WO2021088250A1 - 一种聚酰胺5x工业丝及其制备方法与应用 - Google Patents

一种聚酰胺5x工业丝及其制备方法与应用 Download PDF

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WO2021088250A1
WO2021088250A1 PCT/CN2020/072240 CN2020072240W WO2021088250A1 WO 2021088250 A1 WO2021088250 A1 WO 2021088250A1 CN 2020072240 W CN2020072240 W CN 2020072240W WO 2021088250 A1 WO2021088250 A1 WO 2021088250A1
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Prior art keywords
polyamide
industrial yarn
temperature
heat
yarn
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PCT/CN2020/072240
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English (en)
French (fr)
Inventor
孙朝续
陈万钟
陈树沅
商治国
刘修才
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上海凯赛生物技术股份有限公司
Cibt美国公司
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Application filed by 上海凯赛生物技术股份有限公司, Cibt美国公司 filed Critical 上海凯赛生物技术股份有限公司
Priority to JP2022525981A priority Critical patent/JP2023502885A/ja
Priority to KR1020227019014A priority patent/KR20220101647A/ko
Priority to US17/774,937 priority patent/US20220389620A1/en
Priority to EP20884194.0A priority patent/EP4095292A4/en
Publication of WO2021088250A1 publication Critical patent/WO2021088250A1/zh

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/28—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00—Treatment of filament-forming or like material
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/02—Heat treatment
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/088—Cooling filaments, threads or the like, leaving the spinnerettes
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/12—Stretch-spinning methods
    • D01D5/16—Stretch-spinning methods using rollers, or like mechanical devices, e.g. snubbing pins
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/02—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/06—Load-responsive characteristics
    • D10B2401/063—Load-responsive characteristics high strength

Definitions

  • the invention belongs to the technical field of polyamide materials, and relates to a polyamide 5X industrial yarn and a preparation method and application thereof.
  • melt direct spinning method There are two production processes for industrial yarn: one is to use melt direct spinning method, and the other is to use chip solid-phase tackifying indirect spinning method.
  • polyamide 66 and poly(hexylene terephthalate) have been partially melt-spun directly.
  • Polyamide 6 contains 8-10wt% monomers in the polymer, so it needs to go through a single process to remove the monomers. Currently, it cannot be directly spun. Perform melt spinning.
  • Polyester and nylon industrial yarns have the characteristics of high strength, low elongation, good dimensional stability, fatigue resistance and aging resistance, making them widely used in tire cord, canvas, conveyor belts, airbags, parachutes, ropes, and seat belts. , Industrial filter cloth or tents and other fields. Different application fields have higher requirements for the heat resistance of industrial silk materials.
  • the blending method is mainly carried out by adding heat stabilizer masterbatch.
  • the price of the heat stabilizer masterbatch is high, and during the spinning process, the spinning manufacturer needs to be equipped with the masterbatch on-line device.
  • the equipment investment cost is high.
  • Patent CN110055602A discloses a polyamide 56 high-strength industrial yarn and a preparation method thereof.
  • Conventional polyamide 56 chips are used for spinning, and the polyamide 56 chips are not heat-resistant modified.
  • the industrial yarn prepared by the yarn has poor heat resistance. It cannot be used in areas that require high heat resistance, such as sewing thread, tire cord, air bag yarn, mold release cloth, water cloth, etc.
  • the high-speed winding process is adopted, the winding speed is greater than 4000m/min, the winding speed is high, and the fiber residence time on different heat rollers is relatively shortened, that is, the fiber high temperature setting time is shortened, and the low-magnification drawing process is used, which causes the fiber to crystallize. And the orientation is low, the strength of the prepared fiber is low and the dimensional stability becomes poor.
  • the first object of the present invention is to provide a polyamide 5X industrial yarn with excellent heat resistance and mechanical properties at the same time. After the polyamide 5X industrial yarn is treated at 180°C for 4 hours, the retention rate of heat-resistant fracture strength is ⁇ 90 %; After treatment at 230°C for 30min, the retention rate of heat-resistant fracture strength is ⁇ 90%; the dry heat shrinkage rate is ⁇ 8.0%.
  • the polyamide 5X includes any one of polyamide 56, polyamide 510, polyamide 512, polyamide 513, or polyamide 514. Preferably, it is polyamide 56 or polyamide 510.
  • the present invention optimizes the quality of polyamide 5X, especially polyamide 56 resin: adjusts its viscosity, oligomer content, molecular weight and distribution, moisture content, and secondly optimizes the spinning process of polyamide 5X industrial yarn to improve the quality of polyamide 5X industrial yarn.
  • Crystallinity and orientation increase the setting temperature and increase the winding overfeed ratio, reduce the subsequent stress relaxation, and finally obtain polyamide 56 industrial yarn with excellent mechanical properties and dimensional stability, with a breaking strength of 6.5 cN/dtex or more;
  • the number of broken filaments is less than or equal to 2 times/24h; the production rate is greater than or equal to 90%; the boiling water shrinkage is less than 8.0%; the fineness is 100-3500 dtex; the elongation at break is less than 26%; the crystallinity is more than 70%; the degree of orientation is Above 80%.
  • Polyamide fiber spinning process requires resin to control moisture content, which is generally required to be within the equilibrium moisture content range. If the resin moisture content is too low during the spinning process, the melt viscosity reaction will occur during the melting process, and the amino content will decrease. The fluidity of the body becomes poor, which is not conducive to subsequent stretching, resulting in fiber breakage and low strength; too high moisture content, melt degradation reaction during the melting process, increased amino content, and easy to produce filament breakage, which will eventually cause The production rate is reduced.
  • the moisture content of the polyamide 56 resin is 300-800ppm
  • the relative viscosity of the oil-free yarn of the polyamide 56 industrial yarn is 2.7-4.5
  • the absolute value of the difference between the relative viscosity of the oil-free yarn and the relative viscosity of the resin is ⁇ 0.12
  • no The amino content of the oily silk is 20-50mmol/kg
  • the production rate of the prepared polyamide 56 industrial yarn is ⁇ 90%.
  • the second object of the present invention is to provide a method for preparing polyamide 5X industrial yarn, especially polyamide 56 industrial yarn.
  • the third object of the present invention is to provide an application of polyamide 5X industrial yarn, especially the application of polyamide 56 industrial yarn.
  • the polyamide 56 industrial yarn is used in sewing threads, tire cords, airbag yarns, and release fabrics. , Water cloth, canvas, seat belts, ropes, fishing nets, industrial filter cloth, conveyor belts, parachutes, tents, luggage applications.
  • the solution of the present invention is:
  • the content of copper ion in the polyamide 56 industrial yarn of the present invention is 10-1000 ppm, preferably 30-500 ppm, and more preferably 50-200 ppm; the polyamide 56 industrial yarn is 180°C, After 4h treatment, the retention rate of heat-resistant fracture strength is ⁇ 90%, preferably ⁇ 94%, more preferably ⁇ 98%; after treatment at 230°C for 30min, the retention rate of heat-resistant fracture strength is ⁇ 90%, preferably ⁇ 93%, It is more preferably ⁇ 96%; the dry heat shrinkage rate of the polyamide 56 industrial yarn is ⁇ 8.0%, preferably ⁇ 6.0%, and more preferably ⁇ 4.0%.
  • the polyamide 56 industrial yarn contains a heat stabilizer; preferably, the heat stabilizer includes any one or more of copper acetate, potassium iodide, copper chloride, cuprous iodide, copper oxide, and cuprous oxide
  • the addition amount of the heat stabilizer accounts for 10-2800ppm of the total weight of the production raw materials, preferably 100-2500ppm.
  • the heat stabilizer is a combination of copper acetate and potassium iodide, wherein the molar ratio of copper acetate to potassium iodide is 1:1-15, preferably 1:2-10, more preferably 1:6-8, wherein Preferably, the addition amount of copper acetate is 100-500 ppm, and the addition amount of potassium iodide is 500-2500 ppm.
  • the breaking strength of the polyamide 56 industrial yarn is 6.5 cN/dtex or more, preferably 7.0 cN/dtex or more, and more preferably 8.0 cN/dtex or more.
  • the relative viscosity of the oil-free yarn of the polyamide 56 industrial yarn is 2.7-4.5, and the absolute value of the difference between the relative viscosity of the oil-free yarn and the relative viscosity of the resin is ⁇ 0.12, preferably ⁇ 0.10, more preferably ⁇ 0.08.
  • the oil-free silk amino group content of the polyamide 56 industrial yarn is 20-50 mmol/kg; the absolute value of the difference between the oil-free silk amino group and the resin amino group is ⁇ 5, preferably ⁇ 3, more preferably ⁇ 2.
  • the number of broken single filaments of the polyamide 56 industrial yarn is less than or equal to 2 times/24h, preferably less than or equal to 1 time/24h, more preferably 0 times/24h, and the production rate of the polyamide 56 industrial yarn is greater than or equal to 90%, preferably greater than or equal to 93 %, more preferably ⁇ 96%.
  • the boiling water shrinkage rate of the polyamide 56 industrial yarn is 8.0% or less, preferably 7.0% or less, and more preferably 6.0% or less; and/or, the polyamide 56 industrial yarn has a fineness of 100-3500 dtex, Preferably it is 200-2500 dtex, more preferably 300-1800 dtex; the elongation at break of the polyamide 56 industrial yarn is 26% or less, preferably 22% or less; and/or, the crystallinity of the polyamide 56 industrial yarn It is 70% or more, preferably 72% or more, more preferably 74% or more; and/or, the orientation degree of the polyamide 56 industrial yarn is 80% or more, preferably 82% or more, and more preferably 84% or more.
  • the raw materials for the production of the polyamide 56 industrial yarn include at least: 1,5-pentanediamine and adipic acid; or, polyamide 56 obtained by polymerization of 1,5-pentanediamine and adipic acid as monomers.
  • the 1,5-pentanediamine is prepared from bio-based raw materials through fermentation or enzymatic conversion.
  • the 1,5-pentanediamine is prepared from bio-based raw materials through fermentation or enzymatic conversion.
  • the method for preparing 1,5-pentanediamine disclosed in patent CN109536542A is adopted.
  • the preparation method includes the following steps:
  • the polyamide 56 industrial yarn can adopt two methods: melt direct spinning or chip spinning.
  • the solid phase thickening the viscosity is increased by drying the low-viscosity polyamide 56 resin at a high temperature.
  • the solid phase viscosity increasing temperature is 120-180°C, preferably 150-160°C.
  • the drying time is 10-50h, preferably 15-30h.
  • the solid-phase thickening is carried out by high-temperature drying to remove water, and the polycondensation reaction continues to proceed to obtain a high-viscosity resin.
  • the polyamide 56 industrial yarn is obtained after processing the nascent yarn.
  • 1,5-pentanediamine and adipic acid are polymerized with a heat stabilizer, or in the form of a heat stabilizer masterbatch before polymerizing melt pelletizing on-line injection, or a heat stabilizer masterbatch The form is blended and added during the spinning process.
  • 1,5-pentanediamine and sebacic acid can be polymerized.
  • the content of copper ions in the heat stabilizer masterbatch is 0.5-10 wt%, 0.8-5 wt%, more 1.2-3 wt%.
  • the addition amount of the heat stabilizer masterbatch is 0.3-5.0 wt%, 0.5-3.0 wt%, more 0.8-2.0 wt%.
  • the heat stabilizer masterbatch matrix material is polyamide 6, polyamide 56, polyamide 66, polyamide 510, polyamide 610, polybutylene terephthalate, preferably Polyamide 6, polyamide 56, or polyamide 510, more preferably polyamide 6, polyamide 56.
  • the preparation method of the heat stabilizer masterbatch includes the following steps:
  • the powder obtained in step (1) is mixed with a heat stabilizer and other additives, and granulated.
  • twin-screw melt extrusion granulation can be used.
  • the processing temperature of each zone of the twin-screw extruder is 180-285°C
  • the screw speed is 25-350r/min
  • the vacuum degree is ⁇ -0.1MPa
  • the filter screen is 80 -200 mesh.
  • the base material is polyamide 56
  • the processing temperature of each zone of the twin-screw extruder is 260-275°C
  • the screw speed is 50-350r/min
  • the vacuum degree is ⁇ -0.1MPa
  • the filter screen is 100-150.
  • the added amount of the heat stabilizer is 0.5-20 wt% of the base material.
  • the heat stabilizer is a combination of copper acetate and potassium iodide, wherein the molar ratio of copper acetate to potassium iodide is 1:1-15, preferably 1:2-10, more preferably 1: 5-8.
  • the heat stabilizer is cuprous iodide.
  • the other additives include at least antioxidants and/or lubricants.
  • the polyamide 56 industrial yarn obtains better heat resistance and mechanical properties.
  • the inventor speculates that the melt fluidity of the polyamide 56 is good, and the heat stabilizer is in the polyamide. 56 resin can be distributed uniformly and has good compatibility.
  • polyamide 56 has an even-even carbon arrangement structure with a high ratio of amide bonds, and there are some amide bonds on different molecular chains that are not bonded.
  • Copper ions can play a good complexing effect between the amide bonds, make the polyamide 56 molecular chains more tightly connected, the intermolecular forces are greater, and the mechanical properties of the prepared industrial yarns are increased.
  • additives may be added during the spinning of the polyamide 56 industrial yarn.
  • the additives include: matting agents, flame retardants, antioxidants, ultraviolet absorbers, infrared absorbers, and crystallizing agents. Any one or more of the nucleating agent, fluorescent whitening agent and antistatic agent; preferably, the additive amount of the additive accounts for 0-5 wt% of the total weight of the production raw materials.
  • the antioxidant includes, but is not limited to, one, two or more of the commercially available antioxidant 1010, antioxidant 1098, antioxidant 168, and sodium hypophosphite.
  • the lubricant includes but is not limited to the commercially available P861/3.5, PTS HOB 7119, and the commercially available ET132, ET141 and wax OP.
  • step (1) the polymerization of polyamide 56 specifically includes the following steps:
  • the concentration of the polyamide 56 salt solution is between 40-85%.
  • the temperature of the reaction system at the end of the holding pressure is 230-275°C; and/or,
  • the temperature of the reaction system after the pressure reduction is completed is 240-285°C; and/or, preferably, the temperature after the vacuum is 265-295°C.
  • the relative viscosity of the low-viscosity polyamide 56 resin 96% sulfuric acid is 2.0-2.7, preferably 2.2-2.6, more preferably 2.4-2.5.
  • the relative viscosity of the 96% sulfuric acid of the high-viscosity polyamide 56 resin is 2.7-4.5, preferably 3.2-4.0, more preferably 3.4-3.6; and/or,
  • the content of the high-viscosity polyamide 56 resin oligomer is 0.2-1.0% by weight, preferably 0.4-0.6% by weight; and/or, the number-average molecular weight of the high-viscosity polyamide 56 resin is 18000-40000, preferably 25000-30000, the molecular weight distribution is 0.8-1.8, preferably 1.2-1.5;
  • the moisture content of the high-viscosity polyamide 56 resin is 200-800 ppm, preferably 300-750 ppm, more preferably 350-700 ppm, further preferably 400-600 ppm; and/or,
  • the amino group content of the high-viscosity polyamide 56 resin is 20-50 mmol/kg, preferably 24-45 mmol/kg, more preferably 28-40 mmol/kg, and still more preferably 32-36 mmol/kg.
  • the heating in step (1) is carried out in a screw extruder.
  • the screw extruder is divided into five zones for heating; among them, the temperature in the first zone is 250-290°C, and the temperature in the second zone is 250-290°C. It is 260-300°C, the temperature in zone three is 270-320°C, the temperature in zone four is 280-330°C, and the temperature in zone five is 280-320°C.
  • the spinning process in step (2) includes the following steps: spraying the polyamide 56 resin through the spinneret of the spinning box body to form the spun yarn.
  • the temperature of the spinning box is 270-330°C, more preferably 280-310°C, still more preferably 290-300°C, still more preferably 293-297°C; and/or, the spinning
  • the spinning assembly pressure of the box is 8-25 MPa, preferably 12-20 MPa, more preferably 15-18 MPa; and/or, the spinneret stretch ratio of the spinneret is 50-400, preferably 70- 300, more preferably 80-200, still more preferably 90-100.
  • the treatment process includes the following steps: heat preservation, cooling, oiling, stretching, and winding of the spun out of the spinneret hole to obtain the polymer Amide 56 industrial yarn;
  • the heat preservation is performed by a slow cooling device, the slow cooling temperature is 150-280°C, more preferably 200-240°C, and the slow cooling length is 10-80mm, more preferably 20-50mm; the cooling is through side Blowing for cooling, the wind speed of the side blowing is 0.3-2.0m/s, more preferably 0.6-1.5m/s; the wind temperature of the side blowing is 15-25°C, more preferably 17-23°C, further Preferably it is 19-22°C; the humidity of the side blowing is 60-80%, more preferably 65-75%; and/or,
  • the winding tension during the winding molding is 50-300cN, preferably 80-200cN, more preferably 100-160cN, and still more preferably 120-140cN; or, the winding speed is 2000-3800m/min , Preferably 2500-3500m/min, more preferably 2800-3000m/min; the winding overfeed ratio is ⁇ 5%, preferably ⁇ 4%, and more preferably ⁇ 3%.
  • the stretching process is more than four-stage stretching; preferably, the stretching process is: the nascent yarn after oiling is first fed to the first pair of heat rollers through the godet roller, The first-stage stretching is performed between the first pair of heat rollers and the second pair of heat rollers, and then the second-stage stretching is performed between the second pair of heat rollers and the third pair of heat rollers. Three-stage stretching is performed between the heat roller and the fourth pair of heat rollers and the first heat setting is performed, and then four-stage stretching is performed between the fourth pair of heat rollers and the fifth pair of heat rollers and the second time is performed Heat setting
  • the total stretching ratio of the stretching is 4.0-6.0;
  • the temperature of the first heat setting is 180-250°C, preferably 200-240°C; the temperature of the second heat setting is 200-240°C, preferably 220-230°C.
  • the raw material for the production of the polyamide 5X industrial yarn of the present invention is made by a biological method, which is a green material, does not depend on petroleum resources and does not cause serious pollution to the environment, can reduce carbon dioxide emissions and reduce the greenhouse effect.
  • the polyamide 5X industrial yarn of the present invention has good heat resistance, mechanical properties and dimensional stability.
  • the preparation method of the polyamide 5X industrial yarn of the present invention can add a heat-resistant stabilizer during the polymerization process, which belongs to in-situ polymerization. It can be uniformly distributed in the polyamide 5X resin when the mixing is sufficient, and the normal production is not affected during the spinning process. There are very few broken filaments, and the production rate is increased.
  • the polyamide 5X industrial yarn of the present invention is worth using conventional polyamide 6 and polyamide 66 industrial yarn equipment, without the need to modify the spinning equipment, by optimizing the quality of the polyamide 5X resin and the spinning process. Improve the production rate, reduce production costs, and bring huge benefits to spinning enterprises.
  • Retention rate of heat-resistant fracture strength ((breaking strength before heat treatment-breaking strength after heat treatment)/breaking force before heat treatment)*100%
  • the breaking strength is in accordance with GB/T 14344- Measured in 2008
  • the heat treatment equipment is an oven, the oven temperature is 180°C, and the treatment time is 4h (hours); and the oven temperature is 230°C, and the treatment time is 30min (minutes).
  • Boiling water shrinkage rate among which, the determination of boiling water shrinkage rate refers to GB/6505-2008 "Test Method for Thermal Shrinkage Rate of Chemical Fiber Filament", specifically: take a section of polyamide industrial yarn, pre-tensioned 0.05 ⁇ 0.005cN/ dtex, after marking 50.00cm at the middle ends, wrap it with gauze, put it in boiling water and boil for 30 minutes, then, after the sample is dried, measure the length between the two marked points, and use the following formula to calculate the boiling water shrinkage rate:
  • Boiling water shrinkage ratio ((initial length-length after shrinkage)/initial length)*100%.
  • Relative viscosity The relative viscosity of polyamide oil-free silk (unoiled spun silk) and resin is measured by Ubbelohde viscometer concentrated sulfuric acid method. The steps are as follows: accurately weigh the dried polyamide resin or its Staple fiber sample 0.25 ⁇ 0.0002g, add 50mL concentrated sulfuric acid (96%) to dissolve, measure and record the flow time t 0 of concentrated sulfuric acid and the flow of polyamide 56 slice or its short fiber sample solution in a constant temperature water bath at 25°C Time t.
  • relative viscosity VN t/t 0 ; t-solution flow time; t 0 -solvent flow time.
  • Moisture content measured according to Karl Fischer moisture titrator.
  • Crystallinity and orientation D/max-2550 PC X-ray diffractometer produced by Japan Rigaku Corporation is used to analyze fiber samples, Cu target wavelength The voltage is 20-40kV, the current is 10-450mA, and the range of measuring angle 2 ⁇ is 5-40°.
  • the sample of the polyamide 56 industrial yarn used for testing crystallization is fully cut and the sample mass is greater than 0.2g; the sample of the polyamide 56 industrial yarn used for testing the crystallite orientation is neatly combed, and a bundle of 30mm long is tested.
  • Use software such as origin for data processing, analyze and calculate the crystallinity and orientation of the fiber.
  • ⁇ I c is the total integrated diffraction intensity of the crystalline part
  • ⁇ I a is the integrated scattering intensity of the amorphous part.
  • H i is the half-height width of the i-th peak.
  • Oligomer content water extraction method (weighing), accurately weigh about 8g of polyamide 56 resin dried at 130°C for 7 hours, put it in a 500mL round-bottomed flask, add 400g of water, and reflux in a heating mantle After 36h, the solution was decanted, and the particles were dried in a constant-weight beaker at 130°C for 7 hours, then plastic-sealed in an aluminum-plastic bag, cooled, and weighed to calculate the weight loss.
  • Polyamide 56 resin is prepared by referring to the methods disclosed in CN108503826A and CN108503824A, with a relative viscosity of 2.7-4.5.
  • Production rate the weight of the industrial yarn obtained after spinning and the weight percentage of the resin input.
  • Example 1 Polyamide 56 industrial yarn (933dtex/140f)
  • the preparation method includes the following steps:
  • the low-viscosity polyamide 56 resin prepares a high-viscosity polyamide 56 resin through solid-phase tackification.
  • the temperature of the solid phase thickening is 155°C, and the drying time is 20h.
  • the relative viscosity of the low-viscosity polyamide 56 resin 96% sulfuric acid is 2.4.
  • the high-viscosity polyamide 56 resin 96% sulfuric acid has a relative viscosity of 3.3, an oligomer content of 0.8 wt%, a number average molecular weight of 30,000, a molecular weight distribution of 1.6, a water content of 400 ppm, and an amino group content of 36.5 mmol/kg.
  • the high-viscosity polyamide 56 resin is heated to a molten state to form a polyamide 56 melt.
  • the heating is carried out in a screw extruder, which is divided into five heating zones; among them, one zone The temperature is 255°C, the temperature in the second zone is 270°C, the temperature in the third zone is 280°C, the temperature in the fourth zone is 290°C, and the temperature in the fifth zone is 300°C.
  • the polyamide 56 melt was sprayed through the spinneret of the spinning box to form spun yarn; the temperature of the spinning box was 290° C., the component pressure was 15 MPa, and the spinneret stretch ratio was 150.
  • the heat preservation adopts a slow cooling device, the slow cooling temperature is 220°C, and the slow cooling length is 20 mm;
  • the cooling is performed by side blowing, the wind speed is 1.2m/s, the wind temperature is 22°C, and the humidity is 70%.
  • the stretching process is a four-stage stretching; the stretching process is: the nascent yarn after oiling is first fed to the first pair of heat rollers through the godet roller, and the first pair of heat rollers and the second pair of heat rollers are Perform primary stretching between the rollers, then perform secondary stretching between the second pair of heat rollers and the third pair of heat rollers, and perform three times between the third pair of heat rollers and the fourth pair of heat rollers. Stretching and heat setting for the first time, and then stretched between the fourth pair of heat rollers and the fifth pair of heat rollers and heat setting for the second time; wherein, the total stretching of the stretching
  • the extension is 5.0; the temperature of the first heat setting is 220°C; the temperature of the second heat setting is 230°C.
  • the winding tension during the winding molding is 90 cN, the winding speed is 3500 m/min, and the winding overfeed ratio is 2%.
  • Example 2 Polyamide 56 industrial yarn (830dtex/192f)
  • the preparation method includes the following steps:
  • the low-viscosity polyamide 56 resin prepares a high-viscosity polyamide 56 resin through solid-phase tackification.
  • the temperature of the solid phase thickening is 160° C., and the drying time is 18 hours.
  • the relative viscosity of the low-viscosity polyamide 56 resin 96% sulfuric acid is 2.5.
  • the high-viscosity polyamide 56 resin 96% sulfuric acid has a relative viscosity of 3.5, an oligomer content of 0.6 wt%, a number average molecular weight of 33,000, a molecular weight distribution of 1.5, a moisture content of 450 ppm, and an amino group content of 33.5 mmol/kg.
  • the high-viscosity polyamide 56 resin is heated to a molten state to form a polyamide 56 melt.
  • the heating is carried out in a screw extruder, specifically divided into five heating zones, one zone having a temperature of 265°C, two The zone temperature is 275°C, the temperature in zone three is 285°C, the temperature in zone four is 295°C, and the temperature in zone five is 305°C.
  • the polyamide 56 melt was sprayed through the spinneret of the spinning box to form spun yarn; the temperature of the spinning box was 295° C., the component pressure was 18 MPa, and the spinneret stretch ratio was 180.
  • Example 3 Polyamide 56 industrial yarn (550dtex/96f)
  • the preparation method includes the following steps:
  • the low-viscosity polyamide 56 resin prepares a high-viscosity polyamide 56 resin through solid-phase tackification.
  • the temperature of the solid phase thickening is 160° C., and the drying time is 22 h.
  • the relative viscosity of the low-viscosity polyamide 56 resin 96% sulfuric acid is 2.6.
  • the high-viscosity polyamide 56 resin 96% sulfuric acid has a relative viscosity of 3.0, an oligomer content of 0.8 wt%, a number average molecular weight of 30,000, a molecular weight distribution of 1.6, a water content of 400 ppm, and an amino group content of 42.5 mmol/kg.
  • the high-viscosity polyamide 56 resin is heated to a molten state to form a polyamide 56 melt.
  • the heating is carried out in a screw extruder, which is specifically divided into five heating zones, one zone having a temperature of 248°C, two The temperature in zone is 263°C, the temperature in zone three is 276°C, the temperature in zone four is 285°C, and the temperature in zone five is 293°C.
  • the polyamide 56 melt is sprayed through the spinneret of the spinning box to form the spun yarn; the temperature of the spinning box is 285°C, the component pressure is 16MPa, and the spinneret draw ratio is 100.
  • Example 4 Polyamide 56 industrial yarn (550dtex/96f)
  • the preparation method includes the following steps:
  • the low-viscosity polyamide 56 resin prepares a high-viscosity polyamide 56 resin through solid-phase tackification.
  • the temperature of the solid phase thickening is 150° C., and the drying time is 25 h.
  • the relative viscosity of the low-viscosity polyamide 56 resin 96% sulfuric acid is 2.55.
  • the high-viscosity polyamide 56 resin 96% sulfuric acid has a relative viscosity of 2.9, an oligomer content of 0.8 wt%, a number average molecular weight of 28,000, a molecular weight distribution of 1.5, a moisture content of 300 ppm, and an amino group content of 40.5 mmol/kg.
  • the high-viscosity polyamide 56 resin is heated to a molten state to form a polyamide 56 melt.
  • the heating is carried out in a screw extruder and is specifically divided into five heating zones, one with a temperature of 245°C, two The zone temperature is 260°C, the temperature in zone three is 270°C, the temperature in zone four is 285°C, and the temperature in zone five is 290°C.
  • the polyamide 56 melt was sprayed through the spinneret of the spinning box to form spun yarn; the temperature of the spinning box was 280° C., the component pressure was 10 MPa, and the spinneret stretch ratio was 200.
  • Example 5 Polyamide 56 industrial yarn (233dtex/36f)
  • the preparation method includes the following steps:
  • the low-viscosity polyamide 56 resin prepares a high-viscosity polyamide 56 resin through solid-phase tackification.
  • the solid-phase thickening temperature is 155°C, and the drying time is 25h.
  • the relative viscosity of the low-viscosity polyamide 56 resin 96% sulfuric acid is 2.45.
  • the high-viscosity polyamide 56 resin 96% sulfuric acid has a relative viscosity of 3.6, an oligomer content of 1.0 wt%, a number average molecular weight of 36,000, a molecular weight distribution of 1.7, a water content of 350 ppm, and an amino group content of 46.5 mmol/kg.
  • the high-viscosity polyamide 56 resin is heated to a molten state to form a polyamide 56 melt.
  • the heating is carried out in a screw extruder, and is specifically divided into five heating zones, one with a temperature of 255°C, two The zone temperature is 275°C, the temperature in zone three is 280°C, the temperature in zone four is 295°C, and the temperature in zone five is 310°C.
  • the polyamide 56 melt was sprayed through the spinneret of the spinning box to form spun yarn; the temperature of the spinning box was 295° C., the component pressure was 19 MPa, and the spinneret stretch ratio was 250.
  • the stretching process is a four-stage stretching, and the stretching process is the same as in the first embodiment; the difference is that the total stretching ratio of the stretching is 5.5; and the temperature of the first heat setting is 230°C; The temperature of the second heat setting was 230°C.
  • Example 6 Polyamide 56 industrial yarn (1670dtex/192f)
  • the preparation method includes the following steps:
  • the raw materials 1,5-pentanediamine, adipic acid and water are mixed uniformly, and a heat stabilizer is added to prepare a polyamide 56 salt solution with a concentration of 65%; wherein, the 1,5 -The molar ratio of pentane diamine and adipic acid is 1.1:1.
  • the heat stabilizer is a combination of copper acetate and potassium iodide, the added amount of copper acetate accounts for 200 ppm of the total weight of the production raw materials, and the added amount of potassium iodide accounts for 500 ppm of the total weight of the production raw materials.
  • the low-viscosity polyamide 56 resin prepares a high-viscosity polyamide 56 resin through solid-phase tackification.
  • the solid-phase thickening temperature is 155°C, and the drying time is 30h.
  • the relative viscosity of the low-viscosity polyamide 56 resin 96% sulfuric acid is 2.7.
  • the high-viscosity polyamide 56 resin 96% sulfuric acid has a relative viscosity of 3.8, an oligomer content of 0.8 wt%, a number average molecular weight of 38,000, a molecular weight distribution of 1.5, a water content of 500 ppm, and an amino group content of 42.5 mmol/kg.
  • the high-viscosity polyamide 56 resin is heated to a molten state to form a polyamide 56 melt.
  • the heating is carried out in a screw extruder, which is specifically divided into five heating zones, one with a temperature of 250°C, two The zone temperature is 275°C, the temperature in zone three is 280°C, the temperature in zone four is 295°C, and the temperature in zone five is 305°C.
  • the polyamide 56 melt was sprayed through the spinneret of the spinning box to form spun yarn; the temperature of the spinning box was 290° C., the component pressure was 14 MPa, and the spinneret stretch ratio was 120.
  • the stretching process is a four-stage stretching, and the stretching process is the same as in the first embodiment; the difference is that the total stretching ratio of the stretching is 5.6; the temperature of the first heat setting is 225°C; The temperature of the second heat setting was 235°C.
  • Example 7 Polyamide 56 industrial yarn (2800dtex/480f)
  • the preparation method includes the following steps:
  • the raw materials 1,5-pentanediamine, adipic acid and water are mixed uniformly, and a heat stabilizer is added to prepare a polyamide 56 salt solution with a concentration of 65%; wherein, the 1,5 -The molar ratio of pentane diamine and adipic acid is 1.05:1.
  • the heat stabilizer is a combination of copper acetate and potassium iodide, the added amount of copper acetate accounts for 250 ppm of the total weight of the production raw materials, and the added amount of potassium iodide accounts for 2000 ppm of the total weight of the production raw materials.
  • the low-viscosity polyamide 56 resin prepares a high-viscosity polyamide 56 resin through solid-phase tackification.
  • the solid-phase thickening temperature is 155°C, and the drying time is 30h.
  • the relative viscosity of the low-viscosity polyamide 56 resin 96% sulfuric acid is 2.35.
  • the high-viscosity polyamide 56 resin 96% sulfuric acid has a relative viscosity of 3.2, an oligomer content of 0.8 wt%, a number average molecular weight of 32,000, a molecular weight distribution of 1.5, a moisture content of 450 ppm, and an amino group content of 38.5 mmol/kg.
  • the high-viscosity polyamide 56 resin is heated to a molten state to form a polyamide 56 melt.
  • the heating is carried out in a screw extruder, which is specifically divided into five heating zones, one with a temperature of 258°C, two The temperature in the zone is 276°C, the temperature in zone three is 288°C, the temperature in zone four is 298°C, and the temperature in zone five is 305°C.
  • the polyamide 56 melt was sprayed through the spinneret of the spinning box to form spun yarn; the temperature of the spinning box was 293° C., the component pressure was 12 MPa, and the spinneret stretch ratio was 160.
  • the stretching process is a four-stage stretching, and the stretching process is the same as in the first embodiment; the difference is that the total stretching ratio of the stretching is 4.8; the temperature of the first heat setting is 220°C; The temperature of the second heat setting was 230°C.
  • Example 8 Polyamide 56 industrial yarn (233dtex/36f)
  • the preparation method includes the following steps:
  • the raw materials 1,5-pentanediamine, adipic acid and water are mixed uniformly, and a heat stabilizer is added to prepare a polyamide 56 salt solution with a concentration of 65%; wherein, the 1,5 -The molar ratio of pentane diamine and adipic acid is 1.05:1.
  • the heat stabilizer is a combination of copper acetate and potassium iodide, the added amount of copper acetate accounts for 150 ppm of the total weight of the production raw materials, and the added amount of potassium iodide accounts for 800 ppm of the total weight of the production raw materials.
  • the low-viscosity polyamide 56 resin prepares a high-viscosity polyamide 56 resin through solid-phase tackification.
  • the solid-phase thickening temperature is 155°C, and the drying time is 30h.
  • the relative viscosity of the low-viscosity polyamide 56 resin 96% sulfuric acid is 2.4.
  • the high-viscosity polyamide 56 resin 96% sulfuric acid has a relative viscosity of 3.4, an oligomer content of 0.8 wt%, a number average molecular weight of 33,000, a molecular weight distribution of 1.6, a moisture content of 550 ppm, and an amino group content of 33.5 mmol/kg.
  • the high-viscosity polyamide 56 resin is heated to a molten state to form a polyamide 56 melt.
  • the heating is carried out in a screw extruder, which is specifically divided into five heating zones, one zone having a temperature of 268°C, two The zone temperature is 280°C, the temperature in zone three is 290°C, the temperature in zone four is 295°C, and the temperature in zone five is 303°C.
  • the polyamide 56 melt was sprayed through the spinneret of the spinning box to form spun yarn; the temperature of the spinning box was 298° C., the component pressure was 18 MPa, and the spinneret stretch ratio was 120.
  • the stretching process is a four-stage stretching, and the stretching process is the same as in the first embodiment; the difference is that the total stretching ratio of the stretching is 4.8; the temperature of the first heat setting is 220°C; The temperature of the second heat setting was 230°C.
  • Example 9 Polyamide 56 industrial yarn (933dtex/140f)
  • the preparation method includes the following steps:
  • the low-viscosity polyamide 56 resin prepares a high-viscosity polyamide 56 resin through solid-phase tackification.
  • the temperature of the solid phase thickening is 160°C, and the drying time is 22h.
  • the relative viscosity of the low-viscosity polyamide 56 resin 96% sulfuric acid is 2.4.
  • the high-viscosity polyamide 56 resin 96% sulfuric acid has a relative viscosity of 3.4, an oligomer content of 0.8 wt%, a number average molecular weight of 33,000, a molecular weight distribution of 1.6, a moisture content of 550 ppm, and an amino group content of 33.5 mmol/kg.
  • the high-viscosity polyamide 56 resin is heated to a molten state to form a polyamide 56 melt.
  • the heating is carried out in a screw extruder, which is specifically divided into five heating zones, one zone having a temperature of 268°C, two The zone temperature is 280°C, the temperature in zone three is 290°C, the temperature in zone four is 295°C, and the temperature in zone five is 303°C.
  • the polyamide 56 melt was sprayed through the spinneret of the spinning box to form spun yarn; the temperature of the spinning box was 280° C., the component pressure was 13 MPa, and the spinneret stretch ratio was 150.
  • the stretching process is a four-stage stretching, and the stretching process is the same as in the first embodiment; the difference is that the total stretching ratio of the stretching is 4.8; the temperature of the first heat setting is 210°C; The temperature of the second heat setting was 220°C.
  • Example ten Polyamide 56 industrial yarn (933dtex/140f)
  • the preparation method includes the following steps:
  • the thermal stabilizer masterbatch is injected online before pelletizing of the polymer melt.
  • the copper ion content of the thermal stabilizer masterbatch is 2.0wt%, and the addition amount of the thermal stabilizer masterbatch is 1.5wt%.
  • the base material of the heat stabilizer masterbatch is polyamide 56.
  • the preparation method of the heat stabilizer masterbatch includes the following steps: (a) vacuum drying the base material polyamide 56 and then grinding; the polyamide 56 is 65 parts by weight, the relative viscosity is 2.9, and the number average molecular weight is 24 kg /mol, the molecular weight distribution is 2.1, and the moisture content is 500 ppm.
  • step (b) Mix the powder obtained in step (a) with 12.5 parts by weight of heat stabilizer cuprous iodide, 0.5 parts by weight of lubricant wax OP, and 0.2 parts by weight of antioxidant 168, and use twin-screw melt extrusion granulation to obtain Heat stabilizer masterbatch, the processing temperature of each zone is 251°C in one zone, 264°C in two zone, 269°C in three zone, 273°C in four zone, 276°C in five zone, screw speed 250r/min, filter screen 150 mesh.
  • the low-viscosity polyamide 56 resin prepares a high-viscosity polyamide 56 resin through solid-phase tackification.
  • the solid-phase thickening temperature is 155°C, and the drying time is 25h.
  • the relative viscosity of the low-viscosity polyamide 56 resin 96% sulfuric acid is 2.5.
  • the high-viscosity polyamide 56 resin 96% sulfuric acid has a relative viscosity of 3.7, an oligomer content of 0.6 wt%, a number average molecular weight of 34000, a molecular weight distribution of 1.5, a moisture content of 300 ppm, and an amino group content of 33.8 mmol/kg.
  • the high-viscosity polyamide 56 resin is heated to a molten state to form a polyamide 56 melt.
  • the heating is carried out in a screw extruder, specifically divided into five heating zones, one zone having a temperature of 265°C, two The temperature in zone is 278°C, the temperature in zone three is 288°C, the temperature in zone four is 295°C, and the temperature in zone five is 300°C.
  • the polyamide 56 melt was ejected through the spinneret of the spinning box to form spun yarn; the temperature of the spinning box was 295° C., the component pressure was 14 MPa, and the spinneret stretch ratio was 80.
  • the winding tension during the winding molding is 90 cN, the winding speed is 2600 m/min, and the winding overfeed ratio is 2%.
  • the stretching process is a four-stage stretching, and the stretching process is the same as in the first embodiment; the difference is that the total stretching ratio of the stretching is 5.0; the temperature of the first heat setting is 220°C; The temperature of the second heat setting was 230°C.
  • Example 11 Polyamide 56 industrial yarn (933dtex/140f)
  • the preparation method includes the following steps:
  • the low-viscosity polyamide 56 resin prepares a high-viscosity polyamide 56 resin through solid-phase tackification.
  • the solid phase thickening temperature is 160° C., and the drying time is 28 h.
  • the relative viscosity of the low-viscosity polyamide 56 resin 96% sulfuric acid is 2.4.
  • the high-viscosity polyamide 56 resin 96% sulfuric acid has a relative viscosity of 3.3, an oligomer content of 0.9 wt%, a number average molecular weight of 32,000, a molecular weight distribution of 1.6, a moisture content of 450 ppm, and an amino group content of 36.5 mmol/kg.
  • the high-viscosity polyamide 56 resin is heated to a molten state to form a polyamide 56 melt.
  • the heating is carried out in a screw extruder, and is specifically divided into five heating zones, one with a temperature of 255°C, two The temperature in the zone is 275°C, the temperature in the third zone is 280°C, the temperature in the fourth zone is 290°C, and the temperature in the fifth zone is 305°C.
  • the polyamide 56 melt was sprayed through the spinneret of the spinning box to form spun yarn; the temperature of the spinning box was 295° C., the component pressure was 14 MPa, and the spinneret stretch ratio was 140.
  • the heat stabilizer masterbatch is blended and added by the masterbatch adding device, and the copper ion content in the heat stabilizer masterbatch is 1.8 wt%.
  • the addition amount of heat stabilizer masterbatch is 1.2wt%.
  • the preparation method of the heat stabilizer masterbatch is the same as in Example 10.
  • the winding tension during the winding molding is 90 cN, the winding speed is 3500 m/min, and the winding overfeed ratio is 2%.
  • the stretching process is a four-stage stretching, and the stretching process is the same as in the first embodiment; the difference is that the total stretching ratio of the stretching is 5.0; the temperature of the first heat setting is 220°C; The temperature of the second heat setting was 230°C.
  • Example 12 Polyamide 56 industrial yarn (933dtex/140f)
  • the preparation method includes the following steps:
  • the low-viscosity polyamide 56 resin prepares a high-viscosity polyamide 56 resin through solid-phase tackification.
  • the solid phase thickening temperature is 160° C., and the drying time is 28 h.
  • the relative viscosity of the low-viscosity polyamide 56 resin 96% sulfuric acid is 2.4.
  • the high-viscosity polyamide 56 resin 96% sulfuric acid has a relative viscosity of 3.2, an oligomer content of 0.8 wt%, a number average molecular weight of 30,000, a molecular weight distribution of 1.6, a water content of 400 ppm, and an amino group content of 32.3 mmol/kg.
  • the high-viscosity polyamide 56 resin is heated to a molten state to form a polyamide 56 melt.
  • the heating is carried out in a screw extruder, which is specifically divided into five heating zones, one with a temperature of 250°C, two The zone temperature is 270°C, the temperature in zone three is 285°C, the temperature in zone four is 290°C, and the temperature in zone five is 290°C.
  • the polyamide 56 melt was sprayed through the spinneret of the spinning box to form spun yarn; the temperature of the spinning box was 285° C., the component pressure was 12 MPa, and the spinneret stretch ratio was 180.
  • the heat stabilizer masterbatch is blended and added by the masterbatch adding device, and the copper ion content in the heat stabilizer masterbatch is 1.6 wt%.
  • the addition amount of heat stabilizer masterbatch is 1.5wt%.
  • the base material of the heat stabilizer masterbatch is polyamide 6.
  • the preparation method of the heat stabilizer masterbatch includes the following steps: (a) vacuum drying the base material polyamide 6 and then grinding; the polyamide 6 is 65 parts by weight, the relative viscosity is 2.9, and the number average molecular weight is 24 kg /mol, the molecular weight distribution is 2.1, and the moisture content is 500 ppm.
  • step (b) Mix the powder obtained in step (a) with 15 parts by weight of heat stabilizer cuprous iodide, 0.5 parts by weight of lubricant wax OP, and 0.2 parts by weight of antioxidant 168, and use twin-screw melt extrusion granulation to obtain Heat stabilizer masterbatch, the processing temperature of each zone is 200°C in one zone, 210°C in two zone, 220°C in three zone, 230°C in four zone, 235°C in five zone, screw speed 250r/min, filter screen 150 mesh.
  • the winding tension during the winding molding is 90 cN, the winding speed is 3300 m/min, and the winding overfeed ratio is 2%.
  • the stretching process is a four-stage stretching, and the stretching process is the same as in the first embodiment; the difference is that the total stretching ratio of the stretching is 5.0; the temperature of the first heat setting is 220°C; The temperature of the second heat setting was 230°C.
  • Example 13 Polyamide 56 industrial yarn (933dtex/140f)
  • the preparation method includes the following steps:
  • the relative viscosity of the high-viscosity polyamide 56 melt 96% sulfuric acid is 3.4, the oligomer content is 0.8% by weight, the number average molecular weight is 30,000, the molecular weight distribution is 1.6, the water content is 400ppm, and the amino group content is 32.5mmol/kg .
  • the high-viscosity polyamide 56 melt is transported to the spinning box through a melt booster pump, and the spinning is directly performed.
  • the polyamide 56 melt is sprayed through the spinneret of the spinning box to form spun yarn; the temperature of the spinning box is 280° C., the component pressure is 18 MPa, and the spinneret draw ratio is 200.
  • the winding tension during the winding molding is 90 cN, the winding speed is 2500 m/min, and the winding overfeed ratio is 2%.
  • the stretching process is a four-stage stretching, and the stretching process is the same as in the first embodiment; the difference is that the total stretching ratio of the stretching is 5.0; the temperature of the first heat setting is 220°C; The temperature of the second heat setting was 230°C.
  • Example 14 Polyamide 56 industrial yarn (2800dtex/480f)
  • the preparation method includes the following steps:
  • the raw materials 1,5-pentanediamine, adipic acid and water are uniformly mixed, and a heat stabilizer is added to prepare a polyamide 56 salt solution with a concentration of 65%; wherein, the 1,5 -The molar ratio of pentane diamine and adipic acid is 1.08:1.
  • the heat stabilizer is a combination of copper acetate and potassium iodide, the added amount of copper acetate accounts for 200 ppm of the total weight of the production raw materials, and the added amount of potassium iodide accounts for 700 ppm of the total weight of the production raw materials.
  • the relative viscosity of the high-viscosity polyamide 56 melt 96% sulfuric acid is 3.5, the oligomer content is 1.0% by weight, the number average molecular weight is 34000, the molecular weight distribution is 1.6, the water content is 450 ppm, and the amino group content is 40.5 mmol/kg .
  • the high-viscosity polyamide 56 melt is transported to the spinning box through a melt booster pump, and the spinning is directly performed.
  • the polyamide 56 melt is ejected through the spinneret of the spinning box to form spun yarn; the temperature of the spinning box is 290° C., the component pressure is 12 MPa, and the spinneret stretch ratio is 180.
  • the winding tension during the winding molding is 280 cN, the winding speed is 2900 m/min, and the winding overfeed ratio is 3%.
  • the stretching process is a four-stage stretching, and the stretching process is the same as in the first embodiment; the difference is: the total stretching ratio of the stretching is 4.5; the temperature of the first heat setting is 220°C; The temperature of the second heat setting was 230°C.
  • Example 15 Polyamide 56 industrial yarn (1670dtex/192f)
  • the preparation method is the same as that in Example 6, except that the heat stabilizer is a combination of copper acetate and potassium iodide.
  • the addition amount of copper acetate accounts for 200 ppm of the total weight of the production raw materials, and the addition amount of potassium iodide accounts for 1000 ppm of the total weight of the production raw materials.
  • Example 16 Polyamide 56 industrial yarn (1670dtex/192f)
  • the preparation method is the same as that in Example 6, except that the heat stabilizer is a combination of copper acetate and potassium iodide.
  • the addition amount of copper acetate accounts for 200 ppm of the total weight of the production raw materials, and the addition amount of potassium iodide accounts for 2000 ppm of the total weight of the production raw materials.
  • Example 17 Polyamide 56 industrial yarn (1670dtex/192f)
  • the preparation method is the same as that in Example 6, except that the heat stabilizer is a combination of copper acetate and potassium iodide.
  • the addition amount of copper acetate accounts for 200 ppm of the total weight of the production raw materials, and the addition amount of potassium iodide accounts for 1800 ppm of the total weight of the production raw materials.
  • Example 18 Polyamide 56 industrial yarn (1670dtex/192f)
  • the preparation method is the same as in Example 6, except that the heat stabilizer is a combination of copper acetate and potassium iodide, the addition of copper acetate accounts for 200 ppm of the total weight of the production raw materials, and the addition amount of potassium iodide accounts for 2500 ppm of the total weight of the production raw materials.
  • the heat stabilizer is a combination of copper acetate and potassium iodide
  • the addition of copper acetate accounts for 200 ppm of the total weight of the production raw materials
  • the addition amount of potassium iodide accounts for 2500 ppm of the total weight of the production raw materials.
  • Comparative example 1 Polyamide 56 industrial yarn (933dtex/140f)
  • the preparation method is the same as in Example 1, except that the heat stabilizer copper acetate is not added in the polymerization of 1,5-pentanediamine and adipic acid in step (1).
  • the preparation method is the same as that of Example 1, except that in step 1 of the polymerization, the obtained high-viscosity polyamide 56 resin has a moisture content of 1200 ppm.
  • the preparation method includes the following steps:
  • the raw materials 1,5-pentanediamine, adipic acid and water are mixed uniformly, and a heat stabilizer is added to prepare a polyamide 56 salt solution with a concentration of 60%; wherein, the 1,5 -The molar ratio of pentane diamine and adipic acid is 1.1:1.
  • the heat stabilizer is a combination of copper acetate and potassium iodide, the addition amount of copper acetate accounts for 200 ppm of the total weight of the production raw materials, and the addition amount of potassium iodide accounts for 500 ppm of the total weight of the production raw materials.
  • the low-viscosity polyamide 56 resin 96% sulfuric acid has a relative viscosity of 2.5, an oligomer content of 0.8 wt%, a number average molecular weight of 16000, a molecular weight distribution of 1.5, a water content of 500 ppm, and an amino group content of 42.5 mmol/kg.
  • the low-viscosity polyamide 56 resin is heated to a molten state to form a polyamide 56 melt.
  • the heating is carried out in a screw extruder, and is specifically divided into five heating zones, one with a temperature of 250°C, two The zone temperature is 275°C, the temperature in zone three is 280°C, the temperature in zone four is 295°C, and the temperature in zone five is 305°C.
  • the polyamide 56 melt was sprayed through the spinneret of the spinning box to form spun yarn; the temperature of the spinning box was 290° C., the component pressure was 14 MPa, and the spinneret stretch ratio was 120.
  • the heat preservation adopts a slow cooling device, the slow cooling temperature is 230°C, and the slow cooling length is 40mm; the cooling is side blowing for cooling, the wind speed is 1.1m/s, the wind temperature is 23°C, and the humidity is 75%.
  • the winding tension during the winding molding is 160 cN, the winding speed is 3200 m/min, and the winding overfeed ratio is 3.5%.
  • the stretching process is a four-stage stretching, and the stretching process is the same as in the first embodiment; the difference is that the total stretching ratio of the stretching is 5.6; the temperature of the first heat setting is 225°C; The temperature of the second heat setting was 235°C.
  • the preparation method includes the following steps:
  • the high-viscosity polyamide 6 resin is heated to a molten state to form a polyamide 6 melt.
  • the heating is carried out in a screw extruder, which is specifically divided into five heating zones, the temperature of the first zone is 255°C, and the temperature of the second zone is 270°C, the temperature in zone three is 280°C, the temperature in zone four is 290°C, and the temperature in zone five is 300°C.
  • the high-viscosity polyamide 6 resin 96% sulfuric acid has a relative viscosity of 3.3, an oligomer content of 0.8 wt%, a number average molecular weight of 30,000, a molecular weight distribution of 1.6, a water content of 400 ppm, and an amino content of 36.5 mmol/kg.
  • the polyamide 6 industrial yarn is obtained after the nascent silk is processed, and the treatment process includes the following steps: heat preservation, cooling, oiling, drawing, and winding of the spinneret hole nascent silk ,
  • the polyamide 56 industrial yarn is obtained; the heat preservation is carried out by a slow cooling device, the slow cooling temperature is 220 °C, the slow cooling length is 20 mm; the cooling is side blowing for cooling, the wind speed is 1.2m/s, and the wind temperature is 22 °C, humidity is 70%.
  • the winding tension during the winding molding is 90 cN, the winding speed is 3500 m/min, and the winding overfeed ratio is 2.0%.
  • the stretching process is a four-stage stretching, and the stretching process is the same as in the first embodiment; the difference is that the total stretching ratio of the stretching is 5.0; the temperature of the first heat setting is 220°C; The temperature of the second heat setting was 230°C.
  • the invention improves the uniformity and stability of the polyamide 56 melt by reducing the oil-free filament viscosity and the fluctuation range of amino groups, reduces the number of filament breaks, increases the spinnability, and the production rate of the prepared polyamide 56 industrial yarn ⁇ 95%, the number of broken filaments ⁇ 1 time/24h.
  • the present invention optimizes polyamide 56 resin viscosity, oligomer content, molecular weight and distribution, and moisture content, and secondly optimizes the spinning process of polyamide 56 industrial yarn, which improves the crystallinity and orientation of polyamide 56 industrial yarn and increases the setting Temperature and increase the winding overfeed ratio, reduce the subsequent stress relaxation, and finally obtain polyamide 56 industrial yarn with excellent mechanical properties and dimensional stability.
  • the breaking strength can reach more than 8.0cN/dtex and the breaking elongation rate is 26%. Below; Dry heat shrinkage and boiling water shrinkage can reach below 6%; Crystallinity is above 70%; Orientation is above 80%.

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Abstract

本发明公开了一种聚酰胺5X工业丝，所述聚酰胺5X工业丝在180℃、4h处理后，耐热断裂强力保持率≥90％；在230℃、30min处理后，耐热断裂强力保持率≥90％；干热收缩率为≤8.0％。所述的聚酰胺5X工业丝在缝纫线、轮胎帘子线、气囊丝、脱模布、水布、帆布、安全带、绳索、渔网、工业过滤布、传输带、降落伞、帐篷、箱包领域具有广泛应用。

Description

一种聚酰胺5X工业丝及其制备方法与应用 技术领域
本发明属于聚酰胺材料技术领域，涉及一种聚酰胺5X工业丝及其制备方法和应用。
背景技术
工业丝的生产工艺有两种：一种是采用熔体直接纺丝法，另一种是采用切片固相增粘间接纺丝法。目前聚酰胺66与聚对苯二甲酸已二醇酯已经部分采用熔体直接纺丝，聚酰胺6因聚合物中含有8-10wt％单体，需要经过除单工序去除单体，目前无法直接进行熔体纺丝。
涤纶、锦纶工业丝具有强度高、伸长率低、尺寸稳定性好、耐疲劳和耐老化等特点，使得其广泛应用于轮胎帘子线、帆布、传输带、安全气囊、降落伞、绳索、安全带、工业滤布或帐篷等领域。不同应用领域对工业丝材料耐热性能要求较高，目前主要通过添加热稳定剂母粒进行共混方法。热稳定剂母粒价格高，且在纺丝过程中需要纺丝厂家配备母粒在线装置，设备投资成本大，此外，还需要解决热稳定剂母粒与基体材料相容性问题，如果添加不均匀，纺丝过程中产生断单丝现象，造成工业丝生产制成率降低，甚至影响纤维的力学性能。
专利CN110055602A公开了一种聚酰胺56高强力工业丝及其制备方法，使用常规聚酰胺56切片进行纺丝，未对聚酰胺56切片进行耐热改性，其制备的工业丝耐热性能差，无法应用在对耐热要求高的领域，如缝纫线、轮胎帘子线、气囊丝、脱模布、水布等方面。采用高速卷绕工艺，卷绕速度大于4000m/min，卷绕速度高，纤维在不同热辊上面停留时间相对缩短，即纤维高温定型时间缩变短，其次采用低倍率拉伸工艺，造成纤维结晶与取向偏低，制备的纤维强力偏低与尺寸稳定性变差。
发明内容
本发明的第一个目的在于提供一种同时具有优异耐热性能与力学性能的聚酰胺5X工业丝，所述聚酰胺5X工业丝在180℃、4h处理后，耐热断裂强力保持率≥90％；在230℃、30min处理后，耐热断裂强力保持率≥90％；干热收缩率为≤8.0％。所述聚酰胺5X包括聚酰胺56，聚酰胺510，聚酰胺512、聚酰胺513或聚酰胺514中的任意一种。优选为聚酰胺56或聚酰胺510。
本发明通过优化聚酰胺5X尤其是聚酰胺56树脂质量：调整其粘度、齐聚物含量、分子量及其分布、含水率，其次优化聚酰胺5X工业丝纺丝工艺，提高聚酰胺5X工业丝的结晶度与取向度，增加定型温度与增大卷绕超喂比例，降低其后续应力松弛，最终得到具有优异力学性能与尺寸稳定性能的聚酰胺56工业丝，断裂强度为6.5cN/dtex以上；断单丝次数≤2次/24h；制成率≥90％；沸水收缩率为8.0％以下；纤度为100-3500dtex；断裂伸长率为26％以下；结晶度为70％以上；取向度为80％以上。
聚酰胺类纤维纺丝过程中需要树脂控制含水率，一般要求在平衡含水率范围内，如果纺 丝过程中，树脂含水率过低，熔融过程中发生熔体增粘反应，氨基含量降低，熔体流动性变差，不利于后续拉伸，造成纤维断单丝与强度偏低；含水率过高，熔融过程中发生熔体降解反应，氨基含量增加，容易产生断单丝现象，最终均造成制成率降低。控制纺丝过程中聚酰胺56树脂含水率为300-800ppm，聚酰胺56工业丝的无油丝相对粘度为2.7-4.5，无油丝相对粘度与其树脂相对粘度的差的绝对值≤0.12，无油丝氨基含量为20-50mmol/kg，无油丝氨基与其树脂氨基的差的绝对值≤5。通过降低无油丝粘度与氨基波动范围，提高聚酰胺56熔体均匀性，减少断单丝次数，增加可纺性，制备的聚酰胺56工业丝的制成率≥90％。
本发明的第二个目的在于提供一种聚酰胺5X工业丝，尤其是聚酰胺56工业丝的制备方法。
本发明的第三个目的在于提供一种聚酰胺5X工业丝的应用，尤其是聚酰胺56工业丝的应用，所述聚酰胺56工业丝在缝纫线、轮胎帘子线、气囊丝、脱模布、水布、帆布、安全带、绳索、渔网、工业过滤布、传输带、降落伞、帐篷、箱包领域中的应用。
为达到上述目的，本发明的解决方案是：
[一种聚酰胺5X工业丝]
以聚酰胺56工业丝为例，本发明所述聚酰胺56工业丝中铜离子含量为10-1000ppm，优选为30-500ppm，更优选为50-200ppm；所述聚酰胺56工业丝180℃、4h处理后，耐热断裂强力保持率≥90％，优选为≥94％，更优选为≥98％；230℃、30min处理后，耐热断裂强力保持率≥90％，优选为≥93％，更优选为≥96％；所述聚酰胺56工业丝的干热收缩率为≤8.0％，优选为≤6.0％，更优选为≤4.0％。
所述聚酰胺56工业丝含有热稳定剂；优选地，所述热稳定剂包括：醋酸铜、碘化钾、氯化铜、碘化亚铜、氧化铜、氧化亚铜中的任意一种或几种的组合物；优选地，所述热稳定剂的添加量占生产原料总重量的10-2800ppm，优选为100-2500ppm。
优选地，所述热稳定剂为醋酸铜与碘化钾的组合物，其中醋酸铜与碘化钾的摩尔比为1:1-15，优选为1:2-10，更优选为1:6-8，其中，优选醋酸铜的添加量为100-500ppm，碘化钾的添加量为500-2500ppm。
所述聚酰胺56工业丝的断裂强度为6.5cN/dtex以上，优选为7.0cN/dtex以上，更优选为8.0cN/dtex以上。
所述聚酰胺56工业丝的无油丝相对粘度为2.7-4.5，无油丝相对粘度与其树脂相对粘度的差的绝对值≤0.12，优选为≤0.10，更优选为≤0.08。
所述聚酰胺56工业丝的无油丝氨基含量为20-50mmol/kg；无油丝氨基与其树脂氨基的差的绝对值≤5，优选为≤3，更优选为≤2。
所述聚酰胺56工业丝断单丝次数≤2次/24h，优选≤1次/24h，更优选0次/24h，所述聚酰胺56工业丝的制成率≥90％，优选为≥93％，更优选为≥96％。
所述聚酰胺56工业丝的沸水收缩率为在8.0％以下，优选为在7.0％以下，更优选为在6.0％以下；和/或，所述聚酰胺56工业丝的纤度为100-3500dtex，优选为200-2500dtex，更优选为 300-1800dtex；所述聚酰胺56工业丝的断裂伸长率为26％以下，优选为22％以下；和/或，所述聚酰胺56工业丝的结晶度为70％以上，优选为72％以上，更优选为74％以上；和/或，所述聚酰胺56工业丝的取向度为80％以上，优选为82％以上，更优选为84％以上。
所述聚酰胺56工业丝的生产原料至少包括：1,5-戊二胺和己二酸；或者，以1,5-戊二胺和己二酸为单体聚合得到的聚酰胺56。
所述1,5-戊二胺由生物基原料通过发酵法或酶转化法制备而成。优选地，所述1,5-戊二胺由生物基原料通过发酵法或酶转化法制备而成。例如采用专利CN109536542A公开的1,5-戊二胺制备方法。
[一种聚酰胺5X工业丝的制备方法]
以聚酰胺56工业丝为例，所述制备方法包括如下步骤：
所述聚酰胺56工业丝可以采用熔体直接纺丝或切片纺丝2种方法。
(1)、将1,5-戊二胺和己二酸聚合，获得高粘度聚酰胺56熔体，通过熔体增压泵输送到纺丝箱体，直接进行纺丝；或者，采用切片纺丝，即先制备低粘度聚酰胺56树脂，然后通过固相增粘获得高粘度聚酰胺56树脂，将高粘度聚酰胺56树脂加热至熔融状态，形成聚酰胺56熔体进行纺丝；
所述固相增粘：通过将低粘度聚酰胺56树脂通过高温干燥来提高粘度。优选地，所述固相增粘的温度为120-180℃，优选为150-160℃。干燥时间10-50h，优选为15-30h。所述固相增粘通过高温干燥使水分脱出，缩聚反应继续进行，得到高粘度树脂。
(2)、将所述聚酰胺56熔体进行拉丝，形成初生丝；
(3)、对所述初生丝进行处理后得到所述聚酰胺56工业丝。
其中，在步骤(1)1,5-戊二胺和己二酸聚合过程中加入热稳定剂，或以热稳定剂母粒形式在聚合熔体切粒前在线注入，或以热稳定剂母粒形式在纺丝过程中共混加入。
如果是聚酰胺510工业丝，可以将将1,5-戊二胺和癸二酸聚合。
在本发明一些具体方案中，所述热稳定剂母粒中铜离子含量为0.5-10wt％，为0.8-5wt％，更为1.2-3wt％。
在本发明一些具体方案中，所述热稳定剂母粒添加量为0.3-5.0wt％，为0.5-3.0wt％，更为0.8-2.0wt％。
在本发明一些具体方案中，所述热稳定剂母粒基体材料为聚酰胺6、聚酰胺56、聚酰胺66、聚酰胺510、聚酰胺610、聚对苯二甲酸丁二醇酯，优选为聚酰胺6、聚酰胺56、聚酰胺510，更优选为聚酰胺6、聚酰胺56。
在本发明一些具体方案中，所述热稳定剂母粒的制备方法，包括如下步骤：
(1)将基体材料采用真空或惰性气体干燥，磨粉；
(2)将步骤(1)获得的粉末与热稳定剂、其他添加剂进行混合，造粒。具体可以采用双螺杆熔融挤出造粒，优选地，所述双螺杆挤出机各区加工温度为180-285℃，螺杆转速为 25-350r/min，真空度≤-0.1MPa，过滤网为80-200目。优选地，所述基体材料为聚酰胺56，所述双螺杆挤出机各区加工温度为260-275℃，螺杆转速为50-350r/min，真空度≤-0.1MPa，过滤网为100-150目。所述热稳定剂的添加量是所述基体材料的0.5-20wt％。
在本发明一些具体方案中，所述热稳定剂是醋酸铜与碘化钾的组合物，其中醋酸铜与碘化钾的摩尔比为1:1-15，优选为1:2-10，更优选为1:5-8。在本发明一些具体方案中，所述热稳定剂是碘化亚铜。所述其他添加剂至少包括抗氧化剂和/或润滑剂。
本发明通过在聚合过程中添加上述热稳定剂，使聚酰胺56工业丝获得了更好的耐热和力学性能，发明人推测是由于聚酰胺56熔体流动性好，热稳定剂在聚酰胺56树脂中可以分布均匀，相容性良好，其次聚酰胺56为奇偶碳排列结构，酰胺键比例高，且不同分子链上有部分酰胺键未键合，加入含有铜离子的热稳定剂后，铜离子在酰胺键之间可以起到良好的络合作用，使聚酰胺56分子链间连接的更加紧密，分子间作用力更大，制备的工业丝力学性能增加。
在本发明一些具体方案中，所述聚酰胺56工业丝纺丝过中也可以加入其它添加剂，所述添加剂包括：消光剂、阻燃剂、抗氧化剂、紫外线吸收剂、红外线吸收剂、结晶成核剂、荧光增白剂和抗静电剂中的任意一种或几种；优选地，所述添加剂的添加量占生产原料总重量的0-5wt％。
所述抗氧化剂包括但不限于市售的抗氧剂1010、抗氧剂1098、抗氧剂168、次亚磷酸钠中的一种、两种及其以上复配。所述润滑剂包括但不限于市售的P861/3.5、PTS HOB 7119，和市售的ET132、ET141和wax OP。
在步骤(1)中，聚酰胺56聚合具体包括以下步骤：
(1-1)惰性气体或真空条件下，将1,5-戊二胺、己二酸和水混合均匀，制得聚酰胺56盐溶液；其中，所述1,5-戊二胺和所述己二酸的摩尔比为(0.95-1.2)：1；所述惰性气体包括氮气、氩气或氦气中的一种或几种。
在本发明一些具体方案中，所述聚酰胺56盐溶液的浓度在40～85％之间。
(1-2)将所述聚酰胺56盐溶液加热，反应体系内压力升至0.3-2.5Mpa，排气，保压，再降压使反应体系内压力降至0-0.2MPa，抽真空至真空度-(0.01-0.1)Mpa，所述压力为表压，得到聚酰胺56熔体；
其中，优选地，所述保压结束时反应体系的温度为230-275℃；和/或，
优选地，所述降压结束后反应体系的温度为240-285℃；和/或，优选地，所述抽真空后的温度为265-295℃。
在本发明一些具体方案中，步骤(1)中，所述低粘度聚酰胺56树脂96％硫酸的相对粘度为2.0-2.7，优选为2.2-2.6，更优选为2.4-2.5。
在本发明一些具体方案中，步骤(1)中，所述高粘度聚酰胺56树脂96％硫酸的相对粘度为2.7-4.5，优选为3.2-4.0，更优选为3.4-3.6；和/或，所述高粘度聚酰胺56树脂齐聚物含量为0.2-1.0wt％，优选为0.4-0.6wt％；和/或，所述高粘度聚酰胺56树脂的数均分子量为18000-40000，优选为25000-30000，分子量分布为0.8-1.8，优选为1.2-1.5；
在本发明一些具体方案中，所述高粘度聚酰胺56树脂的含水率为200-800ppm，优选为 300-750ppm，更优选为350-700ppm，进一步优选为400-600ppm；和/或，所述高粘度聚酰胺56树脂氨基含量为20-50mmol/kg，优选为24-45mmol/kg，更优选为28-40mmol/kg，进一步优选为32-36mmol/kg。
在本发明一些具体方案中，步骤(1)中的加热是在螺杆挤出机中进行的，该螺杆挤出机分为五区加热；其中，一区温度为250-290℃，二区温度为260-300℃，三区温度为270-320℃，四区温度为280-330℃，五区温度为280-320℃。
在本发明一些具体方案中，步骤(2)中的纺丝过程包括如下步骤：将所述聚酰胺56树脂经纺丝箱体的喷丝板喷出，形成所述初生丝。
优选地，所述纺丝箱体的温度为270-330℃，更优选为280-310℃，进一步优选为290-300℃，更进一步优选为293-297℃；和/或，所述纺丝箱体的纺丝组件压力为8-25MPa，优选为12-20MPa，进一步优选为15-18MPa；和/或，所述喷丝板的喷丝头拉伸比为50-400，优选为70-300，进一步优选为80-200，更进一步优选为90-100。
在本发明一些具体方案中，步骤(3)中，所述处理过程包括如下步骤：对所述出喷丝孔初生丝进行保温、冷却、上油、拉伸、卷绕成型，得到所述聚酰胺56工业丝；
优选地，所述保温采用缓冷装置进行，缓冷温度为150-280℃，更优选为200-240℃，缓冷长度为10-80mm，更优选为20-50mm；所述冷却为通过侧吹风进行冷却，所述侧吹风的风速为0.3-2.0m/s，更优选为0.6-1.5m/s；所述侧吹风的风温为15-25℃，更优选为17-23℃，进一步优选为19-22℃；所述侧吹风的湿度为60-80％，更优选为65-75％；和/或，
所述卷绕成型时的卷绕张力为50-300cN，优选为80-200cN，进一步优选为100-160cN，更进一步优选为120-140cN；或者，所述卷绕的速度为2000-3800m/min，优选为2500-3500m/min，进一步优选为2800-3000m/min；所述卷绕超喂比例≤5％，优选为≤4％，进一步优选为≤3％。
在本发明一些具体方案中，所述拉伸过程为四级以上拉伸；优选地，所述拉伸过程为：上油后的初生丝首先经过导丝辊喂入第一对热辊，在所述第一对热辊与第二对热辊之间进行一级拉伸，然后在所述第二对热辊与第三对热辊之间进行二级拉伸，在所述第三对热辊与第四对热辊之间进行三级拉伸并进行第一次热定型，接着在所述第四对热辊与第五对热辊之间进行四级拉伸并进行第二次热定型；
其中，优选地：所述拉伸的总拉伸倍数为4.0-6.0；
所述第一次热定型的温度为180-250℃，优选为200-240℃；所述第二次热定型的温度为200-240℃，优选为220-230℃。
采用本发明技术方案可以取得的有益效果包括：
第一、本发明的聚酰胺5X工业丝的生产原料由生物法制成，为绿色材料，不依赖于石油资源并且不会对环境造成严重污染，能够降低二氧化碳的排放，减少温室效应的产生。
第二、本发明的聚酰胺5X工业丝具有较好的耐热性能、力学性能和尺寸稳定性能。
第三、本发明的聚酰胺5X工业丝制备方法可在聚合过程中添加耐热稳定剂，属于原位聚合，混合充分可以在聚酰胺5X树脂中分布均匀，纺丝过程中未影响正常生产，断单丝现象极少，制成率增加。
第四、本发明的聚酰胺5X工业丝采用常规聚酰胺6与聚酰胺66工业丝设备即可值得，无需对纺丝设备进行改造，通过对聚酰胺5X树脂质量与纺丝工艺优化，即可提高制成率，降低生产成本，为纺丝企业带来巨大效益。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚，下面将结合本发明的实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
如下实施例和对比例获得的产品的各特性，按照以下方法测定：
(1)纤度：按照GB/T 14343测定。
(2)断裂强度：按照GB/T 14344-2008测定。
(3)断裂伸长率：按照GB/T 14344-2008测定。
(4)耐热断裂强力保持率：耐热断裂强力保持率＝((热处理前的断裂强力-热处理后的断裂强力)/热处理前的断裂强力)*100％，断裂强力按照GB/T 14344-2008测定，热处理设备为烘箱，烘箱温度为180℃，处理时间为4h(小时)；与烘箱温度为230℃，处理时间为30min(分钟)。
(5)干热收缩率：按照FZ/T 50004规定执行，热处理温度为180℃。
(6)沸水收缩率：其中，沸水收缩率的测定参考GB/6505-2008“化学纤维长丝热收缩率试验方法”，具体为：取一段聚酰胺工业丝，预加张力0.05±0.005cN/dtex，对其中间两端50.00cm进行标记后，用纱布包好，放入沸水中沸煮30min，然后，试样烘干后，测量两标记点间的长度，采用以下公式计算沸水收缩率：
沸水收缩率＝((起始长度-收缩后长度)/起始长度)*100％。
(7)相对粘度：聚酰胺无油丝(未上油的初生丝)与树脂的相对粘度通过乌氏粘度计浓硫酸法进行测定，其步骤如下：准确称量干燥后的聚酰胺树脂或其短纤样品0.25±0.0002g，加入50mL浓硫酸(96％)溶解，在25℃恒温水浴槽中测量并记录浓硫酸的流经时间t 0和聚酰胺56切片或其短纤样品溶液的流经时间t。
相对粘度计算公式为：相对粘度VN＝t/t 0；t—溶液流经时间；t 0—溶剂流经时间。
(8)含水率：按照卡尔费休水份滴定仪测定。
(9)结晶度与取向度：采用日本Rigaku Corporation生产的D/max-2550 PC X射线衍射仪分析纤维样品，Cu靶波长
Figure PCTCN2020072240-appb-000001
电压为20-40kV，电流为10-450mA，测量角度2θ的范围为5-40°。用于测试结晶的聚酰胺56工业丝样品先进行充分剪碎，样品质量大于0.2g；用于测试微晶取向的聚酰胺56工业丝样品梳理整齐，一束长30mm，进行测试。采用origin等软件进行数据处理，分析计算纤维的结晶度和取向度。
计算结晶度的公式：
Figure PCTCN2020072240-appb-000002
其中，∑I c为结晶部分的总衍射积分强度；∑I a为非晶部分的散射积分强度。
计算取向度的公式：
Figure PCTCN2020072240-appb-000003
其中，H i为第i峰的半高峰宽。
(10)制成率：制成率＝((总共投入树脂数量-成品纤维数量)/总共投入树脂数量)*100％。
(11)数均分子量：采用标准的GPC进行测定。
(12)分子量分布：凝胶渗透色谱(GPC)测定。
(13)齐聚物含量：水萃取法(称重)，准确称量130℃下干燥7小时的聚酰胺56树脂约8g，置于500mL圆底烧瓶中，加入400g水，于加热套中回流36h，将溶液倾析，粒子在恒重的烧杯内130℃干燥7小时，后塑封在铝塑袋中降温称重计算其失重。聚酰胺56树脂，是参照CN108503826A和CN108503824A所中公开的方法制备得到，相对粘度为2.7～4.5。
(14)氨基：按照自动滴定仪测定。
(15)断单丝：人工统计纺丝过程中断丝的次数。
(16)制成率：纺丝后获得工业丝的重量与投入的树脂的重量百分比。
如下实施例和对比例中无油丝相对粘度与其树脂相对粘度的差的绝对值、以及无油丝氨基与其树脂氨基的差的绝对值、断单丝(次数/24h)和制成率(％)如后表1所示。获得的聚酰胺56工业丝性能结果如后表2所示。
实施例一：聚酰胺56工业丝(933dtex/140f)
制备方法包括如下步骤：
1、聚合：
(1)氮气条件下，将原料1,5-戊二胺、己二酸和水混合均匀，加入占生产原料总重量200ppm的醋酸铜热稳定剂，制得浓度为60％的聚酰胺56盐溶液；其中，所述1,5-戊二胺和己二酸的摩尔比为1.05：1。
(2)将所述聚酰胺56盐溶液加热，反应体系内压力升至2.2Mpa，排气，保压，保压结束时反应体系的温度为265℃。再降压使反应体系内压力降至0.1MPa，降压结束后反应体系的温度为275℃。抽真空至真空度-0.05Mpa，抽真空后的温度为285℃，获得低粘度聚酰胺56树脂。所述压力均为表压。
(3)所述低粘度聚酰胺56树脂通过固相增粘制备高粘度聚酰胺56树脂。所述固相增粘的温度为155℃，干燥时间为20h。
所述低粘度聚酰胺56树脂96％硫酸的相对粘度为2.4。所述高粘度聚酰胺56树脂96％硫酸的相对粘度为3.3，齐聚物含量为0.8wt％，数均分子量为30000，分子量分布为1.6，含水率为400ppm，氨基含量为36.5mmol/kg。
2、纺丝：
(1)将所述高粘度聚酰胺56树脂加热至熔融状态，形成聚酰胺56熔体，所述加热在螺 杆挤出机中进行，该螺杆挤出机分为五区加热；其中，一区温度为255℃，二区温度为270℃，三区温度为280℃，四区温度为290℃，五区温度为300℃。将所述聚酰胺56熔体经纺丝箱体的喷丝板喷出，形成初生丝；所述纺丝箱体的温度为290℃，组件压力为15MPa，喷丝头拉伸比为150。
(2)对所述初生丝进行保温、冷却、上油、拉伸、卷绕成型，得到所述聚酰胺56工业丝；
所述保温采用缓冷装置进行，缓冷温度为220℃，缓冷长度为20mm；
冷却为侧吹风进行冷却，风速为1.2m/s，风温为22℃，湿度为70％。
所述拉伸过程为四级拉伸；所述拉伸过程为：上油后的初生丝首先经过导丝辊喂入第一对热辊，在所述第一对热辊与第二对热辊之间进行一级拉伸，然后在所述第二对热辊与第三对热辊之间进行二级拉伸，在所述第三对热辊与第四对热辊之间进行三级拉伸并进行第一次热定型，接着在所述第四对热辊与第五对热辊之间进行四级拉伸并进行第二次热定型；其中，所述拉伸的总拉伸倍数为5.0；所述第一次热定型的温度为220℃；所述第二次热定型的温度为230℃。所述卷绕成型时的卷绕张力为90cN，卷绕速度为3500m/min，卷绕超喂比例为2％。
实施例二：聚酰胺56工业丝(830dtex/192f)
制备方法包括如下步骤：
1、聚合：
(1)氮气条件下，将原料1,5-戊二胺、己二酸和水混合均匀，加入占生产原料总重量500ppm的醋酸铜热稳定剂，制得浓度为60％的聚酰胺56盐溶液；其中，所述1,5-戊二胺和己二酸的摩尔比为1.1：1。
(2)将所述聚酰胺56盐溶液加热，反应体系内压力升至2.3Mpa，排气，保压，保压结束时反应体系的温度为255℃。再降压使反应体系内压力降至0MPa，降压结束后反应体系的温度为265℃。抽真空至真空度-0.08Mpa，抽真空后的温度为275℃，获得低粘度聚酰胺56树脂。所述压力均为表压。
(3)所述低粘度聚酰胺56树脂通过固相增粘制备高粘度聚酰胺56树脂。所述固相增粘的温度为160℃，干燥时间为18h。
所述低粘度聚酰胺56树脂96％硫酸的相对粘度为2.5。所述高粘度聚酰胺56树脂96％硫酸的相对粘度为3.5，齐聚物含量为0.6wt％，数均分子量为33000，分子量分布为1.5，含水率为450ppm，氨基含量为33.5mmol/kg。
2、纺丝：
(1)将所述高粘度聚酰胺56树脂加热至熔融状态，形成聚酰胺56熔体，所述加热在螺杆挤出机中进行，具体分为五区加热，一区温度为265℃，二区温度为275℃，三区温度为285℃，四区温度为295℃，五区温度为305℃。将所述聚酰胺56熔体经纺丝箱体的喷丝板喷出，形成初生丝；所述纺丝箱体的温度为295℃，组件压力为18MPa，喷丝头拉伸比为180。
(2)对所述初生丝进行保温、冷却、上油、拉伸、卷绕成型，得到所述聚酰胺56工业丝；所述保温采用缓冷装置进行，缓冷温度为230℃，缓冷长度为30mm；冷却为侧吹风进行冷却， 风速为0.8m/s，风温为23℃，湿度为75％。所述卷绕成型时的卷绕张力为80cN，卷绕的速度为3000m/min，所述卷绕超喂比例为3％。所述拉伸过程为四级拉伸，拉伸过程与实施例一相同；区别在于，所述拉伸的总拉伸倍数为4.8；所述第一次热定型的温度为225℃；所述第二次热定型的温度为240℃。
实施例三：聚酰胺56工业丝(550dtex/96f)
制备方法包括如下步骤：
1、聚合：
(1)氮气条件下，将原料1,5-戊二胺、己二酸和水混合均匀，加入占生产原料总重量150ppm的碘化亚铜热稳定剂，制得浓度为65％的聚酰胺56盐溶液；其中，所述1,5-戊二胺和己二酸的摩尔比为1.1：1。
(2)将所述聚酰胺56盐溶液加热，反应体系内压力升至2.3Mpa，排气，保压，保压结束时反应体系的温度为240℃。再降压使反应体系内压力降至0.1MPa，降压结束后反应体系的温度为270℃。抽真空至真空度-0.05Mpa，抽真空后的温度为280℃，获得低粘度聚酰胺56树脂。所述压力均为表压。
(3)所述低粘度聚酰胺56树脂通过固相增粘制备高粘度聚酰胺56树脂。所述固相增粘的温度为160℃，干燥时间为22h。
所述低粘度聚酰胺56树脂96％硫酸的相对粘度为2.6。所述高粘度聚酰胺56树脂96％硫酸的相对粘度为3.0，齐聚物含量为0.8wt％，数均分子量为30000，分子量分布为1.6，含水率为400ppm，氨基含量为42.5mmol/kg。
2、纺丝：
(1)将所述高粘度聚酰胺56树脂加热至熔融状态，形成聚酰胺56熔体，所述加热在螺杆挤出机中进行，具体分为五区加热，一区温度为248℃，二区温度为263℃，三区温度为276℃，四区温度为285℃，五区温度为293℃。将所述聚酰胺56熔体经纺丝箱体的喷丝板喷出，形成所述初生丝；所述纺丝箱体的温度为285℃，组件压力为16MPa，喷丝头拉伸比为100。
(2)对所述初生丝进行保温、冷却、上油、拉伸、卷绕成型，得到所述聚酰胺56工业丝；所述保温采用缓冷装置进行，缓冷温度为220℃，缓冷长度为25mm；冷却为侧吹风进行冷却，风速为1.4m/s，风温为22℃，湿度为65％。所述卷绕成型时的卷绕张力为55cN，卷绕的速度为2800m/min，所述卷绕超喂比例为2.5％。所述拉伸过程为四级拉伸，拉伸过程与实施例一相同；区别在于，所述拉伸的总拉伸倍数为为5.0；所述第一次热定型的温度为220℃；所述第二次热定型的温度为235℃。
实施例四：聚酰胺56工业丝(550dtex/96f)
制备方法包括如下步骤：
1、聚合：
(1)氮气条件下，将原料1,5-戊二胺、己二酸和水混合均匀，加入占生产原料总重量 250ppm的碘化亚铜热稳定剂，制得浓度为65％的聚酰胺56盐溶液；其中，所述1,5-戊二胺和己二酸的摩尔比为1.12：1。
(2)将所述聚酰胺56盐溶液加热，反应体系内压力升至2.4Mpa，排气，保压，保压结束时反应体系的温度为245℃。再降压使反应体系内压力降至0.1MPa，降压结束后反应体系的温度为275℃。抽真空至真空度-0.07Mpa，抽真空后的温度为280℃，获得低粘度聚酰胺56树脂。所述压力均为表压。
(3)所述低粘度聚酰胺56树脂通过固相增粘制备高粘度聚酰胺56树脂。所述固相增粘的温度为150℃，干燥时间为25h。所述低粘度聚酰胺56树脂96％硫酸的相对粘度为2.55。所述高粘度聚酰胺56树脂96％硫酸的相对粘度为2.9，齐聚物含量为0.8wt％，数均分子量为28000，分子量分布为1.5，含水率为300ppm，氨基含量为40.5mmol/kg。
2、纺丝：
(1)将所述高粘度聚酰胺56树脂加热至熔融状态，形成聚酰胺56熔体，所述加热在螺杆挤出机中进行，具体分为五区加热，一区温度为245℃，二区温度为260℃，三区温度为270℃，四区温度为285℃，五区温度为290℃。将所述聚酰胺56熔体经纺丝箱体的喷丝板喷出，形成初生丝；所述纺丝箱体的温度为280℃，组件压力为10MPa，喷丝头拉伸比为200。
(2)对所述初生丝进行保温、冷却、上油、拉伸、卷绕成型，得到所述聚酰胺56工业丝；所述保温采用缓冷装置进行，缓冷温度为210℃，缓冷长度为25mm；冷却为侧吹风进行冷却，风速为1.3m/s，风温为24℃，湿度为65％。所述卷绕成型时的卷绕张力为55cN，卷绕的速度为2600m/min，所述卷绕超喂比例为2.5％。所述拉伸过程为四级拉伸，拉伸过程与实施例一相同；区别在于，所述拉伸的总拉伸倍数为5.3；所述第一次热定型的温度为225℃；所述第二次热定型的温度为235℃。
实施例五：聚酰胺56工业丝(233dtex/36f)
制备方法包括如下步骤：
1、聚合：
(1)氮气条件下，将原料1,5-戊二胺、己二酸和水混合均匀，加入占生产原料总重量400ppm的碘化亚铜热稳定剂，制得浓度为65％的聚酰胺56盐溶液；其中，所述1,5-戊二胺和己二酸的摩尔比为1.05：1。
(2)将所述聚酰胺56盐溶液加热，反应体系内压力升至2.0Mpa，排气，保压，保压结束时反应体系的温度为260℃。再降压使反应体系内压力降至0.1MPa，降压结束后反应体系的温度为275℃。抽真空至真空度-0.08Mpa，抽真空后的温度为295℃，获得低粘度聚酰胺56树脂。所述压力均为表压。
(3)所述低粘度聚酰胺56树脂通过固相增粘制备高粘度聚酰胺56树脂。所述固相增粘的温度为155℃，干燥时间为25h。
所述低粘度聚酰胺56树脂96％硫酸的相对粘度为2.45。所述高粘度聚酰胺56树脂96％硫酸的相对粘度为3.6，齐聚物含量为1.0wt％，数均分子量为36000，分子量分布为1.7，含水 率为350ppm，氨基含量为46.5mmol/kg。
2、纺丝：
(1)将所述高粘度聚酰胺56树脂加热至熔融状态，形成聚酰胺56熔体，所述加热在螺杆挤出机中进行，具体分为五区加热，一区温度为255℃，二区温度为275℃，三区温度为280℃，四区温度为295℃，五区温度为310℃。将所述聚酰胺56熔体经纺丝箱体的喷丝板喷出，形成初生丝；所述纺丝箱体的温度为295℃，组件压力为19MPa，喷丝头拉伸比为250。
(2)对所述初生丝进行保温、冷却、上油、拉伸、卷绕成型，得到所述聚酰胺56工业丝；所述保温采用缓冷装置进行，缓冷温度为220℃，缓冷长度为20mm；冷却为侧吹风进行冷却，风速为1.0m/s，风温为18℃，湿度为70％。所述卷绕成型时的卷绕张力为23cN，卷绕的速度为2900m/min，所述卷绕超喂比例为1.5％。所述拉伸过程为四级拉伸，所述拉伸过程与实施例一相同；区别在于，所述拉伸的总拉伸倍数为5.5；所述第一次热定型的温度为230℃；所述第二次热定型的温度为230℃。
实施例六：聚酰胺56工业丝(1670dtex/192f)
制备方法包括如下步骤：
1、聚合：
(1)氮气条件下，将原料1,5-戊二胺、己二酸和水混合均匀，加入热稳定剂，制得浓度为65％的聚酰胺56盐溶液；其中，所述1,5-戊二胺和己二酸的摩尔比为1.1：1。所述热稳定剂为醋酸铜与碘化钾的复配，醋酸铜添加量占生产原料总重量的200ppm，碘化钾添加量占生产原料总重量的500ppm。
(2)将所述聚酰胺56盐溶液加热，反应体系内压力升至2.3Mpa，排气，保压，保压结束时反应体系的温度为255℃。再降压使反应体系内压力降至0.1MPa，降压结束后反应体系的温度为270℃。抽真空至真空度-0.01Mpa，抽真空后的温度为280℃，获得低粘度聚酰胺56树脂。所述压力均为表压。
(3)所述低粘度聚酰胺56树脂通过固相增粘制备高粘度聚酰胺56树脂。所述固相增粘的温度为155℃，干燥时间为30h。
所述低粘度聚酰胺56树脂96％硫酸的相对粘度为2.7。所述高粘度聚酰胺56树脂96％硫酸的相对粘度为3.8，齐聚物含量为0.8wt％，数均分子量为38000，分子量分布为1.5，含水率为500ppm，氨基含量为42.5mmol/kg。
2、纺丝：
(1)将所述高粘度聚酰胺56树脂加热至熔融状态，形成聚酰胺56熔体，所述加热在螺杆挤出机中进行，具体分为五区加热，一区温度为250℃，二区温度为275℃，三区温度为280℃，四区温度为295℃，五区温度为305℃。将所述聚酰胺56熔体经纺丝箱体的喷丝板喷出，形成初生丝；所述纺丝箱体的温度为290℃，组件压力为14MPa，喷丝头拉伸比为120。
(2)对所述初生丝进行保温、冷却、上油、拉伸、卷绕成型，得到所述聚酰胺56工业丝；所述保温采用缓冷装置进行，缓冷温度为230℃，缓冷长度为40mm；冷却为侧吹风进行冷却， 风速为1.1m/s，风温为23℃，湿度为75％。所述卷绕成型时的卷绕张力为160cN，卷绕的速度为3200m/min，所述卷绕超喂比例为3.5％。所述拉伸过程为四级拉伸，所述拉伸过程与实施例一相同；区别在于，所述拉伸的总拉伸倍数为5.6；所述第一次热定型的温度为225℃；所述第二次热定型的温度为235℃。
实施例七：聚酰胺56工业丝(2800dtex/480f)
制备方法包括如下步骤：
1、聚合：
(1)氮气条件下，将原料1,5-戊二胺、己二酸和水混合均匀，加入热稳定剂，制得浓度为65％的聚酰胺56盐溶液；其中，所述1,5-戊二胺和己二酸的摩尔比为1.05：1。所述热稳定剂为醋酸铜与碘化钾复配，醋酸铜添加量占生产原料总重量的250ppm，碘化钾添加量占生产原料总重量的2000ppm。
(2)将所述聚酰胺56盐溶液加热，反应体系内压力升至2.2Mpa，排气，保压，保压结束时反应体系的温度为260℃。再降压使反应体系内压力降至0.1MPa，降压结束后反应体系的温度为285℃。抽真空至真空度-0.03Mpa，抽真空后的温度为290℃，获得低粘度聚酰胺56树脂。所述压力均为表压。
(3)所述低粘度聚酰胺56树脂通过固相增粘制备高粘度聚酰胺56树脂。所述固相增粘的温度为155℃，干燥时间为30h。
所述低粘度聚酰胺56树脂96％硫酸的相对粘度为2.35。所述高粘度聚酰胺56树脂96％硫酸的相对粘度为3.2，齐聚物含量为0.8wt％，数均分子量为32000，分子量分布为1.5，含水率为450ppm，氨基含量为38.5mmol/kg。
2、纺丝：
(1)将所述高粘度聚酰胺56树脂加热至熔融状态，形成聚酰胺56熔体，所述加热在螺杆挤出机中进行，具体分为五区加热，一区温度为258℃，二区温度为276℃，三区温度为288℃，四区温度为298℃，五区温度为305℃。将所述聚酰胺56熔体经纺丝箱体的喷丝板喷出，形成初生丝；所述纺丝箱体的温度为293℃，组件压力为12MPa，喷丝头拉伸比为160。
(2)对所述初生丝进行保温、冷却、上油、拉伸、卷绕成型，得到所述聚酰胺56工业丝；所述保温采用缓冷装置进行，缓冷温度为230℃，缓冷长度为20mm；冷却为侧吹风进行冷却，风速为1.2m/s，风温为23℃，湿度为70％。所述卷绕成型时的卷绕张力为280cN，卷绕的速度为2700m/min，所述卷绕超喂比例为3％。
所述拉伸过程为四级拉伸，所述拉伸过程与实施例一相同；区别在于，所述拉伸的总拉伸倍数为4.8；所述第一次热定型的温度为220℃；所述第二次热定型的温度为230℃。
实施例八：聚酰胺56工业丝(233dtex/36f)
制备方法包括如下步骤：
1、聚合：
(1)氮气条件下，将原料1,5-戊二胺、己二酸和水混合均匀，加入热稳定剂，制得浓度为65％的聚酰胺56盐溶液；其中，所述1,5-戊二胺和己二酸的摩尔比为1.05：1。所述热稳定剂为醋酸铜与碘化钾复配，醋酸铜添加量占生产原料总重量的150ppm，碘化钾添加量占生产原料总重量的800ppm。
(2)将所述聚酰胺56盐溶液加热，反应体系内压力升至2.2Mpa，排气，保压，保压结束时反应体系的温度为260℃。再降压使反应体系内压力降至0.1MPa，降压结束后反应体系的温度为285℃。抽真空至真空度-0.01Mpa，抽真空后的温度为290℃，获得低粘度聚酰胺56树脂。所述压力均为表压。
(3)所述低粘度聚酰胺56树脂通过固相增粘制备高粘度聚酰胺56树脂。所述固相增粘的温度为155℃，干燥时间为30h。
所述低粘度聚酰胺56树脂96％硫酸的相对粘度为2.4。所述高粘度聚酰胺56树脂96％硫酸的相对粘度为3.4，齐聚物含量为0.8wt％，数均分子量为33000，分子量分布为1.6，含水率为550ppm，氨基含量为33.5mmol/kg。
2、纺丝：
(1)将所述高粘度聚酰胺56树脂加热至熔融状态，形成聚酰胺56熔体，所述加热在螺杆挤出机中进行，具体分为五区加热，一区温度为268℃，二区温度为280℃，三区温度为290℃，四区温度为295℃，五区温度为303℃。将所述聚酰胺56熔体经纺丝箱体的喷丝板喷出，形成初生丝；所述纺丝箱体的温度为298℃，组件压力为18MPa，喷丝头拉伸比为120。
(2)对所述初生丝进行保温、冷却、上油、拉伸、卷绕成型，得到所述聚酰胺56工业丝；所述保温采用缓冷装置进行，缓冷温度为220℃，缓冷长度为30mm；冷却为侧吹风进行冷却，风速为1.2m/s，风温为23℃，湿度为70％。所述卷绕成型时的卷绕张力为140cN，卷绕的速度为3000m/min，所述卷绕超喂比例为2％。
所述拉伸过程为四级拉伸，所述拉伸过程与实施例一相同；区别在于，所述拉伸的总拉伸倍数为4.8；所述第一次热定型的温度为220℃；所述第二次热定型的温度为230℃。
实施例九：聚酰胺56工业丝(933dtex/140f)
制备方法包括如下步骤：
1、聚合：
(1)氮气条件下，将原料1,5-戊二胺、己二酸和水混合均匀，加入占生产原料总重量的300ppm热稳定剂氯化铜，制得浓度为65％的聚酰胺56盐溶液；其中，所述1,5-戊二胺和己二酸的摩尔比为1.1：1。
(2)将所述聚酰胺56盐溶液加热，反应体系内压力升至2.25Mpa，排气，保压，保压结束时反应体系的温度为260℃。再降压使反应体系内压力降至0.1MPa，降压结束后反应体系的温度为275℃。抽真空至真空度-0.01Mpa，抽真空后的温度为280℃，获得低粘度聚酰胺56树脂。所述压力均为表压。
(3)所述低粘度聚酰胺56树脂通过固相增粘制备高粘度聚酰胺56树脂。所述固相增粘 的温度为160℃，干燥时间为22h。
所述低粘度聚酰胺56树脂96％硫酸的相对粘度为2.4。所述高粘度聚酰胺56树脂96％硫酸的相对粘度为3.4，齐聚物含量为0.8wt％，数均分子量为33000，分子量分布为1.6，含水率为550ppm，氨基含量为33.5mmol/kg。
2、纺丝：
(1)将所述高粘度聚酰胺56树脂加热至熔融状态，形成聚酰胺56熔体，所述加热在螺杆挤出机中进行，具体分为五区加热，一区温度为268℃，二区温度为280℃，三区温度为290℃，四区温度为295℃，五区温度为303℃。将所述聚酰胺56熔体经纺丝箱体的喷丝板喷出，形成初生丝；所述纺丝箱体的温度为280℃，组件压力为13MPa，喷丝头拉伸比为150。
(2)对所述初生丝进行保温、冷却、上油、拉伸、卷绕成型，得到所述聚酰胺56工业丝；所述保温采用缓冷装置进行，缓冷温度为200℃，缓冷长度为40mm；冷却为侧吹风进行冷却，风速为1.3m/s，风温为20℃，湿度为70％。所述卷绕成型时的卷绕张力为90cN，卷绕的速度为2700m/min，所述卷绕超喂比例为2.5％。
所述拉伸过程为四级拉伸，所述拉伸过程与实施例一相同；区别在于，所述拉伸的总拉伸倍数为4.8；所述第一次热定型的温度为210℃；所述第二次热定型的温度为220℃。
实施例十：聚酰胺56工业丝(933dtex/140f)
制备方法包括如下步骤：
1、聚合：
(1)氮气条件下，将原料1,5-戊二胺、己二酸和水混合均匀，制得浓度为65％的聚酰胺56盐溶液；其中，所述1,5-戊二胺和己二酸的摩尔比为1.15：1。
(2)将所述聚酰胺56盐溶液加热，反应体系内压力升至2.3Mpa，排气，保压，保压结束时反应体系的温度为265℃。再降压使反应体系内压力降至0MPa，降压结束后反应体系的温度为275℃。抽真空至真空度-0.04Mpa，抽真空后的温度为285℃，获得低粘度聚酰胺56树脂。所述压力均为表压。
在聚合熔体切粒前在线注入热稳定剂母粒，所述热稳定剂母粒中铜离子含量为2.0wt％，热稳定剂母粒添加量为1.5wt％。所述热稳定剂母粒基体材料为聚酰胺56。所述热稳定剂母粒的制备方法包括如下步骤：(a)将基体材料聚酰胺56真空干燥，然后磨粉；所述聚酰胺56为65重量份，相对粘度为2.9，数均分子量为24kg/mol，分子量分布为2.1，含水率为500ppm。(b)将步骤(a)获得的粉末与12.5重量份热稳定剂碘化亚铜，0.5重量份润滑剂wax OP、0.2重量份抗氧剂168进行混合，采用双螺杆熔融挤出造粒获得热稳定剂母粒，其中各区加工温度为一区251℃，二区264℃，三区269℃，四区273℃，五区276℃，螺杆转速为250r/min，过滤网150目。
(3)所述低粘度聚酰胺56树脂通过固相增粘制备高粘度聚酰胺56树脂。所述固相增粘的温度为155℃，干燥时间为25h。
所述低粘度聚酰胺56树脂96％硫酸的相对粘度为2.5。所述高粘度聚酰胺56树脂96％硫 酸的相对粘度为3.7，齐聚物含量为0.6wt％，数均分子量为34000，分子量分布为1.5，含水率为300ppm，氨基含量为33.8mmol/kg。
2、纺丝：
(1)将所述高粘度聚酰胺56树脂加热至熔融状态，形成聚酰胺56熔体，所述加热在螺杆挤出机中进行，具体分为五区加热，一区温度为265℃，二区温度为278℃，三区温度为288℃，四区温度为295℃，五区温度为300℃。将所述聚酰胺56熔体经纺丝箱体的喷丝板喷出，形成初生丝；所述纺丝箱体的温度为295℃，组件压力为14MPa，喷丝头拉伸比为80。
(2)对所述初生丝进行保温、冷却、上油、拉伸、卷绕成型，得到所述聚酰胺56工业丝；所述保温采用缓冷装置进行，缓冷温度为230℃，缓冷长度为25mm；冷却为侧吹风进行冷却，风速为1.1m/s，风温为22℃，湿度为70％。
所述卷绕成型时的卷绕张力为90cN，卷绕速度为2600m/min，卷绕超喂比例为2％。
所述拉伸过程为四级拉伸，所述拉伸过程与实施例一相同；区别在于，所述拉伸的总拉伸倍数为5.0；所述第一次热定型的温度为220℃；所述第二次热定型的温度为230℃。
实施例十一：聚酰胺56工业丝(933dtex/140f)
制备方法包括如下步骤：
1、聚合：
(1)氮气条件下，将原料1,5-戊二胺、己二酸和水混合均匀，制得浓度为65％的聚酰胺56盐溶液；其中，所述1,5-戊二胺和己二酸的摩尔比为1.06：1。
(2)将所述聚酰胺56盐溶液加热，反应体系内压力升至2.2Mpa，排气，保压，保压结束时反应体系的温度为265℃。再降压使反应体系内压力降至0.1MPa，降压结束后反应体系的温度为275℃。抽真空至真空度-0.06Mpa，抽真空后的温度为285℃，获得低粘度聚酰胺56树脂。所述压力均为表压。
(3)所述低粘度聚酰胺56树脂通过固相增粘制备高粘度聚酰胺56树脂。所述固相增粘的温度为160℃，干燥时间为28h。所述低粘度聚酰胺56树脂96％硫酸的相对粘度为2.4。所述高粘度聚酰胺56树脂96％硫酸的相对粘度为3.3，齐聚物含量为0.9wt％，数均分子量为32000，分子量分布为1.6，含水率为450ppm，氨基含量为36.5mmol/kg。
2、纺丝：
(1)将所述高粘度聚酰胺56树脂加热至熔融状态，形成聚酰胺56熔体，所述加热在螺杆挤出机中进行，具体分为五区加热，一区温度为255℃，二区温度为275℃，三区温度为280℃，四区温度为290℃，五区温度为305℃。将所述聚酰胺56熔体经纺丝箱体的喷丝板喷出，形成初生丝；所述纺丝箱体的温度为295℃，组件压力为14MPa，喷丝头拉伸比为140。
在纺丝过程中通过母粒添加装置共混加入热稳定剂母粒，所述热稳定剂母粒中铜离子含量为1.8wt％。热稳定剂母粒添加量为1.2wt％。所述热稳定剂母粒的制备方法与实施例十相同。
(2)对所述初生丝进行保温、冷却、上油、拉伸、卷绕成型，得到所述聚酰胺56工业丝；所述保温采用缓冷装置进行，缓冷温度为240℃，缓冷长度为20mm；冷却为侧吹风进行冷却， 风速为1.4m/s，风温为22℃，湿度为70％。
所述卷绕成型时的卷绕张力为90cN，卷绕速度为3500m/min，卷绕超喂比例为2％。
所述拉伸过程为四级拉伸，所述拉伸过程与实施例一相同；区别在于，所述拉伸的总拉伸倍数为5.0；所述第一次热定型的温度为220℃；所述第二次热定型的温度为230℃。
实施例十二：聚酰胺56工业丝(933dtex/140f)
制备方法包括如下步骤：
1、聚合：
(1)氮气条件下，将原料1,5-戊二胺、己二酸和水混合均匀，制得浓度为65％的聚酰胺56盐溶液；其中，所述1,5-戊二胺和己二酸的摩尔比为1.08：1。
(2)将所述聚酰胺56盐溶液加热，反应体系内压力升至2.2Mpa，排气，保压，保压结束时反应体系的温度为265℃。再降压使反应体系内压力降至0MPa，降压结束后反应体系的温度为275℃。抽真空至真空度-0.05Mpa，抽真空后的温度为290℃，获得低粘度聚酰胺56树脂。所述压力均为表压。
(3)所述低粘度聚酰胺56树脂通过固相增粘制备高粘度聚酰胺56树脂。所述固相增粘的温度为160℃，干燥时间为28h。所述低粘度聚酰胺56树脂96％硫酸的相对粘度为2.4。所述高粘度聚酰胺56树脂96％硫酸的相对粘度为3.2，齐聚物含量为0.8wt％，数均分子量为30000，分子量分布为1.6，含水率为400ppm，氨基含量为32.3mmol/kg。
2、纺丝：
(1)将所述高粘度聚酰胺56树脂加热至熔融状态，形成聚酰胺56熔体，所述加热在螺杆挤出机中进行，具体分为五区加热，一区温度为250℃，二区温度为270℃，三区温度为285℃，四区温度为290℃，五区温度为290℃。将所述聚酰胺56熔体经纺丝箱体的喷丝板喷出，形成初生丝；所述纺丝箱体的温度为285℃，组件压力为12MPa，喷丝头拉伸比为180。
在纺丝过程中通过母粒添加装置共混加入热稳定剂母粒，所述热稳定剂母粒中铜离子含量为1.6wt％。热稳定剂母粒添加量为1.5wt％。
所述热稳定剂母粒基体材料为聚酰胺6。所述热稳定剂母粒的制备方法包括如下步骤：(a)将基体材料聚酰胺6真空干燥，然后磨粉；所述聚酰胺6为65重量份，相对粘度为2.9，数均分子量为24kg/mol，分子量分布为2.1，含水率为500ppm。(b)将步骤(a)获得的粉末与15重量份热稳定剂碘化亚铜，0.5重量份润滑剂wax OP、0.2重量份抗氧剂168进行混合，采用双螺杆熔融挤出造粒获得热稳定剂母粒，其中各区加工温度为一区200℃，二区210℃，三区220℃，四区230℃，五区235℃，螺杆转速为250r/min，过滤网150目。
(2)对所述初生丝进行保温、冷却、上油、拉伸、卷绕成型，得到所述聚酰胺56工业丝；所述保温采用缓冷装置进行，缓冷温度为225℃，缓冷长度为20mm；冷却为侧吹风进行冷却，风速为1.2m/s，风温为22℃，湿度为70％。
所述卷绕成型时的卷绕张力为90cN，卷绕速度为3300m/min，卷绕超喂比例为2％。
所述拉伸过程为四级拉伸，所述拉伸过程与实施例一相同；区别在于，所述拉伸的总拉伸 倍数为5.0；所述第一次热定型的温度为220℃；所述第二次热定型的温度为230℃。
实施例十三：聚酰胺56工业丝(933dtex/140f)
制备方法包括如下步骤：
1、聚合：
(1)氮气条件下，将原料1,5-戊二胺、己二酸和水混合均匀，加入占生产原料总重量200ppm的热稳定剂碘化亚铜，制得浓度为65％的聚酰胺56盐溶液；其中，所述1,5-戊二胺和己二酸的摩尔比为1.1：1。
(2)将所述聚酰胺56盐溶液加热，反应体系内压力升至2.25Mpa，排气，保压，保压结束时反应体系的温度为265℃。再降压使反应体系内压力降至0.1MPa，降压结束后反应体系的温度为280℃。抽真空至真空度-0.01Mpa，抽真空后的温度为295℃，直接获得高粘度聚酰胺56熔体。所述压力均为表压。
所述高粘度聚酰胺56熔体96％硫酸的相对粘度为3.4，齐聚物含量为0.8wt％，数均分子量为30000，分子量分布为1.6，含水率为400ppm，氨基含量为32.5mmol/kg。
2、纺丝：
(1)将所述高粘度聚酰胺56熔体通过熔体增压泵输送到纺丝箱体，直接进行纺丝。将所述聚酰胺56熔体经纺丝箱体的喷丝板喷出，形成初生丝；所述纺丝箱体的温度为280℃，组件压力为18MPa，喷丝头拉伸比为200。
(2)对所述初生丝进行保温、冷却、上油、拉伸、卷绕成型，得到所述聚酰胺56工业丝；所述保温采用缓冷装置进行，缓冷温度为220℃，缓冷长度为20mm；冷却为侧吹风进行冷却，风速为1.2m/s，风温为22℃，湿度为70％。
所述卷绕成型时的卷绕张力为90cN，卷绕速度为2500m/min，卷绕超喂比例为2％。
所述拉伸过程为四级拉伸，所述拉伸过程与实施例一相同；区别在于，所述拉伸的总拉伸倍数为5.0；所述第一次热定型的温度为220℃；所述第二次热定型的温度为230℃。
实施例十四：聚酰胺56工业丝(2800dtex/480f)
制备方法包括如下步骤：
1、聚合：
(1)氮气条件下，将原料1,5-戊二胺、己二酸和水混合均匀，加入热稳定剂，制得浓度为65％的聚酰胺56盐溶液；其中，所述1,5-戊二胺和己二酸的摩尔比为1.08：1。所述热稳定剂为醋酸铜与碘化钾复配，醋酸铜添加量占生产原料总重量的200ppm，碘化钾添加量占生产原料总重量的700ppm。
(2)将所述聚酰胺56盐溶液加热，反应体系内压力升至2.4Mpa，排气，保压，保压结束时反应体系的温度为265℃。再降压使反应体系内压力降至0.1MPa，降压结束后反应体系的温度为285℃。抽真空至真空度-0.06Mpa，抽真空后的温度为290℃，直接获得高粘度聚酰胺56熔体。所述压力均为表压。
所述高粘度聚酰胺56熔体96％硫酸的相对粘度为3.5，齐聚物含量为1.0wt％，数均分子量为34000，分子量分布为1.6，含水率为450ppm，氨基含量为40.5mmol/kg。
2、纺丝：
(1)将所述高粘度聚酰胺56熔体通过熔体增压泵输送到纺丝箱体，直接进行纺丝。将所述聚酰胺56熔体经纺丝箱体的喷丝板喷出，形成初生丝；所述纺丝箱体的温度为290℃，组件压力为12MPa，喷丝头拉伸比为180。
(2)对所述初生丝进行保温、冷却、上油、拉伸、卷绕成型，得到所述聚酰胺56工业丝；所述保温采用缓冷装置进行，缓冷温度为210℃，缓冷长度为20mm；冷却为侧吹风进行冷却，风速为1.2m/s，风温为23℃，湿度为70％。
所述卷绕成型时的卷绕张力为280cN，卷绕的速度为2900m/min，所述卷绕超喂比例为3％。
所述拉伸过程为四级拉伸，所述拉伸过程与实施例一相同；区别在于：所述拉伸的总拉伸倍数为4.5；所述第一次热定型的温度为220℃；所述第二次热定型的温度为230℃。
实施例十五：聚酰胺56工业丝(1670dtex/192f)
制备方法与实施例六相同，区别在于，所述热稳定剂为醋酸铜与碘化钾的复配，醋酸铜添加量占生产原料总重量的200ppm，碘化钾添加量占生产原料总重量的1000ppm。
实施例十六：聚酰胺56工业丝(1670dtex/192f)
制备方法与实施例六相同，区别在于，所述热稳定剂为醋酸铜与碘化钾的复配，醋酸铜添加量占生产原料总重量的200ppm，碘化钾添加量占生产原料总重量的2000ppm。
实施例十七：聚酰胺56工业丝(1670dtex/192f)
制备方法与实施例六相同，区别在于，所述热稳定剂为醋酸铜与碘化钾的复配，醋酸铜添加量占生产原料总重量的200ppm，碘化钾添加量占生产原料总重量的1800ppm。
实施例十八：聚酰胺56工业丝(1670dtex/192f)
制备方法与实施例六相同，区别在于，所述热稳定剂为醋酸铜与碘化钾的复配，醋酸铜添加量占生产原料总重量的200ppm，碘化钾添加量占生产原料总重量的2500ppm。
对比例一：聚酰胺56工业丝(933dtex/140f)
制备方法与实施例一相同，区别在于，没有在步骤(1)1,5-戊二胺和己二酸聚合中加入热稳定剂醋酸铜。
对比例二：聚酰胺56工业丝(933dtex/140f)
制备方法与实施例一相同，区别在于，步骤1聚合中，获得的高粘度聚酰胺56树脂含水率为1200ppm。
对比例三：聚酰胺56工业丝(1670dtex/192f)
制备方法包括如下步骤：
1、聚合：
(1)氮气条件下，将原料1,5-戊二胺、己二酸和水混合均匀，加入热稳定剂，制得浓度为60％的聚酰胺56盐溶液；其中，所述1,5-戊二胺和己二酸的摩尔比为1.1：1。所述热稳定剂为醋酸铜与碘化钾复配，醋酸铜添加量占生产原料总重量的200ppm，碘化钾添加量占生产原料总重量的500ppm。
(2)将所述聚酰胺56盐溶液加热，反应体系内压力升至2.3Mpa，排气，保压，保压结束时反应体系的温度为255℃。再降压使反应体系内压力降至0.1MPa，降压结束后反应体系的温度为270℃。抽真空至真空度-0.05Mpa，抽真空后的温度为280℃，获得低粘度聚酰胺56树脂。所述压力均为表压。
所述低粘度聚酰胺56树脂96％硫酸的相对粘度为2.5，齐聚物含量为0.8wt％，数均分子量为16000，分子量分布为1.5，含水率为500ppm，氨基含量为42.5mmol/kg。
2、纺丝：
(1)将所述低粘度聚酰胺56树脂加热至熔融状态，形成聚酰胺56熔体，所述加热在螺杆挤出机中进行，具体分为五区加热，一区温度为250℃，二区温度为275℃，三区温度为280℃，四区温度为295℃，五区温度为305℃。将所述聚酰胺56熔体经纺丝箱体的喷丝板喷出，形成初生丝；所述纺丝箱体的温度为290℃，组件压力为14MPa，喷丝头拉伸比为120。
(2)对所述初生丝进行保温、冷却、上油、拉伸、卷绕成型，得到所述聚酰胺56工业丝；
所述保温采用缓冷装置进行，缓冷温度为230℃，缓冷长度为40mm；冷却为侧吹风进行冷却，风速为1.1m/s，风温为23℃，湿度为75％。所述卷绕成型时的卷绕张力为160cN，卷绕的速度为3200m/min，所述卷绕超喂比例为3.5％。所述拉伸过程为四级拉伸，所述拉伸过程与实施例一相同；区别在于，所述拉伸的总拉伸倍数为5.6；所述第一次热定型的温度为225℃；所述第二次热定型的温度为235℃。
对比例四：聚酰胺6工业丝(933dtex/140f)
所述制备方法包括如下步骤：
1、将高粘度聚酰胺6树脂加热至熔融状态，形成聚酰胺6熔体，所述加热在螺杆挤出机中进行，具体分为五区加热，一区温度为255℃，二区温度为270℃，三区温度为280℃，四区温度为290℃，五区温度为300℃。所述高粘度聚酰胺6树脂96％硫酸的相对粘度为3.3，齐聚物含量为0.8wt％，数均分子量为30000，分子量分布为1.6，含水率为400ppm，氨基含量为36.5mmol/kg。
2、将所述聚酰胺6熔体进行纺丝，将所述聚酰胺56熔体经纺丝箱体的喷丝板喷出，形成所述初生丝；所述纺丝箱体的温度为290℃，组件压力为15MPa，喷丝头拉伸比为150。
3、对所述初生丝进行处理后得到所述聚酰胺6工业丝，所述处理过程包括如下步骤：对 所述出喷丝孔初生丝进行保温、冷却、上油、拉伸、卷绕成型，得到所述聚酰胺56工业丝；所述保温采用缓冷装置进行，缓冷温度为220℃，缓冷长度为20mm；冷却为侧吹风进行冷却，风速为1.2m/s，风温为22℃，湿度为70％。
所述卷绕成型时的卷绕张力为90cN，卷绕速度为3500m/min，卷绕超喂比例为2.0％。
所述拉伸过程为四级拉伸，所述拉伸过程与实施例一相同；区别在于，所述拉伸的总拉伸倍数为5.0；所述第一次热定型的温度为220℃；所述第二次热定型的温度为230℃。
以上实施例和对比例中无油丝相对粘度与其树脂相对粘度的差的绝对值、以及无油丝氨基与其树脂氨基的差的绝对值、断单丝(次数/24h)和制成率(％)如表1所示。获得的聚酰胺56工业丝性能结果如表2所示。
表1
Figure PCTCN2020072240-appb-000004
Figure PCTCN2020072240-appb-000005
本发明通过降低无油丝粘度与氨基波动范围，提高了聚酰胺56熔体均匀性和和稳定性，减少了断单丝次数，增加了可纺性，制备的聚酰胺56工业丝的制成率≥95％，断单丝次数≤1次/24h。
表2
Figure PCTCN2020072240-appb-000006
本发明通过优化聚酰胺56树脂粘度、齐聚物含量、分子量及其分布、含水率，其次优化聚酰胺56工业丝纺丝工艺，提高了聚酰胺56工业丝的结晶度与取向度，增加定型温度与增大卷绕超喂比例，降低其后续应力松弛，最终得到具有优异力学性能与尺寸稳定性能的聚酰胺56工业丝，断裂强度可达8.0cN/dtex以上，断裂伸长率为26％以下；干热收缩率和沸水收缩率可达6％以下；结晶度70％以上；取向度80％以上。
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和使用本发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改，并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此，本发明不限于上述实施例，本领域技术人员根据本发明的揭示，不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。

Claims (25)

  1. 一种聚酰胺5X工业丝，其特征在于：所述聚酰胺5X工业丝中铜离子含量为10-1000ppm，所述聚酰胺5X包括聚酰胺56，聚酰胺510，聚酰胺512、聚酰胺513或聚酰胺514中的任意一种。
  2. 如权利要求1所述的聚酰胺5X工业丝，其特征在于：所述聚酰胺5X工业丝中铜离子含量为30-500ppm。
  3. 如权利要求1所述的聚酰胺5X工业丝，其特征在于：所述聚酰胺5X工业丝中铜离子含量为50-200ppm。
  4. 如权利要求1所述的聚酰胺5X工业丝，其特征在于：所述聚酰胺5X工业丝在180℃、4h处理后，耐热断裂强力保持率≥90％；在230℃、30min处理后，耐热断裂强力保持率≥90％；所述聚酰胺5X工业丝的干热收缩率为≤8.0％。
  5. 如权利要求1所述的聚酰胺5X工业丝，其特征在于：所述聚酰胺5X工业丝在180℃、4h处理后，耐热断裂强力保持率为≥93％；在230℃、30min处理后，耐热断裂强力保持率为≥92％；所述聚酰胺5X工业丝的干热收缩率为≤6.0％。
  6. 一种聚酰胺5X工业丝，其特征在于：所述聚酰胺5X工业丝含有热稳定剂，所述热稳定剂包括醋酸铜、碘化钾、氯化铜、碘化亚铜、氧化铜、氧化亚铜中的任意一种或几种的组合；所述热稳定剂的添加量占生产原料总重量的10-2800ppm。
  7. 如权利要求6所述的聚酰胺5X工业丝，其特征在于：所述热稳定剂的添加量占生产原料总重量为100-2500ppm。
  8. 如权利要求6所述的聚酰胺5X工业丝，其特征在于：所述热稳定剂包括碘化钾与醋酸铜的组合物，其中醋酸铜与碘化钾的摩尔比为1:1-15。
  9. 如权利要求1或权利要求6所述的聚酰胺5X工业丝，其特征在于：所述聚酰胺5X工业丝的断裂强度为6.5cN/dtex以上。
  10. 如权利要求1或权利要求6所述的聚酰胺5X工业丝，其特征在于：所述聚酰胺5X工业丝的断裂强度为7.0cN/dtex以上。
  11. 如权利要求1或权利要求6所述的聚酰胺5X工业丝，其特征在于：所述聚酰胺5X工业丝的断裂强度为8.0cN/dtex以上。
  12. 如权利要求1或权利要求6所述的聚酰胺5X工业丝，其特征在于：所述聚酰胺5X工业丝的无油丝相对粘度为2.7-4.5，无油丝相对粘度与其树脂相对粘度的差的绝对值≤0.12。
  13. 如权利要求12所述的聚酰胺5X工业丝，其特征在于：所述聚酰胺5X工业丝的无油丝相对粘度与其树脂相对粘度的差的绝对值为≤0.10，更优选为≤0.08。
  14. 如权利要求1或权利要求6所述的聚酰胺5X工业丝，其特征在于：所述聚酰胺5X工业丝的无油丝氨基含量为20-50mmol/kg；无油丝氨基与其树脂氨基的差的绝对值为≤5。
  15. 如权利要求14所述的聚酰胺5X工业丝，其特征在于：无油丝氨基与其树脂氨基的 差的绝对值为≤3，更优选为≤2。
  16. 如权利要求1或权利要求6所述的聚酰胺5X工业丝，其特征在于：所述聚酰胺5X工业丝断单丝次数≤2次/24h，优选为≤1次/24h，更优选为0次/24h，所述聚酰胺5X工业丝的制成率≥90％，优选为≥93％，更优选为≥96％。
  17. 如权利要求1或权利要求6所述的聚酰胺5X工业丝，其特征在于：所述聚酰胺5X工业丝的沸水收缩率为在8.0％以下，优选为在7.0％以下，更优选为在6.0％以下；和/或，
    所述聚酰胺5X工业丝的纤度为100-3500dtex，优选为200-2500dtex，更优选为300-1800dtex；和/或，
    所述聚酰胺5X工业丝的断裂伸长率为26％以下，优选为22％以下；和/或，
    所述聚酰胺5X工业丝的结晶度为70％以上，优选为72％以上，更优选为74％以上；和/或，
    所述聚酰胺5X工业丝的取向度为80％以上，优选为82％以上，更优选为84％以上。
  18. 如权利要求1或权利要求6所述的聚酰胺5X工业丝，其特征在于：所述聚酰胺5X工业丝的生产原料至少包括：1,5-戊二胺和己二酸；或者，以1,5-戊二胺和己二酸为单体聚合得到的聚酰胺5X；优选地，所述1,5-戊二胺由生物基原料通过发酵法或酶转化法制备而成。
  19. 一种如权利要求1-18任一项所述的聚酰胺5X工业丝的制备方法，其特征在于：所述制备方法包括如下步骤：
    (1)、将1,5-戊二胺和己二酸聚合，获得高粘度聚酰胺5X熔体，通过熔体增压泵输送到纺丝箱体，直接进行纺丝；或者，采用切片纺丝，即先制备低粘度聚酰胺5X树脂，然后通过固相增粘获得高粘度聚酰胺5X树脂，将高粘度聚酰胺5X树脂加热至熔融状态，形成聚酰胺5X熔体进行纺丝；
    (2)、将步骤(1)获得的聚酰胺5X熔体进行拉丝，形成初生丝；
    (3)、对所述初生丝进行处理后得到所述聚酰胺5X工业丝；
    其中，在步骤(1)1,5-戊二胺和己二酸聚合过程中加入热稳定剂，或以热稳定剂母粒形式在聚合熔体切粒前在线注入，或以热稳定剂母粒形式在纺丝过程中共混加入；
    所述热稳定剂母粒中铜离子含量为0.5-10wt％，优选为0.8-5wt％，更优选为1.2-3wt％；
    所述热稳定剂母粒添加量为0.3-5.0wt％，优选为0.5-3.0wt％，更优选为0.8-2.0wt％；
    所述热稳定剂母粒基体材料包括聚酰胺6、聚酰胺56、聚酰胺66、聚酰胺510、聚酰胺610、聚对苯二甲酸丁二醇酯中的任意一种或几种的组合，优选为聚酰胺6、聚酰胺56、聚酰胺510，更优选为聚酰胺6、聚酰胺56；
    优选地，所述制备方法还包括加入其它添加剂的步骤，所述其它添加剂包括：消光剂、阻燃剂、抗氧化剂、紫外线吸收剂、红外线吸收剂、结晶成核剂、荧光增白剂和抗静电剂中的任意一种或几种；优选地，所述其它添加剂的添加量占生产原料总重量的0.01-5wt％。
  20. 根据权利要求19所述的制备方法，其特征在于，步骤(1)具体包括以下步骤：
    (1-1)惰性气体或真空条件下，将1,5-戊二胺、己二酸和水混合均匀，制得聚酰胺5X 盐溶液；其中，所述1,5-戊二胺和己二酸的摩尔比为(0.95-1.2)：1；
    (1-2)将所述聚酰胺5X盐溶液加热，反应体系内压力升至0.3-2.5Mpa，排气，保压，再降压使反应体系内压力降至0-0.2MPa，抽真空至真空度-(0.01-0.1)Mpa，所述压力为表压，得到聚酰胺5X熔体；
    其中，优选地，所述保压结束时反应体系的温度为230-275℃；和/或，
    优选地，所述降压结束后反应体系的温度为240-285℃；和/或，
    优选地，所述抽真空后的温度为265-295℃。
  21. 根据权利要求19所述的制备方法，其特征在于：步骤(1)中，
    所述低粘度聚酰胺5X树脂96％硫酸的相对粘度为2.0-2.7，优选为2.2-2.6，更优选为2.4-2.5；和/或，
    所述高粘度聚酰胺5X树脂96％硫酸的相对粘度为2.7-4.5，优选为3.2-4.0，更优选为3.4-3.6；和/或，
    所述高粘度聚酰胺5X树脂齐聚物含量为0.2-1.0wt％，优选为0.4-0.6wt％；和/或，
    所述高粘度聚酰胺5X树脂的数均分子量为18000-40000，优选为25000-30000，分子量分布为0.8-1.8，优选为1.2-1.5；和/或，
    所述高粘度聚酰胺5X树脂的含水率为200-800ppm，优选为300-750ppm，更优选为350-700ppm，进一步优选为400-600ppm；和/或，
    所述高粘度聚酰胺5X树脂氨基含量为20-50mmol/kg，优选为24-45mmol/kg，更优选为28-40mmol/kg，进一步优选为32-36mmol/kg；和/或，
    优选地，步骤(1)中的加热在螺杆挤出机中进行，所述螺杆挤出机分为五区加热；
    其中，一区温度为250-290℃，二区温度为260-300℃，三区温度为270-320℃，四区温度为280-330℃，五区温度为280-320℃。
  22. 根据权利要求19所述的制备方法，其特征在于：步骤(2)具体包括如下步骤：
    将所述聚酰胺5X熔体经纺丝箱体的喷丝板喷出，形成所述初生丝；
    优选地，所述纺丝箱体的温度为270-330℃，更优选为280-310℃，进一步优选为290-300℃，更进一步优选为293-297℃；和/或，
    所述纺丝箱体的纺丝组件压力为8-25MPa，优选为12-20MPa，进一步优选为15-18MPa；和/或，
    所述喷丝板的喷丝头拉伸比为50-400，优选为70-300，进一步优选为80-200，更进一步优选为90-100。
  23. 根据权利要求19所述的制备方法，其特征在于：步骤(3)具体包括如下步骤：
    对所述出喷丝孔初生丝进行保温、冷却、上油、拉伸、卷绕成型，得到所述聚酰胺5X工业丝；
    优选地，所述保温采用缓冷装置进行，缓冷温度为150-280℃，更优选为200-240℃，缓冷长度为10-80mm，更优选为20-50mm；所述冷却通过侧吹风进行冷却，所述侧吹风的风速 为0.3-2.0m/s，更优选为0.6-1.5m/s；所述侧吹风的风温为15-25℃，更优选为17-23℃，进一步优选为19-22℃；所述侧吹风的湿度为60-80％，更优选为65-75％；和/或，
    所述卷绕成型时的卷绕张力为50-300cN，优选为80-200cN，进一步优选为100-160cN，更进一步优选为120-140cN；或者，
    所述卷绕的速度为2000-3800m/min，优选为2500-3500m/min，进一步优选为2800-3000m/min；所述卷绕超喂比例≤5％，优选为≤4％，进一步为优选≤3％。
  24. 根据权利要求19所述的制备方法，其特征在于：所述拉伸为四级以上拉伸；
    优选地，所述拉伸的过程包括：上油后的初生丝首先经过导丝辊喂入第一对热辊，在所述第一对热辊与第二对热辊之间进行一级拉伸，然后在所述第二对热辊与第三对热辊之间进行二级拉伸，在所述第三对热辊与第四对热辊之间进行三级拉伸并进行第一次热定型，接着在所述第四对热辊与第五对热辊之间进行四级拉伸并进行第二次热定型；
    其中，优选地：所述拉伸的总拉伸倍数为4.0-6.0；
    所述第一次热定型的温度为180-250℃，优选为200-240℃；
    所述第二次热定型的温度为200-240℃，优选为220-230℃；
  25. 权利要求1至18任一项所述的聚酰胺5X工业丝在缝纫线、轮胎帘子线、气囊丝、脱模布、水布、帆布、安全带、绳索、渔网、工业过滤布、传输带、降落伞、帐篷、箱包领域的应用。
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