adipic acid, end-capping agent, antioxidant and water uniformly to obtain a 60wt.% polyamide 66 salt solution; wherein, the molar ratio of hexamethylenediamine and adipic acid is (1-1.06): 1; and

3) Mix the polyamide 56 salt solution and the polyamide 66 salt solution according to the molar ratio of polyamide 56 salt and polyamide 66 salt 85:15, heat and concentrate, first perform prepolymerization, and raise the pressure in the reaction system to 2.45Mpa, exhaust and maintain pressure, and then reduce the pressure to reduce the pressure in the reaction system to 0MPa gauge pressure, and then carry out final polycondensation under vacuum conditions, and vacuumize to -0.07MPa to obtain a copolyamide melt, and finally pelletize and drying to obtain a copolyamide resin.

In the step 2), the temperature of the reaction system at the end of the pressure holding is 260° C.; the temperature of the reaction system after the depressurization is 265° C.; the temperature after the vacuum is 273° C.;

In the step 3), the drying treatment equipment is a continuous dehumidification heat nitrogen dryer, the drying treatment temperature is 90° C., and the drying treatment time is 22 hours.

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

Example 2

Copolyamide resin preparation method comprises the steps:

1) Under nitrogen, mix 1,5-pentanediamine, adipic acid, end-capping agent, antioxidant and water uniformly to prepare a 60wt.% polyamide 56 salt solution; wherein, 1,5-pentanediamine The molar ratio of diamine and adipic acid is (1-1.06): 1;

2) Under nitrogen conditions, mix hexamethylenediamine, adipic acid, end-capping agent, antioxidant and water uniformly to obtain a 60wt.% polyamide 66 salt solution; wherein, the molar ratio of hexamethylenediamine and adipic acid is (1-1.06): 1; and

3) Mix polyamide 56 salt solution and polyamide 66 salt solution according to the molar ratio of polyamide 56 salt and polyamide 66 salt 70:30, heat and concentrate, first perform prepolymerization, and raise the pressure in the reaction system to 2.25MPa, exhaust and maintain pressure, and then reduce the pressure to reduce the pressure in the reaction system to 0MPa gauge pressure, and then carry out final polycondensation under vacuum conditions, and vacuumize to -0.08MPa to obtain a copolyamide melt, and finally pelletize and drying to obtain a copolyamide resin.

In the step 2), the temperature of the reaction system at the end of the pressure holding is 260° C.; the temperature of the reaction system after the depressurization is 265° C.; the temperature after the vacuum is 272° C.;

In the step 3), the drying treatment equipment is a continuous dehumidification heat nitrogen dryer, the drying treatment temperature is 110° C., and the drying treatment time is 12 hours.

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

Example 3-A

Copolyamide resin preparation method comprises the steps:

1) Under nitrogen, mix 1,5-pentanediamine, adipic acid, end-capping agent, antioxidant and water uniformly to prepare a 60wt.% polyamide 56 salt solution; wherein, 1,5-pentanediamine The molar ratio of diamine and adipic acid is (1-1.04): 1;

2) Under nitrogen conditions, mix hexamethylenediamine, adipic acid, end-capping agent, antioxidant and water uniformly to obtain a 60wt.% polyamide 66 salt solution; wherein, the molar ratio of hexamethylenediamine and adipic acid is (1-1.05): 1; and

3) Mix the polyamide 56 salt solution and the polyamide 66 salt solution according to the molar ratio of polyamide 56 salt and polyamide 66 salt 60:40, heat and concentrate, first perform pre-polymerization, and raise the pressure in the reaction system to 2.2MPa, exhaust and keep the pressure, and then reduce the pressure to reduce the pressure in the reaction system to 0MPa gauge pressure, and then carry out the final polycondensation under vacuum conditions, and vacuumize until the vacuum degree is -0.05MPa to obtain a copolyamide melt, and finally pelletize and drying to obtain a copolyamide resin.

In the step 2), the temperature of the reaction system at the end of the pressure holding is 262° C.; the temperature of the reaction system after the depressurization is 266° C.; the temperature after the vacuum is 270° C.;

In the step 3), the drying treatment equipment is a continuous dehumidification heat nitrogen dryer, the drying treatment temperature is 105° C., and the drying treatment time is 16 hours.

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

Embodiment 3-B～Embodiment 3-F

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

Example 4

Copolyamide resin preparation method comprises the steps:

1) Under nitrogen, mix 1,5-pentanediamine, adipic acid, end-capping agent, antioxidant and water uniformly to prepare a 60wt.% polyamide 56 salt solution; wherein, 1,5-pentanediamine The molar ratio of diamine and adipic acid is (1-1.08):1;

2) Under nitrogen conditions, mix hexamethylenediamine, adipic acid, end-capping agent, antioxidant and water uniformly to obtain a 60wt.% polyamide 66 salt solution; wherein, the molar ratio of hexamethylenediamine and adipic acid is (1-1.07): 1; and

3) Mix the polyamide 56 salt solution and the polyamide 66 salt solution according to the molar ratio of polyamide 56 salt and polyamide 66 salt 35:65, heat and concentrate, first perform pre-polymerization, and raise the pressure in the reaction system to 2.3MPa, exhaust and maintain pressure, and then reduce the pressure to reduce the pressure in the reaction system to 0MPa gauge pressure, and then carry out final polycondensation under vacuum conditions, and vacuumize to -0.04MPa to obtain a copolyamide melt, and finally pelletize and drying to obtain a copolyamide resin.

In the step 2), the temperature of the reaction system at the end of the pressure holding is 258° C.; the temperature of the reaction system after the depressurization is 265° C.; the temperature after the vacuum is 275° C.;

In the step 3), the drying treatment equipment is a continuous dehumidification heat nitrogen dryer, the drying treatment temperature is 95° C., and the drying treatment time is 20 h.

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

Example 5

Copolyamide resin preparation method comprises the steps:

1) Under nitrogen, mix 1,5-pentanediamine, adipic acid, end-capping agent, antioxidant and water uniformly to prepare a 60wt.% polyamide 56 salt solution; wherein, 1,5-pentanediamine The molar ratio of diamine and adipic acid is (1-1.05): 1;

2) Under nitrogen conditions, mix hexamethylenediamine, adipic acid, end-capping agent, antioxidant and water uniformly to obtain a 60wt.% polyamide 66 salt solution; wherein, the molar ratio of hexamethylenediamine and adipic acid is (1-1.08): 1; and

3) Mix the polyamide 56 salt solution and the polyamide 66 salt solution according to the molar ratio of polyamide 56 salt and polyamide 66 salt 20:80, heat and concentrate, first perform prepolymerization, and raise the pressure in the reaction system to 2.4MPa, exhaust and maintain the pressure, and then reduce the pressure to reduce the pressure in the reaction system to 0MPa gauge pressure, and then carry out the final polycondensation under vacuum conditions, in which the vacuum is vacuumed to -0.08MPa to obtain a copolyamide melt, and finally pelletized and drying to obtain a copolyamide resin.

In the step 2), the temperature of the reaction system at the end of the pressure holding is 258° C.; the temperature of the reaction system after the depressurization is 265° C.; the temperature after the vacuum is 276° C.;

In the step 3), the drying treatment equipment is a continuous dehumidification heat nitrogen dryer, the drying treatment temperature is 110° C., and the drying treatment time is 16 hours.

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

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

Table 1 Resin raw materials and resin performance test results

Embodiment 6-15

Copolyamide fully drawn silk preparation method comprises the steps:

1) heating the copolyamide resin prepared in the above examples to a molten state to form a copolyamide melt;

2) The copolyamide melt is transported into the spinning box through the melt pipeline, and after being accurately metered by the metering pump, it is injected into the spinning assembly and extruded from the spinneret hole, wherein the monomer is set under the spinneret suction device; and

3) Cooling, oiling, stretching, setting, and winding the extruded as-spun fibers to obtain the fully drawn copolyamide filaments.

The heating in step 1) is carried out with a screw, and the screw is in a four-zone heating mode, wherein the temperature of the first zone is 260°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 temperature of the spinning box is 290° C.; the assembly pressure is 15 MPa. The cooling wind speed is 0.42m/s; the wind temperature is 18°C; and the wind humidity is 80%. The oiling rate is 1.1%. The stretching ratio is 1.65, and the setting temperature is 160°C. The winding speed is 4800m/min.

See Table 2 for the performance indexes of the resin materials used in Examples 6-15 and the fully drawn copolyamide yarns.

Table 2 Performance indicators of copolyamide and copolyamide fully drawn yarn

Examples 16-19

Copolyamide industrial yarn preparation method comprises the steps:

1) The copolyamide resin prepared in the above examples is solid-phase increased to 3.2, heated to a molten state to form a copolyamide melt;

2) The copolyamide melt is transported into the spinning box through the melt pipeline, and after being accurately metered by the metering pump, it is injected into the spinning assembly and extruded from the spinneret hole, wherein the monomer is set under the spinneret suction device;

3) heat preservation, cooling, oiling, pre-network, multi-stage stretching, tension setting, relaxation setting, main network, and winding of the prepared as-spun yarn to obtain the 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 as-spun yarn after oiling is first fed to the first pair of hot rollers, and between the first pair of hot rollers and the second The first stage pre-stretching is carried out between two pairs of hot rollers, and then the second stage main stretch is carried out between the second pair of hot rollers and the third pair of hot rollers. The third stage of main stretching and tension heat setting is carried out between the hot rollers, followed by the fourth secondary stretching and relaxation heat setting between the fourth pair of hot rollers and the fifth pair of hot rollers, and finally rolling around the shape.

The heating in step 1) is carried out with a screw, and the screw is in a four-zone heating mode, wherein the temperature of the first zone is 265°C; the temperature of the second zone is 275°C; the temperature of the third zone is 285°C; and the temperature of the fourth zone is 295°C.

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

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

The oiling rate is 1.2%.

The total draw 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.

See Table 3 for the resin raw materials used in Examples 16-19 and the performance indexes of the copolyamide industrial yarn.

Table 3 Performance index of copolyamide industrial yarn

Examples 20-23

Copolyamide continuous bulking filament preparation method comprises the steps:

1) heating the copolyamide resin prepared in the above examples to a molten state to form a copolyamide melt;

2) The copolyamide melt is transported into the spinning box through the melt pipeline, and after being accurately metered by the metering pump, it is injected into the spinning assembly and extruded from the spinneret hole, wherein the monomer is set under the spinneret suction device; and

3) Cooling, oiling, stretching, shaping, expansion machine deformation, cold drum cooling, main network, and winding of the prepared as-spun yarn to obtain the continuous bulked filament of the copolyamide;

The heating in step 1) is carried out with a screw, and the screw is in 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 temperature of the spinning box is 285° C.; the assembly pressure is 10 MPa. The cooling wind speed is 0.5m/s; the wind temperature is 20°C; and the wind humidity is 80%. The oiling rate is 1.1%. The expansion deformation temperature is 230°C. The winding speed during the winding forming is 3000m/min.

See Table 4 for the performance indexes of the resin materials used in Examples 20-23 and the continuous bulked copolyamide filaments.

Table 4 Performance index of copolyamide continuous bulked filament

Examples 24-27

Copolyamide monofilament preparation method comprises the steps:

1) the copolyamide resin prepared by the above examples is heated to a molten state to form a copolyamide melt;

2) The copolyamide melt is transported into the spinning box body through the melt pipeline, and after being accurately metered by the metering pump, it is injected into the spinning assembly and extruded from the spinneret hole;

3) cooling the as-spun filaments in a water bath, primary stretching, secondary stretching, heat setting, and winding forming to obtain the copolyamide monofilament.

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

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

In step 3): the cooling temperature of the water bath is 30°C, the primary stretching ratio is 3.0, the secondary 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 speed of winding forming is 180m/min.

See Table 5 for the performance indicators of the resin raw materials and copolyamide monofilaments used in Examples 24-27.

Table 5 Copolyamide monofilament performance index

The above is only a preferred embodiment of the present invention, it should be pointed out that for those of ordinary skill in the art, without departing from the concept of the present invention, some improvements and modifications can also be made, and these improvements and modifications should also be regarded as within the protection scope of the present invention.

Claims (11)

1. A copolyamide resin, characterized in that, the copolyamide resin comprises 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 mole fraction ratio of the segment A) to the segment B) is (95:5)-(5:95), and the amino-terminal content of the copolyamide resin is 30-80 mmol/kg, further 35 -75 mmol/kg, further 40-60 mmol/kg.
2. The copolyamide resin according to claim 1, characterized in that, the molar ratio of the segment A) to the segment B) is (95:5)-(20:80), further (95:5 )-(35:65), further (95:5)-(50:50); and/or,

   The relative viscosity of the copolyamide resin is 2.4-3.7, further 2.5-3.5, further 2.65-3.0; and/or,

   The amino group content of the copolyamide resin is 45-52.5 mmol/kg; and/or,

   The oligomer content of the copolyamide is ≤ 1.0 wt%, further ≤ 0.8 wt%, further ≤ 0.6 wt%; and/or,

   The yellowness index of the copolyamide resin is ≤6.5, further ≤6, further ≤4; and/or,

   The number average molecular weight of the copolyamide resin is 1.5*10 ⁴ -4.0*10 ⁴ g/mol, further 1.8*10 ⁴ -3.5*10 ⁴ g/mol, further 2.2*10 ⁴ -3.0*10 ⁴ g/mol; and/or,

   The molecular weight distribution of the copolyamide resin is 1.4-2.5, further 1.6-2.4, further 1.8-2.3; and/or,

   Additives are contained in the copolyamide resin, and the additives include any one of end-capping agent, catalyst, flame retardant, antioxidant, ultraviolet absorber, infrared absorber, crystallization nucleating agent, fluorescent whitening agent and antistatic agent. One or a combination of two or more, the end-capping agent includes: any one or a combination of two or more of C2-C16 aliphatic carboxylic acids and C7-C9 aromatic carboxylic acids.
3. Copolyamide resin according to claim 2, is characterized in that the preparation raw material of described copolyamide resin comprises 1,5-pentanediamine, hexamethylenediamine, adipic acid monomer, and the addition amount of described additive accounts for 1, Less than 1% by weight of the total weight of 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 a combination of two or more of acetic acid, adipic acid, decadioic acid, undecanedioic acid, and dodecanedioic acid; and/ or,

   The end-capping agent is a combination of C2～C16 aliphatic carboxylic acids and C7～C9 aromatic carboxylic acids, and the mass ratio of the C6～C9 aliphatic carboxylic acids to C7～C16 aromatic carboxylic acids is ( 8-1): 1, further (5-1): 1; and/or,

   The end-capping agent is a combination of decanedidioic acid and terephthalic acid, the mass ratio of the decanedidioic acid to terephthalic acid is (8-1): 1, further (5-1) : 1; and/or,

   The capping agent is a combination of decadioic acid and benzoic acid, the mass ratio of the decadioic acid to benzoic acid is (8-1): 1, further (5-1): 1; and /or,

   The content of the end-capping agent accounts for 300-10000ppm, further 800-7000ppm of the total weight of 1,5-pentanediamine, hexamethylenediamine, and adipic acid monomer; and/or,

   The antioxidant includes any one or a combination of two or more of sodium hypophosphite, calcium hypophosphite, phosphorous acid, antioxidant 1010, and antioxidant 1097; and/or,

   The content of the antioxidant accounts for 5-300ppm, further 10-200ppm, of the total weight of 1,5-pentanediamine, hexamethylenediamine, and adipic acid monomers.
4. A kind of preparation method of copolyamide resin is characterized in that, comprises the 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 according to a certain molar ratio and Mix the water evenly to directly prepare the mixed salt solution;

   2) Heating and concentrating the mixed salt solution, first performing pre-polymerization, increasing the pressure in the reaction system to 0.3-2.45MPa, exhausting and maintaining the pressure, and then reducing the pressure to reduce the pressure in the reaction system to a gauge pressure of 0-0.3MPa, Then carry out the final polycondensation under vacuum conditions, and vacuumize until the degree of vacuum is - (0.01-0.08) MPa to obtain a copolyamide melt, and finally pelletize and dry to obtain a copolyamide resin.
5. The preparation method of copolyamide resin according to claim 4, is characterized in that, contains additive in described polyamide 56 salt solution and/or polyamide 66 salt solution, or, in step 1) and/or step 2) Add additives at any stage.
6. The preparation method of copolyamide resin according to claim 5, is characterized in that, described additive comprises end-capping agent, catalyst, flame retardant, antioxidant, ultraviolet absorber, infrared absorber, crystallization nucleating agent, fluorescence enhancer Any one or a combination of two or more of whitening agents and antistatic agents;

   Further, the end-capping agent includes any one or a combination of two or more of C2-C16 aliphatic carboxylic acids and C7-C9 aromatic carboxylic acids, and the amount of the end-capping agent added accounts for 1, The total weight of 5-pentanediamine, hexamethylenediamine, and adipic acid monomers is 300-10000ppm, further 800-7000ppm.
7. The preparation method of copolyamide resin according to claim 4, characterized in that, in step 1), the concentration of the polyamide 56 salt solution is 30-90wt.%, further 60-75wt.%; and/or ,

   In step 1), the concentration of the polyamide 66 salt solution is 20-70wt.%, further 50-60wt.%; and/or,

   In step 1), in the mixed salt solution, the mole fraction ratio of the polyamide 56 salt in the polyamide 56 salt solution to the 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); and / or,

   In step 2), the temperature of the reaction system at the end of the pressure holding is 220-260°C; and/or,

   In step 2), the temperature of the reaction system is 240-280° C. after the depressurization; and/or,

   In step 2), the temperature after vacuuming is 260-290°C; and/or,

   In step 2), the equipment for drying treatment is a vacuum drum dryer or a continuous dehumidification heat nitrogen dryer; and/or,

   In step 2), the temperature of the drying treatment is 80-120°C, further 90-115°C; and/or,

   In step 2), the drying time is 8-25 hours, further 13-20 hours.
8. A kind of copolyamide fiber, it is characterized in that, described copolyamide fiber comprises undrawn yarn (UDY), pre-oriented yarn (POY), highly oriented yarn (HOY), fully oriented yarn (FOY), fully drawn yarn ( FDY), drawn false twisted yarn (DTY), continuously bulked textured filament (BCF), staple fiber, industrial yarn, and monofilament; and/or,

   The boiling water shrinkage of the copolyamide fiber is ≤25%, further ≤23%, further ≤20%, further ≤15%; and/or,

   The breaking strength of the copolyamide fiber is ≥ 2.2 cN/dtex, further ≥ 3.5 cN/dtex, further ≥ 3.8 cN/dtex, further ≥ 4.2 cN/dtex, further ≥ 6 cN/dtex; and/or or,

   The elongation at break of the copolyamide fiber is ≤55%, further ≤50%, further ≤45%, further ≤40%; and/or,

   The initial modulus of the copolyamide fiber is ≤55cN/dtex, further ≤53cN/dtex, further ≤50cN/dtex; and/or,

   The thermal crimp rate of the copolyamide fiber is ≥ 35%, further ≥ 40%, further ≥ 45%; and/or,

   The moisture regain of the copolyamide fiber is ≤5.0%, further ≤4.8%, further ≤4.7%; and/or,

   The dyeing uniformity (gray card) of the copolyamide fiber is ≥ 3.5, further ≥ 4.0, further ≥ 4.5; and/or,

   The soaping fastness of the copolyamide fiber: the color fastness to fading is ≥3.5, further ≥4.0, further ≥4.5; and/or, the staining fastness of the copolyamide fiber is ≥3.5 , further to ≥4.0 level, and further to ≥4.5 level.
9. A kind of preparation method of copolyamide fiber is characterized in that, it comprises the steps:

   1) heating the copolyamide resin to a molten state to form a copolyamide melt;

   2) The copolyamide melt is transported into the spinning box through the melt pipeline, and after being accurately metered by the metering pump, it is injected into the spinning assembly, and extruded from the spinneret hole to obtain as-spun filaments, wherein the spinneret below the spinneret Provide unit suction; and

   3) Post-processing the as-spun filaments to obtain copolyamide fibers. The post-processing includes: cooling, and/or oiling, and/or stretching, and/or setting.
10. The preparation method of copolyamide fibers according to claim 9, wherein the heating in step 1) is carried out with a screw, and the screw is in a four-zone heating mode, wherein the temperature in one zone is 220-270° C., and further is 230-265°C; the temperature in zone 2 is 230-280°C, further 240-275°C; the temperature in zone 3 is 240-290°C, further 250-285°C; and the temperature in zone 4 is 250-300°C, further 260°C -295°C; and/or,

    Step 2) The temperature of the spinning box is 260-300°C, further 270-295°C; and/or,

    Step 2) The pressure of the spinning pack is 10-17MPa, further 12-15MPa; and/or,

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

    Step 3) the stretch ratio is 1.3-5.5, further 1.5-4.8; and/or,

    Step 3) The setting temperature is 140-210°C, further 150-180°C; and/or,

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

    Step 3) The post-treatment described includes: cooling, oiling, stretching, shaping, and winding the extruded as-spun yarn to obtain the fully drawn copolyamide yarn; further, the oiling rate is 0.4-1.2%, further 0.45-1.1%; and/or,

    Step 3) The post-treatment includes: heat preservation, cooling, oiling, pre-network, multi-stage stretching, tension setting, relaxation setting, main network, and winding of the prepared as-spun silk to obtain the copolyamide industrial yarns; and/or,

    Step 3) The post-treatment includes: cooling the prepared as-spun silk, oiling, stretching, shaping, deforming in an expander, cold drum cooling, main network, and winding to obtain the continuous expanded copolyamide filament; and/or,

    The post-treatment in step 3) includes: cooling the as-spun yarn in a water bath, primary drawing, secondary drawing, heat setting, and winding forming to obtain the copolyamide monofilament.
11. An application of the copolyamide fiber as claimed in claim 8 in the fields of knitted and woven fabrics, carpet yarns, blended yarns, monofilaments or industrial yarns.