WO2017133085A1 - 一种尼龙6聚合方法及其熔体直纺方法 - Google Patents

一种尼龙6聚合方法及其熔体直纺方法 Download PDF

Info

Publication number
WO2017133085A1
WO2017133085A1 PCT/CN2016/080024 CN2016080024W WO2017133085A1 WO 2017133085 A1 WO2017133085 A1 WO 2017133085A1 CN 2016080024 W CN2016080024 W CN 2016080024W WO 2017133085 A1 WO2017133085 A1 WO 2017133085A1
Authority
WO
WIPO (PCT)
Prior art keywords
nylon
spinning
polymer
melt
temperature
Prior art date
Application number
PCT/CN2016/080024
Other languages
English (en)
French (fr)
Inventor
王朝生
王华平
汤廉
李益仁
朴宏
李建武
汪丹越
Original Assignee
东华大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 东华大学 filed Critical 东华大学
Priority to EP16888909.5A priority Critical patent/EP3412704A4/en
Publication of WO2017133085A1 publication Critical patent/WO2017133085A1/zh

Links

Images

Classifications

    • 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
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14—Lactams
    • C08G69/16—Preparatory processes
    • 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
    • D01D5/253—Formation of filaments, threads, or the like with a non-circular cross section; Spinnerette packs therefor
    • 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
    • D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
    • 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
    • D01F1/08—Addition of substances to the spinning solution or to the melt for forming hollow filaments
    • 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
    • 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
    • D01F1/103—Agents inhibiting growth of microorganisms
    • 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
    • D01F1/106—Radiation shielding agents, e.g. absorbing, reflecting agents
    • 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
    • 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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent

Definitions

  • the invention belongs to the technical field and relates to a nylon 6 polymerization method and a melt direct spinning method thereof.
  • nylon fiber Due to its excellent physical and mechanical properties and textile processing properties, nylon fiber ranks first in the synthetic fiber family for a long period of time since its inception, but due to price and production cost constraints and polyester fiber The rapid development is now the second largest production of synthetic fibers. In 2013, China's nylon production was 2,112,800 tons, an increase of 12.44% year-on-year, and the output accounted for 6.3% of the total synthetic fiber production.
  • Nylon fiber has excellent physical properties unmatched by polyester fiber. For example, nylon fiber has high breaking strength, wear resistance is the crown of textile universal fiber, good hygroscopicity, excellent elastic recovery rate and fatigue resistance, and good dyeability.
  • nylon fiber In addition to clothing and decoration, nylon fiber has a wide range of applications in other industries, such as tire cord fabrics, automotive textiles, filter materials, and BCF carpet bulk yarns.
  • nylon fiber There are many varieties of nylon fiber, the main varieties are nylon 6 and nylon 66 fiber. Due to historical reasons and different specific conditions of different countries, the focus of each country is different. The United States, Britain and other countries mainly produce nylon 66, Germany, Italy, Japan and Eastern European countries mainly use nylon 6, and China mainly produces nylon 6 fiber.
  • Caprolactam continuous hydrolysis polymerization is the most widely used nylon 6 polymerization process.
  • the conversion rate of caprolactam is generally about 90%, which means that about 10% of the caprolactam and oligomers remain in the polymer (in which the monomer accounts for about 75%, low).
  • the polymer accounts for about 25%, and the oligomer is mainly a cyclic dimer. It is usually removed by hot water in the industry and is therefore also called hot water extractables.
  • the hot water extractable content should be less than 1.5%.
  • the industry needs to extract the polyamide 6 slices before spinning.
  • the content of hot water extractables in polycaprolactam slices should be less than 0.5% (excellent), but the process needs to consume a large amount.
  • the polymer, and thus the melt spinning of polyamide 6, became one of the constraints of the development of polyamide 6 fibers. Therefore, by developing a new polymerization process, reducing the oligomer content produced in the lactam hydrolysis polymerization process, the nylon 6 melt direct spinning has become a trend of industrial development.
  • the main method for reducing the content of oligomers in the hydrolysis polymerization of caprolactam is to control the polymerization temperature, because the polymerization of caprolactam is a balanced relationship with temperature change, which is more favorable for oligomer formation with increasing temperature.
  • it is a cyclic oligomer, so that the oligomer content, that is, low-temperature polymerization, can be effectively controlled by controlling the polymerization temperature.
  • the polymerization temperature needs to be at least 10 ° C below the melting point of polyamide 6.
  • the polymerization temperature at this time still cannot control the oligomer in the range of meltable direct spinning, and there is another one for low temperature polymerization.
  • the disadvantage is that the reaction rate is slow, and the obtained polymer has a low molecular weight; while the polymerization at a lower temperature is actually divided into two parts, one is a melt polymerization process, and the other is a solid phase polymerization process, solid phase polymerization.
  • the process is to obtain a polymer with sufficient molecular weight for product development, but no effective method for converting a solid polymer formed at a low temperature into a suitable spinning method has been found.
  • the fiber is spun from a low temperature polymer, it must be The polymer is first melted, however, at this time, with the balance of time and temperature, a low molecular compound is formed, the amount of which is compatible with the temperature at the time of melting, and always higher than that at the time of low temperature polymerization, so that There is no advantage compared to the normal polymerization method.
  • the invention obtains a certain molecular weight by preparing a polyamide 6 prepolymer at a low temperature, preliminarily controlling the content of the oligomer in the melt, and then strengthening the kinetics of the polycondensation reaction to complete the polymerization before the cyclic oligomer is formed in a large amount.
  • Nylon 6 polymer melt This method can avoid the formation of a large amount of cyclic oligomers over time at a relatively high temperature in the reaction time period at a high temperature.
  • the technical problem to be solved by the present invention is to provide a nylon 6 polymerization method and a melt direct spinning method thereof.
  • the nylon 6 polymerization method of the invention adopts the method of segmental polymerization to prepare nylon 6, and the specific preparation method is as follows:
  • the first stage is a ring-opening reaction stage: pre-polymerization of caprolactam, water and catalyst at a temperature of 150-220 ° C and a pressure of 0.1-5 MPa; this process is the action of caprolactam under pressure and ring-opening agent water
  • the lower ring opens to form aminocaproic acid, and the aminocaproic acid further opens the caprolactam by an addition reaction to form a short segment, which also increases the ring opening ratio of caprolactam.
  • the polymerization temperature used in this process is lower due to the formation of cyclic oligomers. It is a thermodynamic equilibrium process. The temperature drop is beneficial to reduce the content of cyclic oligomers.
  • nylon 6 which is short-segment is formed at this stage.
  • the nylon 6 molecular chain segment is rigid, and the activation energy of terminal amino back biting is improved.
  • the possibility of cyclic oligomers is reduced, resulting in lower levels of cyclic oligomers;
  • the obtained product has a number average molecular weight of 1000-2000, an oligomer content of 10-30%, a cyclic dimer content of 0.1% or less, and a melt viscosity of 1-10 Pa ⁇ s;
  • the second stage is a pre-polycondensation stage: the product obtained by the ring-opening reaction is subjected to a polycondensation reaction under the conditions of a pressure of 10-200 Pa and a temperature of 180-220 ° C; the purpose of this process is to pass the short-chain segment obtained in the first stage through polycondensation. Increase the molecular weight and remove most of the small molecules such as monomer and water. This process needs to be carried out under low pressure conditions. For nylon 6, when the molecular weight increases to about 5000, it is the molecular chain entanglement point. The viscosity of the polymer melt increases greatly with the increase of the molecular weight.
  • the process needs to be kept at a lower temperature, and the melt viscosity must be kept at a low level to facilitate small Molecular extraction is required, so the molecular weight of the polymer needs to be controlled near the entanglement point.
  • the third stage is the kinetic strengthening stage of polycondensation reaction: polymerization under the condition of pressure of 10-100Pa, the polymerization temperature is gradually increased from 180-220 °C to 220-280 °C; the obtained molecular weight of the melt is 11400-45600, and the relative viscosity is 2.0.
  • the oligomer content is less than 1.5%, wherein the cyclic dimer content is 0.2% or less; the purpose of this process is to increase the molecular weight of the polymer to the target molecular weight, then it is necessary to increase the polymerization temperature, but in order to avoid the melt in At higher temperatures, the oligomer content increases with the increase of residence time, it is necessary to quickly remove small molecules, and quickly increase the molecular weight of the polymer to the target molecular weight; to ensure that small molecules can be quickly removed to achieve fast viscosity-increasing
  • the purpose is to ensure that the melt viscosity is at a low level; the polymerization temperature is gradually increased from 180-220 °C to 220-280 °C, which is a stepwise heating method, because the melt viscosity increases as the molecular weight increases, in order to ensure When the melt viscosity is at a low level, the temperature is raised, but considering the high temperature is favorable for the formation of oligomers, the gradient heating method
  • a nylon 6 polymerization method as described above having a water content of 1 to 20% by weight of caprolactam and a catalyst content of 1 to 20% by weight of caprolactam.
  • the amino acid is an aliphatic amino acid or an aromatic amino acid
  • the amino acid of the family amino acid is a benzene ring in the main chain or on the branch, which is phenylalanine.
  • the step temperature rise means that the temperature is raised from 180-220 ° C to 220-280 ° C into 2-10 stages, so that the temperature gradually rises as the polycondensation reaction progresses.
  • a nylon 6 polymerization method employs a liquid phase thickening kettle to effect the kinetic strengthening process of the polycondensation reaction.
  • the fuel, the negative ion generating material, the fluorescent material, the carbon nanotubes or the graphene are added in an amount of 0.01 to 10% by weight based on the caprolactam.
  • the antioxidant is an antioxidant 1010, an antioxidant 168 or an antioxidant 616
  • the anti-UV agent is salicylic acid, benzophenone benzotriazole, titanium oxide, oxidation Zinc, calcium carbonate, talc, SEED
  • antibacterial agent is nano titanium dioxide, zinc oxide, iron oxide, chitosan, nano silver, nano copper or quaternary ammonium salt compound
  • flame retardant is zinc borate, tetrabromobisphenol A , bis(hexachlorocyclopentadienyl)cyclooctane, ammonium polyphosphate, decabromodiphenyl ether or 1,3,6-tris(4,6-diamino-2-thiotriazine)hexane and three a mixture of polycyanic acid
  • the negative ion generating material is chert, tourmaline, opal or genius
  • the fluorescent material is a sulphide or aluminate of an alkaline earth metal
  • a chain extender is further added to achieve a rapid viscosity-increasing effect, and the chain extender is added in an amount of 0.01 wt% to 1.2 wt% of caprolactam;
  • the invention also provides a melt direct spinning method of a nylon 6 polymer, which is directly spun according to a nylon 6 spinning process after the end of the polycondensation reaction kinetic strengthening process, and the spinning temperature is 240. -280 ° C, the first godet speed is 4000-4500 m / min, the second godet speed is 5000-6000 m / min, the draw ratio is 1.1-1.5 times, the cooling air temperature is 15-25 ° C, the wind speed is 0.5 -1 m/s, relative humidity of 60% - 90%, to obtain a fully drawn yarn.
  • a melt straight spinning method of a nylon 6 polymer as described above the nylon 6 polymer is directly spun in a nylon 6 spinning process immediately after the kinetic strengthening process of the polycondensation reaction, and the spinning temperature is 240- 280 ° C, spinning speed of 700-1500 m / min, cooling air temperature of 20-30 ° C, wind speed of 0.3-1 m / s, relative humidity of 60% -80%, to obtain unoriented yarn.
  • a melt straight spinning method of a nylon 6 polymer as described above the nylon 6 polymer is directly spun in a nylon 6 spinning process immediately after the kinetic strengthening process of the polycondensation reaction, and the spinning temperature is 240- 280 ° C, spinning speed of 4000-4500 m / min, cooling air temperature of 15-25 ° C, wind speed of 0.3-0.6 m / s, relative humidity of 60% -80%, to obtain pre-oriented yarn.
  • a melt straight spinning method of a nylon 6 polymer as described above the nylon 6 polymer is directly spun in a nylon 6 spinning process immediately after the kinetic strengthening process of the polycondensation reaction, and the spinning temperature is 240- The 280 ° C, the spinning speed is 4500-6000 m / min, the cooling air temperature is 15-20 ° C, the wind speed is 0.3-0.5 m / s, the relative humidity is 80% -90%, and the highly oriented yarn is obtained.
  • a melt straight spinning method of a nylon 6 polymer as described above the nylon 6 polymer is directly spun in a nylon 6 spinning process to obtain a puffed textured yarn after the kinetic strengthening process of the polycondensation reaction, and the spinning is performed.
  • the temperature is 240-280 ° C
  • the cooling air temperature is 20-30 ° C
  • the wind speed is 0.3-1 m/s
  • the relative humidity is 60%-80%
  • the feeding roller temperature is 60-120 ° C
  • the stretching roll temperature is 100-190.
  • feeding speed is 300-1000m/min
  • stretching speed is 1000-3500m/min
  • stretching ratio is 3.5-5 times
  • deformation hot air temperature is 190-230°C
  • air injection pressure is 196kPa-490kPa
  • roll The winding speed is 600-3000 m/min and the cooling air temperature is 25 °C.
  • nylon 6 a melt-spinning method of a nylon 6 polymer as described above, the nylon 6 polymer being directly applied to the composite spinning after the end of the polycondensation reaction kinetic strengthening process, the composite spinning is a side-by-side type Core type, island type, orange type or multi-core type composite spinning; the other components of the composite spinning except nylon 6 are nylon 6T, nylon 612, nylon 610, nylon 1212, nylon 46, nylon 410, One of nylon 11, nylon 12, nylon 26, nylon 212, branched nylon, water-soluble polyester, the mass ratio of the nylon 6 polymer to another component is 3:7-7:3.
  • a melt direct spinning method of a nylon 6 polymer as described above the spinning microporous cross-sectional shape of the spinning is triangular, cross, polygonal, hollow fiber, U-shaped, T-shaped, Y-shaped, polygonal or industrial Glyph.
  • nylon is nylon 6, nylon 6T, nylon 612, nylon 610, nylon 1212, nylon 46, nylon 410, nylon 11, nylon 12, nylon 26, nylon 212, one or more of branched nylon
  • polyester is one of polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, water-soluble polyester And above
  • polyethylene glycol has a molecular weight ranging from 400 to 20,000, a polyethylene glycol end group is a hydroxyl group, or a polyethylene glycol having a modified terminal group of a carboxyl group and/or an amino group.
  • the material, carbon nanotubes or graphene is in an amount of 10-30% by weight of the functional masterbatch.
  • the coloring agent used in the masterbatch is phthalocyanine red, phthalocyanine blue, phthalocyanine green, light fast red, macromolecular red, macromolecular yellow , permanent solid yellow, permanent solid purple, azo red, cadmium red, cadmium
  • a melt-spinning method of a nylon 6 polymer as described above after the kinetic strengthening process of the polycondensation reaction is completed, a polymer chip is added on-line during the melt transfer process, and the mixture is uniformly mixed.
  • the yarn was directly spun according to the nylon 6 spinning process, and the polymer chip was added in an amount of 5 to 50% by weight of the nylon 6 melt.
  • nylon is one of nylon 6, nylon 6T, nylon 612, nylon 610, nylon 1212, nylon 46, nylon 410, nylon 11, nylon 12, nylon 26, nylon 212, and branched nylon.
  • polyethylene glycol has a molecular weight ranging from 400 to 20,000, a polyethylene glycol end group is a hydroxyl group, or a polyethylene glycol having a modified terminal group of a carboxyl group and/or an amino group.
  • the invention also provides a nylon 6 polymer spun into a fiber woven fabric, the nylon polymer is spun into nylon 6 fiber, and then woven or knitted to form a fabric, the fabric is plain, twill, satin One of them is then dyed to obtain fabrics of different specifications.
  • the dyeing production process of the fabric is: pre-treatment desizing-hot water cleaning fabric-heating dyeing-fixing-cooling cleaning-clothing machine waterproofing stereotype-finished product inspection-finished product winding.
  • the pretreatment desizing temperature is 60-80 ° C
  • the desizing time is 6-12 h
  • the desizing assistant formula is: soda ash 10-20 g / L, deoiling spirit 10-15 g / L .
  • the temperature rising dyeing process is a starting dyeing temperature of 30-40 ° C, heating at a rate of 1-3 ° C / min, heating to 90-95 ° C and then holding for 40 min; the dye concentration is 0.5-2% (omf), the bath ratio is 1:10-20.
  • the fixing process is a temperature of 90-95 ° C, a fixing time of 20-60 min, a fixing agent concentration of 0.5-2% (omf), and a bath ratio of 1:10-20.
  • the auxiliary agent is added in an amount of 5-10 g/L, the auxiliary agent is a soft water agent, and is a NORM02; leveling agent is ACID03. Or ACID16; retarder, ammonium sulfate.
  • the invention provides a device for a nylon 6 polymerization method.
  • the function of the silo is to store caprolactam, which is connected to the raw material heating tank through a pipeline.
  • the raw material heating tank functions to melt the caprolactam;
  • the pressurized open loop kettle is heated by the pipeline and the raw material.
  • the tanks are connected, and the function of the pressurized open-loop kettle is to promote the hydrolysis and ring opening of caprolactam by means of pressurization to obtain a prepolymer having a low cyclic oligomer content;
  • the polycondensation kettle is connected to the pressurized open-loop kettle through a pipe, and is polycondensed.
  • the function of the kettle is to pre-condense the product of the pressurized open-loop kettle to the molecular weight near the molecular chain entanglement point, and to remove a large amount of unreacted monomer, at which time the melt viscosity is low, so the conditions for the polycondensation are required.
  • the liquid phase thickening kettle is connected to the polycondensation tank through a pipeline. The liquid phase thickening kettle is used to strengthen the product of the polycondensation kettle by high vacuum polycondensation kinetics to the target molecular weight, and the unreacted monomer and moisture are fast.
  • the melt viscosity is high, so the conditions for the polycondensation are high; in the polycondensation kettle, the liquid phase thickening kettle is connected to the buffer tank through the pipeline, and the function of the buffer tank is to collect The small molecule extracted from the polycondensation kettle and the liquid phase thickening kettle is sent to the concentration tank; the concentration tank and the buffer tank are connected by a pipeline, and the function of the concentration tank is to concentrate the monomer conveyed in the buffer tank. And re-delivered to the raw material heating tank to continue to participate in the reaction. Was sent to the concentrator for concentration and property reuse; The resulting melt is directly conveyed to a spinning pack for spinning, followed by weaving, dyeing, to obtain a final product.
  • the invention adopts low temperature polymerization to prepare a prepolymer, and realizes effective control of the cyclic dimer, mainly relying on the following mechanism:
  • the positive reaction is a cyclic dimer ring-opening addition reaction
  • the reverse reaction is a terminal amino occlusion reaction
  • the relationship between the reaction rate constant k and the temperature can be obtained. It can be seen from the formula that the higher the activation energy of the reaction, the more sensitive the reaction rate constant is to the change of temperature, and the activation energy of the addition polymerization of the cyclic dimer. It is smaller than the activation energy of the ring-forming reaction, and therefore, the polymerization temperature is increased to facilitate the progress of the cyclization reaction, thereby increasing the content of the cyclic low molecular substance.
  • the polymerization process of the invention is simple, and the utilization rate of caprolactam is improved, the energy consumption is reduced, and the production cost of nylon 6 is lowered.
  • the invention firstly forms a prepolymer at a low temperature prepolymerization at 150-220 ° C to ensure that the prepolymer in the system has high activity and contains a low cyclic oligomer, especially a ring two.
  • the polymer is then polymerized by a polycondensation reaction kinetic strengthening method to complete the polymerization before the cyclic oligomer is formed in a large amount to obtain a nylon 6 polymer melt having a certain molecular weight.
  • the method can avoid the melt at a higher temperature, and the cyclic oligomer can be formed in a large amount with time, effectively reducing the content of the cyclic oligomer, and the obtained extractable content of the melt is ⁇ 2%, cyclic dimer content ⁇ 0.2%, product relative viscosity of 2.0 ⁇ 6.0, can be used for melt direct spinning polyamide melt.
  • Figure 1 is a structural diagram of the unstable treatment of cyclic dimers.
  • a nylon 6 polymerization method is prepared by a stepwise polymerization method, and the specific preparation method is as follows:
  • the obtained product has a number average molecular weight of 1000, an oligomer content of 30%, a cyclic dimer content of 0.1% or less, and a melt viscosity of 1 Pa ⁇ s;
  • the second stage is a pre-polycondensation stage: the product obtained by the ring-opening reaction is subjected to a polycondensation reaction under the conditions of a pressure of 10 Pa and a temperature of 220 ° C, and the pre-polycondensation reaction time is 1 h;
  • the third stage is the kinetic strengthening phase of the polycondensation reaction: polymerization at a pressure of 10 Pa, and the polymerization temperature is gradually increased from 220 ° C to 280 ° C (divided into 2 stages, the first stage is raised from 220 ° C to 250 ° C, the second stage is from 250 ° C rose to 280 ° C), the polycondensation reaction kinetic strengthening process time is 90min;
  • the obtained melt had a molecular weight of 11,400, a relative viscosity of 2.0, an oligomer content of 1.5% or less, and a cyclic dimer content of 0.2% or less; and a nylon 6 polymer was obtained after the kinetic strengthening of the polycondensation reaction.
  • a nylon 6 polymerization method is prepared by a stepwise polymerization method, and the specific preparation method is as follows:
  • the obtained product has a number average molecular weight of 1500, an oligomer content of 20%, a cyclic dimer content of 0.1% or less, and a melt viscosity of 5 Pa ⁇ s;
  • the second stage is a pre-polycondensation stage: the product obtained by the ring-opening reaction is subjected to a polycondensation reaction under the conditions of a pressure of 200 Pa and a temperature of 180 ° C, and the pre-polycondensation reaction time is 3 h;
  • the obtained prepolymer has a melt molecular weight of 5,000, an oligomer content of 4%, wherein the cyclic dimer content is 0.1%, and the melt viscosity is 50 Pa ⁇ s;
  • the third stage is the kinetic strengthening stage of polycondensation reaction: polymerization is carried out under the condition of pressure of 100Pa, and the polymerization temperature is gradually increased from 180 °C to 220 °C (divided into four stages, respectively 180 ° C - 190 ° C - 200 ° C - 210 ° C - 220 °C), the kinetic strengthening process time of the polycondensation reaction is 10 min;
  • the obtained melt has a molecular weight of 20520, a relative viscosity of 2.8, an oligomer content of 1.5% or less, wherein the cyclic dimer content is 0.2% or less; and a nylon 6 polymer is obtained after the kinetic strengthening of the polycondensation reaction is completed.
  • a nylon 6 polymerization method is prepared by a stepwise polymerization method, and the specific preparation method is as follows:
  • the obtained product has a number average molecular weight of 2000, an oligomer content of 10%, a cyclic dimer content of 0.1% or less, and a melt viscosity of 100 Pa ⁇ s;
  • the second stage is a pre-polycondensation stage: the product obtained by the ring-opening reaction is subjected to a polycondensation reaction under the conditions of a pressure of 100 Pa and a temperature of 200 ° C, and the pre-polycondensation reaction time is 1.5 h;
  • the obtained prepolymer has a melt molecular weight of 6000, an oligomer content of 2%, wherein the cyclic dimer content is 0.1%, and the melt viscosity is 100 Pa ⁇ s;
  • the third stage is the kinetic strengthening stage of polycondensation reaction: polymerization at a pressure of 50Pa, and the polymerization temperature is gradually increased from 200 °C to 280 °C (divided into 6 stages, respectively 200 ° C - 210 ° C - 220 ° C - 230 ° C - 240 °C-260°C-280°C), the kinetic strengthening process time of the polycondensation reaction is 10min;
  • the obtained melt had a molecular weight of 34,200, a relative viscosity of 4.0, an oligomer content of 1.5% or less, and a cyclic dimer content of 0.2% or less.
  • a nylon 6 polymer was obtained.
  • the obtained product has a number average molecular weight of 1800, an oligomer content of 15%, a cyclic dimer content of 0.1% or less, and a melt viscosity of 60 Pa ⁇ s;
  • the second stage is a pre-polycondensation stage: the product obtained by the ring-opening reaction is subjected to a polycondensation reaction under the conditions of a pressure of 150 Pa and a temperature of 210 ° C, and the pre-polycondensation reaction time is 2 h;
  • the obtained prepolymer has a melt molecular weight of 4500 and an oligomer content of 6%, wherein the cyclic dimer content is 0.1%, and the melt viscosity is 80 Pa ⁇ s;
  • the third stage is the kinetic strengthening stage of polycondensation reaction: polymerization under the condition of pressure 80 Pa, the polymerization temperature is gradually increased from 210 ° C to 280 ° C (divided into 5 stages, respectively 210 ° C - 220 ° C - 230 ° C - 240 ° C - 260 °C-280 ° C), the kinetic strengthening process time of the polycondensation reaction is 20 min;
  • the obtained melt has a molecular weight of 13680, a relative viscosity of 2.2, an oligomer content of 1.5% or less, wherein the cyclic dimer content is 0.2% or less; and a nylon 6 polymer is obtained after the kinetic strengthening of the polycondensation reaction is completed.
  • a nylon 6 polymerization method is prepared by a stepwise polymerization method, and the specific preparation method is as follows:
  • the first stage is a ring-opening reaction stage: pre-polymerization of caprolactam, water and catalyst at a temperature of 150 ° C and a pressure of 5 MPa, the ring-opening reaction time is 10 h; wherein the water content is 1 wt% of caprolactam, the catalyst The content is 20% by weight of caprolactam, and the catalyst is phenylalanine;
  • the obtained product has a number average molecular weight of 1200, an oligomer content of 25%, a cyclic dimer content of 0.1% or less, and a melt viscosity of 6 Pa ⁇ s;
  • the second stage is a pre-polycondensation stage: the product obtained by the ring-opening reaction is subjected to a polycondensation reaction under the conditions of a pressure of 10 Pa and a temperature of 220 ° C, and the pre-polycondensation reaction time is 2 h;
  • the obtained prepolymer has a melt molecular weight of 5,500, an oligomer content of 5%, wherein the cyclic dimer content is 0.1%, and the melt viscosity is 75 Pa ⁇ s;
  • the third stage is the kinetic strengthening stage of polycondensation reaction: polymerization at a pressure of 10 Pa, and the polymerization temperature is gradually increased from 220 ° C to 280 ° C (divided into 6 stages, respectively 220 ° C - 230 ° C - 240 ° C - 250 ° C - 260 °C-270°C-280°C), the kinetic strengthening process time of the polycondensation reaction is 30min;
  • the obtained melt had a molecular weight of 22,800, a relative viscosity of 3.0, an oligomer content of 1.5% or less, and a cyclic dimer content of 0.2% or less; and a nylon 6 polymer was obtained after the kinetic strengthening of the polycondensation reaction was completed.
  • a nylon 6 polymerization method is prepared by a stepwise polymerization method, and the specific preparation method is as follows:
  • the obtained product has a number average molecular weight of 1900, an oligomer content of 25%, a cyclic dimer content of 0.1% or less, and a melt viscosity of 10 Pa ⁇ s;
  • the second stage is a pre-polycondensation stage: the product obtained by the ring-opening reaction is subjected to a polycondensation reaction under the conditions of a pressure of 150 Pa and a temperature of 210 ° C, and the pre-polycondensation reaction time is 2.5 h;
  • the obtained prepolymer has a melt molecular weight of 5,200, an oligomer content of 7%, wherein the cyclic dimer content is 0.1%, and the melt viscosity is 90 Pa ⁇ s;
  • the third stage is the kinetic strengthening stage of polycondensation reaction: polymerization under the condition of pressure 80 Pa, the polymerization temperature is gradually increased from 210 ° C to 280 ° C (divided into 7 stages, respectively 210 ° C - 220 ° C - 230 ° C - 240 ° C - 250 °C-260°C-270°C-280°C), the kinetic strengthening process time of polycondensation reaction is 40min;
  • the obtained melt has a molecular weight of 29640, a relative viscosity of 3.6, an oligomer content of 1.5% or less, wherein the cyclic dimer content is 0.2% or less; and a nylon 6 polymer is obtained after the kinetic strengthening of the polycondensation reaction is completed.
  • a nylon 6 polymerization method is prepared by a stepwise polymerization method, and the specific preparation method is as follows:
  • the first stage is a ring-opening reaction stage: pre-polymerization of caprolactam, water and catalyst at a temperature of 200 ° C and a pressure of 3 MPa, the ring-opening reaction time is 8 h; wherein the water content is 15 wt% of caprolactam, the catalyst The content is 10% by weight of caprolactam, the catalyst is H 3 PO 4 ; the lactone is added at the same time, the added amount is 40% by weight of caprolactam;
  • the obtained product has a number average molecular weight of 1600, an oligomer content of 15%, a cyclic dimer content of 0.1% or less, and a melt viscosity of 30 Pa ⁇ s;
  • the second stage is the pre-polycondensation stage: the product obtained by the ring-opening reaction is subjected to a polycondensation reaction under the conditions of a pressure of 150 Pa and a temperature of 210 ° C, and the pre-polycondensation reaction time is 1 h; and the molecular weight stabilizer H(CH 2 ) b NH 2 is simultaneously added.
  • the obtained prepolymer has a melt molecular weight of 4500 and an oligomer content of 7%, wherein the cyclic dimer content is 0.1%, and the melt viscosity is 90 Pa ⁇ s;
  • the third stage is the kinetic strengthening stage of polycondensation reaction: polymerization under the condition of pressure 80 Pa, the polymerization temperature is gradually increased from 210 ° C to 280 ° C (divided into 7 stages, respectively 210 ° C - 220 ° C - 230 ° C - 240 ° C - 250 °C-260°C-270°C-280°C), the kinetic strengthening process time of the polycondensation reaction is 50min;
  • a nylon 6 polymerization method is prepared by a stepwise polymerization method, and the specific preparation method is as follows:
  • the first stage is a ring-opening reaction stage: pre-polymerization of caprolactam, water and catalyst at a temperature of 200 ° C and a pressure of 3 MPa, the ring-opening reaction time is 10 h; wherein the water content is 15 wt% of caprolactam, the catalyst The content is 10% by weight of caprolactam, and the catalyst is H 2 SO 4 ;
  • the obtained product has a number average molecular weight of 2000, an oligomer content of 10%, a cyclic dimer content of 0.1% or less, and a melt viscosity of 10 Pa ⁇ s;
  • the obtained prepolymer has a melt molecular weight of 5,700, an oligomer content of 2%, wherein the cyclic dimer content is 0.1%, and the melt viscosity is 100 Pa ⁇ s;
  • the obtained melt has a molecular weight of 45,600, a relative viscosity of 5.0, an oligomer content of 1.5% or less, wherein the cyclic dimer content is 0.2% or less; and the nylon 6 polymer is obtained after the kinetic strengthening of the polycondensation reaction is completed.
  • a nylon 6 polymerization method is prepared by a stepwise polymerization method, and the specific preparation method is as follows:
  • the first stage is a ring-opening reaction stage: pre-polymerization of caprolactam, water and catalyst at a temperature of 200 ° C and a pressure of 3 MPa, the ring-opening reaction time is 5 h; wherein the water content is 15 wt% of caprolactam, the catalyst The content is 10wt% of caprolactam, the catalyst is HNO 3 and NH 3 , the mass ratio is 2:1; the flame retardant zinc borate is added at the same time, the added amount is 5wt% of caprolactam
  • the obtained product has a number average molecular weight of 1500, an oligomer content of 25%, a cyclic dimer content of 0.1% or less, and a melt viscosity of 8 Pa ⁇ s;
  • the second stage is the pre-polycondensation stage: the product obtained by the ring-opening reaction is subjected to a polycondensation reaction under the conditions of a pressure of 150 Pa and a temperature of 210 ° C, and the pre-polycondensation reaction time is 2 h; at the same time, a chain extender bisacyl dicaprolactam is added, and the chain extender is added. The amount added is 1% by weight of caprolactam;
  • the obtained prepolymer has a melt molecular weight of 4,500, an oligomer content of 2%, wherein the cyclic dimer content is 0.1%, and the melt viscosity is 10 Pa ⁇ s;
  • the obtained melt has a molecular weight of 39,900, a relative viscosity of 4.5, an oligomer content of 1.5% or less, wherein the cyclic dimer content is 0.2% or less; and a nylon 6 polymer is obtained after the kinetic strengthening of the polycondensation reaction is completed.
  • a nylon 6 polymerization method is prepared by a stepwise polymerization method, and the specific preparation method is as follows:
  • the obtained product has a number average molecular weight of 2000, an oligomer content of 30%, a cyclic dimer content of 0.1% or less, and a melt viscosity of 5 Pa ⁇ s;
  • the second stage is the pre-polycondensation stage: the product obtained by the ring-opening reaction is subjected to a polycondensation reaction under the conditions of a pressure of 150 Pa and a temperature of 180 ° C, and the pre-polycondensation reaction time is 3 hours; and the molecular weight stabilizer diamine H 2 N (CH) is simultaneously added.
  • aromatic dibasic acid phthalic acid the mass ratio of diamine to phthalic acid is 1:2
  • the stabilizer is added in an amount of 8 wt% of caprolactam; Adding an anion generating material, kiwi, in an amount of 8 wt% of caprolactam;
  • the obtained prepolymer has a melt molecular weight of 4000, an oligomer content of 2%, wherein the cyclic dimer content is 0.1%, and the melt viscosity is 800 Pa ⁇ s;
  • the third stage is the kinetic strengthening stage of polycondensation reaction: using liquid phase thickening kettle, the polymerization is carried out under the pressure of 80Pa, and the polymerization temperature is gradually increased from 180 °C to 280 °C (divided into 10 stages, respectively 180 ° C -190 ° C - 200 ° C - 210 ° C - 220 ° C - 230 ° C - 240 ° C - 250 ° C - 260 ° C - 270 ° C - 280 ° C), polycondensation reaction kinetic strengthening process time is 80 min; at the same time adding chain extender phosphate, chain extender The amount added is 0.5% by weight of caprolactam;
  • the obtained melt had a molecular weight of 15,960, a relative viscosity of 2.5, an oligomer content of 1.5% or less, and a cyclic dimer content of 0.2% or less; and a nylon 6 polymer was obtained after the kinetic strengthening of the polycondensation reaction.
  • a nylon 6 polymerization method is prepared by a stepwise polymerization method, and the specific preparation method is as follows:
  • the obtained product has a number average molecular weight of 1800, an oligomer content of 20%, a cyclic dimer content of 0.1% or less, and a melt viscosity of 90 Pa ⁇ s;
  • the second stage is the pre-polycondensation stage: the product obtained by the ring-opening reaction is subjected to a polycondensation reaction under the conditions of a pressure of 150 Pa and a temperature of 210 ° C, and the pre-polycondensation reaction time is 1 h; and the molecular weight stabilizer H(CH 2 ) b NH 2 is simultaneously added.
  • b 16 the amount added is 0.01 wt% of caprolactam;
  • the obtained prepolymer has a melt molecular weight of 5,000, an oligomer content of 5%, a cyclic dimer content of 0.1%, and a melt viscosity of 950 Pa ⁇ s;
  • the third stage is the kinetic strengthening stage of polycondensation reaction: polymerization under the condition of pressure 80 Pa, the polymerization temperature is gradually increased from 210 ° C to 280 ° C (divided into 7 stages, respectively 210 ° C - 220 ° C - 230 ° C - 240 ° C - 250 °C-260°C-270°C-280°C), the kinetic strengthening process of polycondensation reaction is 50min; at the same time, the fluorescent material with aluminate as the luminescent substrate and rare earth lanthanide lanthanum as activator is added, and the amount of caprolactam is added. 10wt%; simultaneously adding a chain extender diisocyanate, the chain extender is added in an amount of 0.5% by weight of caprolactam;
  • the obtained melt had a molecular weight of 3,1920, a relative viscosity of 3.8, an oligomer content of 1.5% or less, and a cyclic dimer content of 0.2% or less; and a nylon 6 polymer was obtained after the kinetic strengthening of the polycondensation reaction was completed.
  • the nylon 6 polymer of Example 1 was directly spun according to the nylon 6 spinning process after the end of the polycondensation reaction kinetic strengthening process, the spinning temperature was 240 ° C, the first godet speed was 4500 m / min, and the second The speed of the godet is 5000 m/min, the draw ratio is 1.5 times, the cooling air temperature is 15 ° C, the wind speed is 0.5 m/s, and the relative humidity is 90%, and the fully drawn yarn is obtained.
  • the spinning microporous cross-sectional shape of the above spinning is a triangle
  • the above-mentioned nylon 6 polymer is added with functional masterbatch or masterbatch in the melt transfer process, and uniformly mixed, and then directly spun according to the nylon 6 spinning process, the amount of addition is 1 wt% of nylon 6 polymer.
  • the matrix of the functional masterbatch or masterbatch is nylon 6.
  • the functional adjuvant contained in the functional masterbatch is an antioxidant 1010 in an amount of 30% by weight of the functional masterbatch.
  • the colorant used in the masterbatch is phthalocyanine red.
  • the polymer chips are added on-line during the melt transfer process, and immediately mixed and directly spun according to the nylon 6 spinning process, and the polymer chip addition amount is 5 wt% of the nylon 6 melt.
  • the polymer slice is polyethylene terephthalate.
  • the nylon 6 polymer of Example 2 was directly spun according to the nylon 6 spinning process after the end of the kinetic strengthening process of the polycondensation reaction, the spinning temperature was 280 ° C, the first godet speed was 4000 m / min, and the second The godet speed was 6000 m/min, the draw ratio was 1.1 times, the cooling air temperature was 25 ° C, the wind speed was 1 m/s, and the relative humidity was 60%, and the fully drawn yarn was obtained.
  • the spinning microporous cross-sectional shape of the above spinning is a cross shape
  • the above-mentioned nylon 6 polymer is added with functional masterbatch or masterbatch in the melt transfer process, and uniformly mixed, and then directly spun according to the nylon 6 spinning process, the amount of addition is 30% by weight of the nylon 6 polymer.
  • the matrix of the functional masterbatch or masterbatch is nylon 6T.
  • the functional adjuvant contained in the functional masterbatch is an antioxidant 168 in an amount of 10% by weight of the functional masterbatch.
  • the colorant used in the masterbatch is phthalocyanine blue.
  • the polymer chips are added on-line during the melt transfer process, and immediately mixed and directly spun according to the nylon 6 spinning process, and the polymer chip addition amount is 50% by weight of the nylon 6 melt.
  • the polymer slice was nylon 6.
  • the nylon 6 polymer of Example 3 was directly spun according to the nylon 6 spinning process after the end of the kinetic strengthening process of the polycondensation reaction, the spinning temperature was 260 ° C, and the first godet speed was 4300 m/min, the second The speed of the godet was 5500 m/min, the draw ratio was 1.3 times, the cooling air temperature was 20 ° C, the wind speed was 0.8 m/s, and the relative humidity was 70%, and the fully drawn yarn was obtained.
  • the above-mentioned nylon 6 polymer is added with functional masterbatch or masterbatch in the melt transfer process, and uniformly mixed, and then directly spun according to the nylon 6 spinning process, the amount of addition is 5 wt% of nylon 6 polymer.
  • the matrix of the functional masterbatch or masterbatch is nylon 612 and polyethylene terephthalate.
  • the functional adjuvant contained in the functional masterbatch is an antioxidant 616 in an amount of 15% by weight of the functional masterbatch.
  • the colorant used in the masterbatch is phthalocyanine green.
  • the polymer chips are added on-line during the melt transfer process, and immediately mixed and directly spun according to the nylon 6 spinning process, and the polymer chip addition amount is 10% by weight of the nylon 6 melt.
  • the polymer chip was polyethylene glycol (polyethylene glycol having a molecular weight of 400 and polyethylene glycol end groups being a hydroxyl group).
  • the nylon 6 polymer of Example 4 was directly spun according to the nylon 6 spinning process after the end of the polycondensation reaction kinetic strengthening process, the spinning temperature was 270 ° C, the first godet speed was 4250 m / min, and the second The speed of the godet was 5000 m/min, the draw ratio was 1.4 times, the cooling air temperature was 23 ° C, the wind speed was 0.8 m/s, and the relative humidity was 80%, and the fully drawn yarn was obtained.
  • the spinning microporous cross-sectional shape of the above spinning is hollow fiber
  • the above-mentioned nylon 6 polymer is added with functional masterbatch or masterbatch in the melt transfer process, and uniformly mixed, and then directly spun according to the nylon 6 spinning process, the amount of addition is 10% by weight of the nylon 6 polymer.
  • the matrix of the functional masterbatch or masterbatch is nylon 610 and polybutylene terephthalate.
  • the functional adjuvant contained in the functional masterbatch is an anti-UV agent salicylic acid in an amount of 20% by weight of the functional masterbatch. Used in the masterbatch The colorant is light fast red.
  • the polymer chips are added on-line during the melt transfer process, and immediately mixed and directly spun according to the nylon 6 spinning process, and the polymer chip addition amount is 15% by weight of the nylon 6 melt.
  • the polymer chips were polybutylene terephthalate and nylon 6T.
  • the nylon 6 polymer of Example 5 was directly spun according to the nylon 6 spinning process after the kinetic strengthening process of the polycondensation reaction, the spinning temperature was 240 ° C, the spinning speed was 1500 m / min, and the cooling air temperature was 30. °C, wind speed of 0.3 m / s, relative humidity of 60%, to obtain unoriented yarn.
  • the spinning microporous cross-sectional shape of the above spinning is U-shaped
  • the above-mentioned nylon 6 polymer is added with functional masterbatch or masterbatch in the melt transfer process, and uniformly mixed, and then directly spun according to the nylon 6 spinning process, the amount of addition is 12% by weight of nylon 6 polymer.
  • the matrix of the functional masterbatch or masterbatch is polytrimethylene terephthalate.
  • the functional adjuvant contained in the functional masterbatch is an anti-UV agent benzophenone-based benzotriazole system in an amount of 25 wt% of the functional masterbatch.
  • the colorant used in the masterbatch is macromolecular red.
  • the polymer chips are added on-line during the melt transfer process, and immediately mixed and directly spun according to the nylon 6 spinning process, and the polymer chip addition amount is 20% by weight of the nylon 6 melt.
  • the polymer chips were nylon 612 and polyethylene glycol (polyethylene glycol having a molecular weight of 10,000 and a modified terminal group being a carboxyl group).
  • the nylon 6 polymer of Example 6 was directly spun according to the nylon 6 spinning process after the end of the polycondensation reaction kinetic strengthening process, the spinning temperature was 280 ° C, the spinning speed was 700 m / min, and the cooling air temperature was 20 °C, wind speed 1m / s, relative humidity of 80%, to obtain unoriented yarn.
  • the spinning microporous cross-sectional shape of the above spinning is T-shaped;
  • the above-mentioned nylon 6 polymer is added with functional masterbatch or masterbatch in the melt transfer process, and uniformly mixed, and then directly spun according to the nylon 6 spinning process, the amount of addition is 1 wt% of nylon 6 polymer.
  • the matrix of the functional masterbatch or masterbatch is nylon 410 and a water soluble polyester.
  • the functional additive contained in the functional masterbatch is an anti-UV agent talc powder in an amount of 30% by weight of the functional masterbatch.
  • the colorant used in the masterbatch is macromolecular yellow.
  • the above nylon 6 polymer is added online after the end of the polycondensation reaction kinetic strengthening process during the melt transport process.
  • the pellets were directly spun in a nylon 6 spinning process immediately after mixing, and the polymer chips were added in an amount of 25 wt% of the nylon 6 melt.
  • the polymer slice is polytrimethylene terephthalate.
  • the nylon 6 polymer of Example 7 was directly spun according to the nylon 6 spinning process after the kinetic strengthening process of the polycondensation reaction, the spinning temperature was 260 ° C, the spinning speed was 900 m/min, and the cooling air temperature was 25 °C, wind speed 0.5m / s, relative humidity of 70%, to obtain unoriented yarn.
  • the spinning microporous cross-sectional shape of the above spinning is Y-shaped;
  • the above-mentioned nylon 6 polymer is added with functional masterbatch or masterbatch in the melt transfer process, and uniformly mixed, and then directly spun according to the nylon 6 spinning process, the amount of addition is 30% by weight of the nylon 6 polymer.
  • the matrix of the functional masterbatch or masterbatch is polyethylene glycol (molecular weight 400, polyethylene glycol end groups are hydroxyl groups).
  • the functional additive contained in the functional masterbatch is an anti-ultraviolet agent calcium carbonate in an amount of 10% by weight of the functional masterbatch.
  • the colorant used in the masterbatch is permanent yellow.
  • the polymer chips are added on-line during the melt transfer process, and immediately mixed and directly spun according to the nylon 6 spinning process, and the polymer chip addition amount is 30% by weight of the nylon 6 melt.
  • the polymer section was nylon 612.
  • the nylon 6 polymer of Example 8 was directly spun according to the nylon 6 spinning process after the end of the polycondensation reaction kinetic strengthening process, the spinning temperature was 270 ° C, the spinning speed was 1000 m/min, and the cooling air temperature was 28 °C, wind speed 0.6m / s, relative humidity of 65%, to obtain unoriented yarn.
  • the spinning microporous cross-sectional shape of the above spinning is a polygon
  • the above-mentioned nylon 6 polymer is added with functional masterbatch or masterbatch in the melt transfer process, and uniformly mixed, and then directly spun according to the nylon 6 spinning process, the amount of addition is 15% by weight of nylon 6 polymer.
  • the matrix of the functional masterbatch or masterbatch is nylon 212 and polyethylene glycol (molecular weight 20,000, polyethylene glycol end groups are hydroxyl groups).
  • the functional auxiliary contained in the functional masterbatch is an antibacterial agent nano titanium dioxide in an amount of 10% by weight of the functional masterbatch.
  • the colorant used in the masterbatch is Pigment Red 179.
  • the polymer chips are added on-line during the melt transfer process, and immediately mixed and directly spun according to the nylon 6 spinning process, and the polymer chip addition amount is 35 wt% of the nylon 6 melt.
  • the polymer chip was polyethylene glycol (polyethylene glycol having a molecular weight of 400 modified amino group).
  • the nylon 6 polymer of Example 9 was directly spun according to the nylon 6 spinning process after the kinetic strengthening process of the polycondensation reaction, the spinning temperature was 280 ° C, the spinning speed was 4000 m/min, and the cooling air temperature was 15 °C, wind speed of 0.3 m / s, relative humidity of 80%, to obtain pre-oriented yarn.
  • the spinning microporous cross-sectional shape of the above spinning is in an I-shape
  • the above-mentioned nylon 6 polymer is added with functional masterbatch or masterbatch in the melt transfer process, and uniformly mixed, and then directly spun according to the nylon 6 spinning process, the amount of addition is 20% by weight of nylon 6 polymer.
  • the matrix of the functional masterbatch or masterbatch is nylon 11.
  • the functional auxiliary contained in the functional masterbatch is zinc oxide, an antibacterial agent, in an amount of 30% by weight of the functional masterbatch.
  • the colorant used in the masterbatch is Pigment Blue 60.
  • the polymer chips are added on-line during the melt transfer process, and immediately mixed and directly spun according to the nylon 6 spinning process, and the polymer chip addition amount is 40% by weight of the nylon 6 melt.
  • the polymer chip is a water soluble polyester.
  • the nylon 6 polymer of Example 10 was directly spun according to the nylon 6 spinning process after the kinetic strengthening process of the polycondensation reaction, the spinning temperature was 240 ° C, the spinning speed was 4500 m / min, and the cooling air temperature was 25 °C, wind speed 0.6m / s, relative humidity of 60%, to obtain pre-oriented yarn.
  • the spinning microporous cross-sectional shape of the above spinning is a triangle
  • the above-mentioned nylon 6 polymer is added with functional masterbatch or masterbatch in the melt transfer process, and uniformly mixed, and then directly spun according to the nylon 6 spinning process, the amount of addition is 30% by weight of the nylon 6 polymer.
  • the matrix of the functional masterbatch or masterbatch is a branched nylon.
  • the functional adjuvant contained in the functional masterbatch is an antibacterial agent iron oxide in an amount of 15% by weight of the functional masterbatch.
  • the colorant used in the masterbatch is Solvent Violet 59.
  • the polymer chips are added on-line during the melt transfer process, and immediately mixed and directly spun according to the nylon 6 spinning process, and the polymer chip addition amount is 45 wt% of the nylon 6 melt.
  • the polymer section was nylon 1212.
  • the nylon 6 polymer of Example 11 was directly spun according to the nylon 6 spinning process after the end of the polycondensation reaction kinetic strengthening process, the spinning temperature was 260 ° C, the spinning speed was 4300 m / min, and the cooling air temperature was 20 °C, wind speed of 0.4 m / s, relative humidity of 70%, to obtain pre-oriented yarn.
  • the spinning microporous cross-sectional shape of the above spinning is a cross shape
  • the above-mentioned nylon 6 polymer is added with functional masterbatch or masterbatch in the melt transfer process, and uniformly mixed, and then directly spun according to the nylon 6 spinning process, the amount of addition is 1 wt% of nylon 6 polymer.
  • the matrix of the functional masterbatch or masterbatch is polyethylene terephthalate.
  • the colorant used in the masterbatch is Solvent Red 181.
  • the polymer chips are added on-line during the melt transfer process, and immediately mixed and directly spun according to the nylon 6 spinning process, and the polymer chip addition amount is 50% by weight of the nylon 6 melt.
  • the polymer chips are polytrimethylene terephthalate and a water soluble polyester.
  • the nylon 6 polymer of Example 1 was directly spun according to the nylon 6 spinning process after the end of the polycondensation reaction kinetic strengthening process, the spinning temperature was 270 ° C, the spinning speed was 4400 m / min, and the cooling air temperature was 23 °C, wind speed 0.5m / s, relative humidity of 75%, to obtain pre-oriented yarn.
  • the spinning microporous cross-sectional shape of the above spinning is polygonal;
  • the above-mentioned nylon 6 polymer is added with functional masterbatch or masterbatch in the melt transfer process, and uniformly mixed, and then directly spun according to the nylon 6 spinning process, the amount of addition is 15% by weight of nylon 6 polymer.
  • the matrix of the functional masterbatch or masterbatch is nylon 1212.
  • the colorant used in the masterbatch is Solvent Blue 132.
  • the polymer chips are added on-line during the melt transfer process, and immediately mixed and directly spun according to the nylon 6 spinning process, and the polymer chip addition amount is 5 wt% of the nylon 6 melt.
  • the polymer slice is polyethylene terephthalate.
  • the nylon 6 polymer of Example 2 was directly spun according to the nylon 6 spinning process after the kinetic strengthening process of the polycondensation reaction, the spinning temperature was 280 ° C, the spinning speed was 4500 m/min, and the cooling air temperature was 15 °C, wind speed 0.5m / s, relative humidity of 90%, to obtain highly oriented filaments.
  • the spinning microporous cross-sectional shape of the above spinning is hollow fiber
  • the above-mentioned nylon 6 polymer is added with functional masterbatch or masterbatch in the melt transfer process, and uniformly mixed, and then directly spun according to the nylon 6 spinning process, the amount of addition is 30% by weight of the nylon 6 polymer.
  • the matrix of the functional masterbatch or masterbatch is polybutylene terephthalate.
  • the functional auxiliary contained in the functional masterbatch is a flame retardant zinc borate at a content of 10% by weight of the functional masterbatch.
  • the colorant used in the masterbatch is Solvent Green 29.
  • the polymer chips are added on-line during the melt transfer process, and immediately mixed and directly spun according to the nylon 6 spinning process, and the polymer chip addition amount is 10% by weight of the nylon 6 melt.
  • the polymer chip is a water soluble polyester.
  • the nylon 6 polymer of Example 3 was directly spun according to the nylon 6 spinning process after the kinetic strengthening process of the polycondensation reaction, the spinning temperature was 240 ° C, the spinning speed was 6000 m / min, and the cooling air temperature was 20 °C, wind speed of 0.3 m / s, relative humidity of 80%, to obtain highly oriented filaments.
  • the spinning microporous cross-sectional shape of the above spinning is U-shaped
  • the above-mentioned nylon 6 polymer is added with functional masterbatch or masterbatch in the melt transfer process, and uniformly mixed, and then directly spun according to the nylon 6 spinning process, the amount of addition is 1 wt% of nylon 6 polymer.
  • the matrix of the functional masterbatch or masterbatch is nylon 12.
  • the functional additive contained in the functional masterbatch is a flame retardant ammonium polyphosphate at a content of 30% by weight of the functional masterbatch.
  • the colorant used in the masterbatch is Solvent Yellow 135.
  • the polymer chips are added on-line during the melt transfer process, and immediately mixed and directly spun according to the nylon 6 spinning process, and the polymer chip addition amount is 15% by weight of the nylon 6 melt.
  • the polymer chips are nylon 46 and nylon 410.
  • the nylon 6 polymer of Example 4 was directly spun according to the nylon 6 spinning process after the end of the polycondensation reaction kinetic strengthening process, the spinning temperature was 250 ° C, the spinning speed was 4700 m / min, and the cooling air temperature was 18 °C, wind speed of 0.4 m / s, relative humidity of 85%, to obtain highly oriented filaments.
  • the spinning microporous cross-sectional shape of the above spinning is T-shaped;
  • the above-mentioned nylon 6 polymer is added with functional masterbatch or masterbatch in the melt transfer process, and uniformly mixed, and then directly spun according to the nylon 6 spinning process, the amount of addition is 20% by weight of nylon 6 polymer.
  • the matrix of the functional masterbatch or masterbatch is nylon 26.
  • the functional auxiliary contained in the functional masterbatch is a mixture of 1,3,6-tris(4,6-diamino-2-thiotriazine)hexane and cyanuric acid, and the content is functional. 15% by weight of the masterbatch. Place The colorants used in the color masterbatch are Solvent Yellow 135 and Pigment Red 179.
  • the polymer chips are added on-line during the melt transfer process, and immediately mixed and directly spun according to the nylon 6 spinning process, and the polymer chip addition amount is 20% by weight of the nylon 6 melt.
  • the polymer section was nylon nylon 46.
  • the nylon 6 polymer of Example 5 was directly spun according to the nylon 6 spinning process after the kinetic strengthening process of the polycondensation reaction, the spinning temperature was 260 ° C, the spinning speed was 4800 m / min, and the cooling air temperature was 16 °C, wind speed of 0.4 m / s, relative humidity of 88%, to obtain highly oriented filaments.
  • the spinning microporous cross-sectional shape of the above spinning is Y-shaped;
  • the polymer section is polyethylene glycol (molecular weight 20,000, polyethylene glycol end group is hydroxyl group).
  • the nylon 6 polymer of Example 6 was directly spun in accordance with the nylon 6 spinning process to obtain a puffed textured yarn after the completion of the kinetic strengthening process of the polycondensation reaction.
  • the spinning temperature was 280 ° C
  • the cooling air temperature was 20 ° C
  • the wind speed was 0.3. m/s, relative humidity is 80%
  • feed roller temperature is 60 ° C
  • stretching roll temperature is 190 ° C
  • feed speed is 300 m / min
  • tensile speed is 1000 m / min
  • draw ratio is 3.5 times
  • deformation The hot air temperature was 230 ° C
  • the air injection pressure was 490 kPa
  • the winding speed was 600 m/min
  • the cooling air temperature was 25 ° C.
  • the spinning microporous cross-sectional shape of the above spinning is a polygon
  • the above-mentioned nylon 6 polymer is added with functional masterbatch or masterbatch in the melt transfer process, and uniformly mixed, and then directly spun according to the nylon 6 spinning process, the amount of addition is 30% by weight of the nylon 6 polymer.
  • the matrix of the functional masterbatch or masterbatch is polytrimethylene terephthalate and a water soluble polyester.
  • the functional additive contained in the functional masterbatch is a negative ion generating material tourmaline in an amount of 30% by weight of the functional masterbatch.
  • the colorant used in the masterbatch is Solvent Violet 37.
  • the polymer chips are added on-line during the melt transfer process, and immediately mixed and directly spun according to the nylon 6 spinning process, and the polymer chip addition amount is 30% by weight of the nylon 6 melt.
  • the polymer slice is polybutylene terephthalate.
  • the nylon 6 polymer of Example 7 was directly spun in accordance with the nylon 6 spinning process to obtain a puffed textured yarn after the completion of the kinetic strengthening process of the polycondensation reaction.
  • the spinning temperature was 240 ° C
  • the cooling air temperature was 30 ° C
  • the wind speed was 1 m. / s, relative humidity is 60%
  • feeding roller temperature is 120 ° C
  • stretching roller temperature is 100 ° C
  • feeding speed is 1000 m / min
  • stretching speed is 3500 m / min
  • stretching ratio is 5 times
  • heat of deformation The air temperature was 190 ° C
  • the air injection pressure was 196 kPa
  • the winding speed was 3000 m/min
  • the cooling air temperature was 25 ° C.
  • the spinning microporous cross-sectional shape of the above spinning is in an I-shape
  • the above-mentioned nylon 6 polymer is added with functional masterbatch or masterbatch in the melt transfer process, and uniformly mixed, and then directly spun according to the nylon 6 spinning process, the amount of addition is 1 wt% of nylon 6 polymer.
  • the matrix of the functional masterbatch or masterbatch is nylon 46.
  • the functional auxiliary contained in the functional masterbatch is a fluorescent material (using an alkaline earth metal sulfide, an aluminate as a light-emitting substrate, and a rare earth lanthanide lanthanum, cerium, lanthanum or cerium as an activator). It is 10% by weight of the functional masterbatch.
  • the colorant used in the masterbatch is Solvent Red 143.
  • the nylon 6 polymer of Example 8 was directly spun in accordance with the nylon 6 spinning process to obtain a puffed textured yarn after the completion of the kinetic strengthening process of the polycondensation reaction.
  • the spinning temperature was 260 ° C
  • the cooling air temperature was 25 ° C
  • the wind speed was 0.5. m/s, relative humidity is 70%
  • feed roller temperature is 80 ° C
  • stretching roll temperature is 120 ° C
  • feed speed is 500 m / min
  • tensile speed is 2000 m / min
  • draw ratio is 4 times
  • deformation The hot air temperature was 200 ° C
  • the air injection pressure was 300 kPa
  • the winding speed was 1000 m/min
  • the cooling air temperature was 25 °C.
  • the spinning microporous cross-sectional shape of the above spinning is a triangle
  • the above-mentioned nylon 6 polymer is added with functional masterbatch or masterbatch in the melt transfer process, and uniformly mixed, and then directly spun according to the nylon 6 spinning process, the amount of addition is 10% by weight of the nylon 6 polymer.
  • the matrix of the functional masterbatch or masterbatch is nylon 6T.
  • the functional auxiliary contained in the functional masterbatch is an anion generating material opal in an amount of 25 wt% of the functional masterbatch.
  • the colorant used in the masterbatch is Solvent Blue 94.
  • the polymer chips are added on-line during the melt transfer process, and immediately mixed and directly spun according to the nylon 6 spinning process, and the polymer chip addition amount is 40% by weight of the nylon 6 melt.
  • the polymer slice is polytrimethylene terephthalate.
  • the nylon 6 polymer of Example 9 was directly spun in accordance with the nylon 6 spinning process to obtain a puffed textured yarn after the completion of the kinetic strengthening process of the polycondensation reaction.
  • the spinning temperature was 270 ° C
  • the cooling air temperature was 28 ° C
  • the wind speed was 0.8. m/s, relative humidity is 75%
  • feed roller temperature is 100 ° C
  • draw roll temperature is 150 ° C
  • feed speed is 800 m / min
  • draw speed is 3000 m / min
  • draw ratio is 4.5 times
  • deformation The hot air temperature was 210 ° C
  • the air injection pressure was 350 kPa
  • the winding speed was 2000 m/min
  • the cooling air temperature was 25 ° C.
  • the spinning microporous cross-sectional shape of the above spinning is a cross shape
  • the above-mentioned nylon 6 polymer is added with functional masterbatch or masterbatch in the melt transfer process, and uniformly mixed, and then directly spun according to the nylon 6 spinning process, the amount of addition is 20% by weight of nylon 6 polymer.
  • the matrix of the functional masterbatch or masterbatch is nylon 212.
  • the functional additive contained in the functional masterbatch is an anion generating material genius stone in an amount of 20% by weight of the functional masterbatch.
  • the colorant used in the masterbatch is carbon black.
  • the polymer chips are added on-line during the melt transfer process, and immediately mixed and directly spun according to the nylon 6 spinning process, and the polymer chip addition amount is 45 wt% of the nylon 6 melt.
  • the polymer slice is polybutylene terephthalate.
  • nylon 6 polymer of Example 10 is directly applied to the composite spinning after the end of the polycondensation reaction kinetic strengthening process, the composite spinning is a side-by-side type, and the other component of the composite spinning except nylon 6 is Nylon 6T, the mass ratio of the nylon 6 polymer to the other component was 3:7.
  • the spinning microporous cross-sectional shape of the above spinning is polygonal;
  • the above-mentioned nylon 6 polymer is added with functional masterbatch or masterbatch in the melt transfer process, and uniformly mixed, and then directly spun according to the nylon 6 spinning process, the amount of addition is 1 wt% of nylon 6 polymer.
  • the matrix of the functional masterbatch or masterbatch is polytrimethylene terephthalate.
  • the functional auxiliary contained in the functional masterbatch is a flame retardant bis(hexachlorocyclopentadienyl)cyclooctane in an amount of 20% by weight of the functional masterbatch.
  • the colorant used in the masterbatch is Pigment Yellow 184.
  • nylon 6 polymer of Example 11 is directly applied to the composite spinning after the end of the polycondensation reaction kinetic strengthening process, and the composite spinning is an island-in-the-sea type; the other component of the composite spinning except nylon 6 is Nylon 610, the mass ratio of the nylon 6 polymer to the other component is 7:3.
  • the spinning microporous cross-sectional shape of the above spinning is hollow fiber
  • the above-mentioned nylon 6 polymer is added with functional masterbatch or masterbatch in the melt transfer process, and uniformly mixed, and then directly spun according to the nylon 6 spinning process, the amount of addition is 30% by weight of the nylon 6 polymer.
  • the matrix of the functional masterbatch or masterbatch is nylon 610.
  • the functional additive contained in the functional masterbatch is the flame retardant decabromodiphenyl ether in an amount of 20% by weight of the functional masterbatch.
  • the colorant used in the masterbatch is iron oxide red.
  • the polymer chips are added on-line during the melt transfer process, and immediately mixed and directly spun according to the nylon 6 spinning process, and the polymer chip addition amount is 50% by weight of the nylon 6 melt.
  • the polymer chip is a water soluble polyester.
  • Example 34 Nylon 6 polymer spun into fiber woven fabric
  • the pretreatment desizing temperature is 80 ° C
  • the desizing time is 6 h
  • the desizing assistant formula is: soda ash 10 g / L, deoiling spirit 15 g / L.
  • the temperature rising dyeing process is a starting dyeing temperature of 40 ° C, heating at a rate of 1 ° C / min, heating to 90 ° C and then holding for 40 min; the dye concentration is 2% (omf), the bath ratio is 1:10.
  • the fixing process was performed at a temperature of 90 ° C and a fixing time of 60 min; a fixing agent concentration of 2% (omf) and a bath ratio of 1:10.
  • an auxiliary agent is added, and the auxiliary agent is added in an amount of 5 g/L, and the auxiliary agent includes a softener NORM02, a leveling agent ACID03, and a retarding agent ammonium sulfate.
  • Example 35 Nylon 6 polymer spun into fiber woven fabric
  • the nylon 6 fiber obtained by spinning the nylon polymer described in Example 2 was then knitted to form a fabric which was twill and then dyed to obtain a cloth of different specifications.
  • the dyeing production process of the fabric is: pre-treatment desizing - hot water cleaning fabric - heating dyeing - fixing color - cooling cleaning - fabric machine waterproof stereotype - finished product inspection - finished product rolling.
  • the pretreatment desizing temperature is 60 ° C
  • the desizing time is 12 h
  • the desizing assistant formula is: soda ash 20 g / L, deoiling spirit 10 g / L.
  • the temperature rising dyeing process is that the initial dyeing temperature is 30 ° C, the temperature is raised at a rate of 3 ° C / min, the temperature is raised to 95 ° C and then kept for 40 min; the dye concentration is 0.5% (omf), and the bath ratio is 1:20.
  • the fixing process was a temperature of 95 ° C, a fixing time of 20 min, a fixing agent concentration of 0.5% (omf), and a bath ratio of 1:20.
  • an auxiliary agent is added, and the auxiliary agent is added in an amount of 10 g/L, and the auxiliary agent includes a water softener NORM02, a leveling agent ACID16, and a retarding agent ammonium sulfate.
  • Example 36 Nylon 6 polymer spun into fiber woven fabric
  • the nylon 6 fiber obtained by spinning the nylon polymer described in Example 3 was then woven into a fabric which was satin-printed and then dyed to obtain a cloth of different specifications.
  • the dyeing production process of the fabric is: pre-treatment desizing - hot water cleaning fabric - heating dyeing - fixing color - cooling cleaning - fabric machine waterproof stereotype - finished product inspection - finished product rolling.
  • the pretreatment desizing temperature is 70 ° C
  • the desizing time is 8 h
  • the desizing assistant formula is: soda ash 15 g / L, deoiling spirit 12 g / L.
  • the temperature rising dyeing process is that the initial dyeing temperature is 35 ° C, the temperature is raised at a rate of 2 ° C / min, the temperature is raised to 92 ° C and then kept for 40 min; the concentration of the dye is 0.8% (omf), and the bath ratio is 1:15.
  • the fixing process was a temperature of 92 ° C, a fixing time of 30 min, a fixing agent concentration of 0.8% (omf), and a bath ratio of 1:15.
  • an auxiliary agent is added, and the auxiliary agent is added in an amount of 7 g/L, and the auxiliary agent includes a softener NORM02, a leveling agent ACID03, and a retarding agent ammonium sulfate.
  • Example 37 Fabric woven from nylon 6 polymer into fibers
  • the nylon 6 fiber obtained by spinning the nylon polymer described in Example 4 was then knitted to form a fabric which was plain and then dyed to obtain a cloth of different specifications.
  • the dyeing production process of the fabric is: pre-treatment desizing - hot water cleaning fabric - heating dyeing - fixing color - cooling cleaning - fabric machine waterproof stereotype - finished product inspection - finished product rolling.
  • the pretreatment desizing temperature is 750 ° C
  • the desizing time is 10 h
  • the desizing aid formula is: soda ash 18 g / L, degreasing Spirit 13g / L.
  • the temperature rising dyeing process has a dyeing temperature of 38 ° C, a temperature increase of 2 ° C / min, a temperature increase to 93 ° C and then 40 min; a dye concentration of 1.5% (omf), a bath ratio of 1:18.
  • the fixing process was a temperature of 93 ° C, a fixing time of 40 min, a fixing agent concentration of 1.5% (omf), and a bath ratio of 1:18.
  • an auxiliary agent is added, and the auxiliary agent is added in an amount of 5-10 g/L, and the auxiliary agent includes a softener NORM02, a leveling agent ACID16, and a retarding agent ammonium sulfate.
  • the silo 1 functions to store caprolactam, which is connected to a raw material heating tank 3 through a pipe, and the raw material heating tank 3 functions to melt caprolactam; 4 is connected to the raw material heating tank 3 through a pipe, and the function of the pressurized open-loop kettle 4 is to promote the hydrolysis and opening of the caprolactam by means of pressure to obtain a prepolymer having a low cyclic oligomer content;
  • the polycondensation kettle 5 passes through the pipeline Connected to the pressurized open-loop kettle 4, the function of the polycondensation tank 5 is to pre-condense the product of the pressurized open-loop kettle 4 to a molecular weight near the molecular chain entanglement point, and to remove a large amount of unreacted monomers.
  • the melt viscosity is low, so the conditions for the polycondensation are not high; the liquid phase thickening kettle 6 is connected to the polycondensation vessel 5 through a pipe, and the liquid phase thickening kettle 6 functions to pass the product of the polycondensation kettle 5 through high vacuum polycondensation reaction power.
  • the melt viscosity is higher, so the conditions for polycondensation are high; in the polycondensation kettle 5, the liquid phase thickening kettle 6 and the buffer tank 7 connected by pipes, buffer tank 7
  • the function is to collect the small molecules extracted from the polycondensation kettle 5 and the liquid phase thickening kettle 6, and transport them to the concentration tank 8; the concentration tank 8 and the buffer tank 7 are connected by a pipeline, and the function of the concentration tank 8 is to buffer
  • the monomer conveyed from the tank 7 is concentrated and re-delivered into the raw material heating tank 3 to continue to participate in the reaction. It is sent to a concentrator 8 for concentration and property reuse; the resulting melt is directly conveyed to a spinning pack for spinning, followed by weaving, dyeing, to obtain a final product.
  • the caprolactam passes through the silo 1 to the raw material heating tank 3, and the caprolactam is melted and then sent to the pressurized open-loop kettle 4. After the end of the ring opening, the prepolymer obtained is sent to the polycondensation kettle 5 for vacuum polycondensation, and the obtained polymer is transported.
  • the liquid phase thickening kettle 6 is subjected to high vacuum polycondensation, and the obtained melt is directly conveyed to a spinning pack for spinning, followed by weaving and dyeing to obtain a final product.
  • the caprolactam extracted in 5, 6 will be sent to a concentrator 8 for concentration and property reuse.
  • the obtained product has a number average molecular weight of 2000, an oligomer content of 30%, a cyclic dimer content of 0.1% or less, and a melt viscosity of 5 Pa ⁇ s;
  • the second stage is the pre-polycondensation stage: the product obtained by the ring-opening reaction is subjected to a polycondensation reaction under the conditions of a pressure of 150 Pa and a temperature of 180 ° C, and the pre-polycondensation reaction time is 3 hours; and the molecular weight stabilizer diamine H 2 N (CH) is simultaneously added.
  • aromatic dibasic acid terephthalic acid the mass ratio of diamine to terephthalic acid is 1:1
  • the obtained prepolymer has a melt molecular weight of 4000, an oligomer content of 2%, wherein the cyclic dimer content is 0.1%, and the melt viscosity is 800 Pa ⁇ s;
  • the third stage is the liquid phase thickening stage: using a liquid phase thickening kettle, the polymerization is carried out under the pressure of 80Pa, and the polymerization temperature is gradually increased from 180 °C to 280 °C (divided into 10 stages, respectively, 180 ° C - 190 ° C - 200 °C-210°C-220°C-230°C-240°C-250°C-260°C-270°C-280°C), the liquid phase viscosity increasing reaction time is 80min; at the same time adding the chain extender phosphate ester, the amount of chain extender added Is 0.5% by weight of caprolactam;
  • the obtained melt had a molecular weight of 15,960, a relative viscosity of 2.5, an oligomer content of 1.5% or less, and a cyclic dimer content of 0.2% or less.
  • a nylon 6 polymer was obtained.
  • the nylon 6 polymer of Example 39 was directly spun according to the nylon 6 spinning process immediately after the end of the liquid phase thickening reaction, the spinning temperature was 250 ° C, the spinning speed was 4500 m / min, and the cooling air temperature was 25 ° C. The wind speed was 0.6 m/s and the relative humidity was 70% to obtain a pre-oriented yarn.
  • the spinning microporous cross-sectional shape of the above spinning is U-shaped
  • the above-mentioned nylon 6 polymer is added with functional masterbatch or masterbatch in the melt transfer process, and uniformly mixed, and then directly spun according to the nylon 6 spinning process, and the amount of addition is nylon. 6 wt% of the polymer.
  • the matrix of the functional masterbatch or masterbatch is a branched nylon.
  • the functional auxiliary contained in the functional masterbatch is carbon nanotubes in an amount of 15% by weight of the functional masterbatch.
  • the colorant used in the masterbatch is Pigment Brown 41.
  • the above-mentioned nylon 6 polymer is added with a polymer chip on the line during the melt transportation, and immediately mixed and then directly spun according to the nylon 6 spinning process, and the polymer chip is added in a nylon amount. 65% by weight of the melt.
  • the polymer section was nylon 1212.
  • a nylon 6 polymerization method is prepared by a stepwise polymerization method, and the specific preparation method is as follows:
  • the obtained product has a number average molecular weight of 2000, an oligomer content of 30%, a cyclic dimer content of 0.1% or less, and a melt viscosity of 5 Pa ⁇ s;
  • the second stage is the pre-polycondensation stage: the product obtained by the ring-opening reaction is subjected to a polycondensation reaction under the conditions of a pressure of 100 Pa and a temperature of 190 ° C, and the pre-polycondensation reaction time is 3 hours; at the same time, the molecular weight stabilizer diamine o-phenylenediamine is added.
  • the obtained prepolymer has a melt molecular weight of 4000, an oligomer content of 2%, wherein the cyclic dimer content is 0.1%, and the melt viscosity is 800 Pa ⁇ s;
  • the third stage is the liquid phase thickening stage: using a liquid phase thickening kettle, the polymerization is carried out under the pressure of 80Pa, and the polymerization temperature is gradually increased from 180 °C to 280 °C (divided into 10 stages, respectively, 180 ° C - 190 ° C - 200 °C-210°C-220°C-230°C-240°C-250°C-260°C-270°C-280°C), the liquid phase viscosity increasing reaction time is 80min; at the same time adding the chain extender phosphate ester, the amount of chain extender added Is 0.5% by weight of caprolactam;
  • the obtained melt had a molecular weight of 15,960, a relative viscosity of 2.5, an oligomer content of 1.5% or less, and a cyclic dimer content of 0.2% or less.
  • a nylon 6 polymer was obtained.
  • the nylon 6 polymer of Example 41 was directly spun according to the nylon 6 spinning process after the end of the liquid phase thickening reaction, the spinning temperature was 270 ° C, the spinning speed was 4500 m / min, and the cooling air temperature was 25 ° C. The wind speed was 0.6 m/s and the relative humidity was 75%, and a pre-oriented yarn was obtained.
  • the spinning microporous cross-sectional shape of the above spinning is U-shaped
  • the above-mentioned nylon 6 polymer is added with functional masterbatch or masterbatch in the melt transfer process, and uniformly mixed, and then directly spun according to the nylon 6 spinning process, and the amount of addition is nylon. 6 wt% of the polymer.
  • the matrix of the functional masterbatch or masterbatch is a branched nylon.
  • the functional auxiliary contained in the functional masterbatch is graphene in an amount of 15% by weight of the functional masterbatch.
  • the colorant used in the masterbatch is Pigment Yellow 184.
  • nylon 6 polymer is added with a polymer chip on the line during the melt transportation, and immediately mixed and then directly spun according to the nylon 6 spinning process, and the polymer chip is added in a nylon amount. 6 melt 45wt%.
  • the polymer section was nylon 1212.
  • a nylon 6 polymerization method is prepared by a stepwise polymerization method, and the specific preparation method is as follows:
  • the second stage is a pre-polycondensation stage: the product obtained by the ring-opening reaction is subjected to a polycondensation reaction under the conditions of a pressure of 160 Pa and a temperature of 200 ° C, and the pre-polycondensation reaction time is 2.5 h;
  • the obtained prepolymer has a melt molecular weight of 5,200, an oligomer content of 7%, wherein the cyclic dimer content is 0.1%, and the melt viscosity is 90 Pa ⁇ s;
  • the third stage is the liquid phase viscosity-increasing stage: polymerization is carried out under the pressure of 80Pa, and the polymerization temperature is gradually increased from 210 °C to 280 °C (divided into 7 stages, respectively 210 ° C - 220 ° C - 230 ° C - 240 ° C - 250 ° C -260 ° C - 270 ° C - 280 ° C), liquid phase viscosity increasing reaction time is 40 min;
  • the spinning microporous cross-sectional shape of the above spinning is T-shaped;
  • the above-mentioned nylon 6 polymer is added with a polymer chip on the line during the melt transportation, and immediately mixed and then directly spun according to the nylon 6 spinning process, and the polymer chip is added in a nylon amount. 65% by weight of the melt.
  • the polymer slice is polytrimethylene terephthalate.
  • the first stage is a ring-opening reaction stage: pre-polymerization of caprolactam, water and catalyst at a temperature of 210 ° C and a pressure of 1 MPa, the ring-opening reaction time is 8 h; wherein the water content is 15 wt% of caprolactam, the catalyst The content is 10% by weight of caprolactam, the catalyst is H 3 PO 4 ; the lactone is added at the same time, the added amount is 40% by weight of caprolactam;
  • the obtained product has a number average molecular weight of 1600, an oligomer content of 15%, a cyclic dimer content of 0.1% or less, and a melt viscosity of 30 Pa ⁇ s;
  • the second stage is the pre-polycondensation stage: the product obtained by the ring-opening reaction is subjected to a polycondensation reaction under the conditions of a pressure of 150 Pa and a temperature of 210 ° C, and the pre-polycondensation reaction time is 1 h; and the molecular weight stabilizer H(CH 2 ) b NH 2 is simultaneously added.
  • the obtained prepolymer has a melt molecular weight of 4500 and an oligomer content of 7%, wherein the cyclic dimer content is 0.1%, and the melt viscosity is 90 Pa ⁇ s;
  • the third stage is the liquid phase viscosity-increasing stage: polymerization is carried out under the pressure of 80Pa, and the polymerization temperature is gradually increased from 210 °C to 280 °C (divided into 7 stages, respectively 210 ° C - 220 ° C - 230 ° C - 240 ° C - 250 ° C -260 ° C - 270 ° C - 280 ° C), liquid phase viscosity increasing reaction time is 50 min;
  • the nylon 6 polymer of Example 45 was directly spun according to the nylon 6 spinning process immediately after the end of the liquid phase thickening reaction, the spinning temperature was 260 ° C, the spinning speed was 900 m / min, and the cooling air temperature was 25 ° C. The wind speed was 0.5 m/s and the relative humidity was 70%, and unoriented yarn was obtained.
  • the above-mentioned nylon 6 polymer is added with functional masterbatch or masterbatch in the melt transfer process, and uniformly mixed, and then directly spun according to the nylon 6 spinning process, and the amount of addition is nylon. 6 wt% of the polymer.
  • the matrix of the functional masterbatch or masterbatch is polyethylene glycol (molecular weight 400, polyethylene glycol end groups are hydroxyl groups).
  • the functional additive contained in the functional masterbatch is an anti-ultraviolet agent calcium carbonate in an amount of 10% by weight of the functional masterbatch.
  • the colorants used in the masterbatch were azo red and cadmium red, and the mass ratio of azo red and cadmium red was 1:1.
  • the above-mentioned nylon 6 polymer is added with a polymer chip on the line during the melt transportation, and immediately mixed and then directly spun according to the nylon 6 spinning process, and the polymer chip is added in a nylon amount. 6 30% by weight of the melt.
  • the polymer section was nylon 612.
  • the first stage is a ring-opening reaction stage: pre-polymerization of caprolactam, water and catalyst at a temperature of 150 ° C and a pressure of 5 MPa, the ring-opening reaction time is 10 h; wherein the water content is 15 wt% of caprolactam, the catalyst The content is 10% by weight of caprolactam, and the catalyst is H 2 SO 4 ;
  • the obtained product has a number average molecular weight of 2000, an oligomer content of 10%, a cyclic dimer content of 0.1% or less, and a melt viscosity of 10 Pa ⁇ s;
  • the obtained prepolymer has a melt molecular weight of 5,700, an oligomer content of 2%, wherein the cyclic dimer content is 0.1%, and the melt viscosity is 100 Pa ⁇ s;
  • the nylon 6 polymer of Example 47 was directly spun according to the nylon 6 spinning process immediately after the end of the liquid phase thickening reaction, the spinning temperature was 270 ° C, the spinning speed was 1000 m / min, and the cooling air temperature was 28 ° C. The wind speed was 0.6 m/s and the relative humidity was 65%, and unoriented yarn was obtained.
  • the above-mentioned nylon 6 polymer is added with a polymer chip on the line during the melt transportation, and immediately mixed and then directly spun according to the nylon 6 spinning process, and the polymer chip is added in a nylon amount. 65% by weight of the melt.
  • the polymer chip was polyethylene glycol (polyethylene glycol having a molecular weight of 400 modified amino group).
  • a nylon 6 polymerization method is prepared by a stepwise polymerization method, and the specific preparation method is as follows:
  • the obtained product has a number average molecular weight of 2000, an oligomer content of 30%, a cyclic dimer content of 0.1% or less, and a melt viscosity of 5 Pa ⁇ s;
  • the second stage is a pre-polycondensation stage: the product obtained by the ring-opening reaction is subjected to a polycondensation reaction under the conditions of a pressure of 150 Pa and a temperature of 180 ° C, and the pre-polycondensation reaction time is 3 hours; at the same time, the molecular weight stabilizer diamine m-phenylenediamine and the molecular weight stabilizer are added.
  • the aromatic dibasic acid naphthalene dicarboxylic acid (the mass ratio of the diamine to the naphthalene dicarboxylic acid is 1:2), the stabilizer is added in an amount of 8 wt% of the caprolactam; and the anion generating material icochite is added, and the amount of the caprolactam is 8 wt. %;
  • the obtained prepolymer has a melt molecular weight of 4000, an oligomer content of 2%, wherein the cyclic dimer content is 0.1%, and the melt viscosity is 800 Pa ⁇ s;
  • the third stage is the liquid phase thickening stage: using a liquid phase thickening kettle, the polymerization is carried out under the pressure of 80Pa, and the polymerization temperature is gradually increased from 180 °C to 280 °C (divided into 10 stages, respectively, 180 ° C - 190 ° C - 200 °C-210°C-220°C-230°C-240°C-250°C-260°C-270°C-280°C), the liquid phase viscosity increasing reaction time is 80min; at the same time adding the chain extender phosphate ester, the amount of chain extender added Is 0.5% by weight of caprolactam;
  • the nylon 6 polymer of Example 49 was directly spun according to the nylon 6 spinning process immediately after the end of the liquid phase thickening reaction, the spinning temperature was 240 ° C, the spinning speed was 4500 m / min, and the cooling air temperature was 25 ° C. The wind speed was 0.6 m/s and the relative humidity was 60% to obtain a pre-oriented yarn.
  • the above-mentioned nylon 6 polymer is added with functional masterbatch or masterbatch in the melt transfer process, and uniformly mixed, and then directly spun according to the nylon 6 spinning process, and the amount of addition is nylon. 6 wt% of the polymer.
  • the matrix of the functional masterbatch or masterbatch is a branched nylon.
  • the functional adjuvant contained in the functional masterbatch is an antibacterial agent iron oxide in an amount of 15% by weight of the functional masterbatch.
  • the colorant used in the masterbatch is iron oxide yellow, pigment green 36, pigment yellow 214, and the mass ratio of iron oxide yellow, pigment green 36, and pigment yellow 214 is 2:1:1.
  • the above-mentioned nylon 6 polymer is added with a polymer chip on the line during the melt transportation, and immediately mixed and then directly spun according to the nylon 6 spinning process, and the polymer chip is added in a nylon amount. 65% by weight of the melt.
  • the polymer section was nylon 1212.
  • a nylon 6 polymerization method is prepared by a stepwise polymerization method, and the specific preparation method is as follows:
  • the obtained product has a number average molecular weight of 2000, an oligomer content of 30%, a cyclic dimer content of 0.1% or less, and a melt viscosity of 5 Pa ⁇ s;
  • the second stage is the pre-polycondensation stage: the product obtained by the ring-opening reaction is subjected to a polycondensation reaction under the conditions of a pressure of 150 Pa and a temperature of 180 ° C, and the pre-polycondensation reaction time is 3 hours; and the molecular weight stabilizer diamine H 2 N (CH) is simultaneously added.
  • the obtained prepolymer has a melt molecular weight of 4000, an oligomer content of 2%, wherein the cyclic dimer content is 0.1%, and the melt viscosity is 800 Pa ⁇ s;
  • the third stage is the liquid phase thickening stage: using a liquid phase thickening kettle, the polymerization is carried out under the pressure of 80Pa, and the polymerization temperature is gradually increased from 180 °C to 280 °C (divided into 10 stages, respectively, 180 ° C - 190 ° C - 200 °C-210°C-220°C-230°C-240°C-250°C-260°C-270°C-280°C), the liquid phase viscosity increasing reaction time is 80min; at the same time adding the chain extender phosphate ester, the amount of chain extender added Is 0.5% by weight of caprolactam;
  • the obtained melt had a molecular weight of 15,960, a relative viscosity of 2.5, an oligomer content of 1.5% or less, and a cyclic dimer content of 0.2% or less.
  • a nylon 6 polymer was obtained.
  • nylon 6 polymer of Example 51 is directly applied to the composite spinning after the end of the liquid phase thickening reaction, the composite spinning is a side-by-side type, and the other component of the composite spinning except nylon 6 is nylon. 6T, the mass ratio of the nylon 6 polymer to another component is 3:7.
  • the spinning microporous cross-sectional shape of the above spinning is polygonal;
  • the above-mentioned nylon 6 polymer is added with functional masterbatch or masterbatch in the melt transfer process, and uniformly mixed, and then directly spun according to the nylon 6 spinning process, and the amount of addition is nylon. 6 wt% of the polymer.
  • the matrix of the functional masterbatch or masterbatch is polytrimethylene terephthalate.
  • the functional auxiliary contained in the functional masterbatch is a flame retardant bis(hexachlorocyclopentadienyl)cyclooctane in an amount of 20% by weight of the functional masterbatch.
  • the colorants used in the masterbatch were Pigment Orange 43 and Pigment Orange 68, and the mass ratio of Pigment Orange 43 to Pigment Orange 68 was 1:1.
  • the above-mentioned nylon 6 polymer is added with a polymer chip on the line during the melt transportation, and immediately mixed and then directly spun according to the nylon 6 spinning process, and the polymer chip is added in a nylon amount. 6 50% by weight of the melt.
  • the polymer slice is polybutylene terephthalate.
  • a nylon 6 polymerization method is prepared by a stepwise polymerization method, and the specific preparation method is as follows:
  • the obtained product has a number average molecular weight of 2000, an oligomer content of 30%, a cyclic dimer content of 0.1% or less, and a melt viscosity of 5 Pa ⁇ s;
  • the second stage is the pre-polycondensation stage: the product obtained by the ring-opening reaction is subjected to a polycondensation reaction under the conditions of a pressure of 150 Pa and a temperature of 180 ° C, and the pre-polycondensation reaction time is 3 hours; and the molecular weight stabilizer diamine p-phenylenediamine and the molecular weight stabilizer are simultaneously added.
  • Aromatic dibasic acid The isophthalic acid (the mass ratio of the diamine to the isophthalic acid is 1:2), the stabilizer is added in an amount of 8 wt% of the caprolactam; and the anion generating material is added to the icyrite in an amount of 8 wt% of the caprolactam;
  • the obtained prepolymer has a melt molecular weight of 4000, an oligomer content of 2%, wherein the cyclic dimer content is 0.1%, and the melt viscosity is 800 Pa ⁇ s;
  • the third stage is the liquid phase thickening stage: using a liquid phase thickening kettle, the polymerization is carried out under the pressure of 80Pa, and the polymerization temperature is gradually increased from 180 °C to 280 °C (divided into 10 stages, respectively, 180 ° C - 190 ° C - 200 °C-210°C-220°C-230°C-240°C-250°C-260°C-270°C-280°C), the liquid phase viscosity increasing reaction time is 80min; at the same time adding the chain extender phosphate ester, the amount of chain extender added Is 0.5% by weight of caprolactam;
  • the obtained melt had a molecular weight of 15,960, a relative viscosity of 2.5, an oligomer content of 1.5% or less, and a cyclic dimer content of 0.2% or less.
  • a nylon 6 polymer was obtained.
  • nylon 6 polymer of Example 53 is directly applied to the composite spinning after the end of the liquid phase thickening reaction, the composite spinning is a side-by-side type, and the other component of the composite spinning except nylon 6 is nylon. 6T, the mass ratio of the nylon 6 polymer to another component is 3:7.
  • the spinning microporous cross-sectional shape of the above spinning is polygonal;
  • the above-mentioned nylon 6 polymer is added with functional masterbatch or masterbatch in the melt transfer process, and uniformly mixed, and then directly spun according to the nylon 6 spinning process, and the amount of addition is nylon. 6 wt% of the polymer.
  • the matrix of the functional masterbatch or masterbatch is polytrimethylene terephthalate.
  • the functional auxiliary contained in the functional masterbatch is a flame retardant bis(hexachlorocyclopentadienyl)cyclooctane in an amount of 20% by weight of the functional masterbatch.
  • the colorant used in the masterbatch is Pigment Orange 43.
  • the above-mentioned nylon 6 polymer is added with a polymer chip on the line during the melt transportation, and immediately mixed and then directly spun according to the nylon 6 spinning process, and the polymer chip is added in a nylon amount. 6 50% by weight of the melt.
  • the polymer slice is polybutylene terephthalate.
  • a nylon 6 polymerization method is prepared by a stepwise polymerization method, and the specific preparation method is as follows:
  • the obtained melt had a molecular weight of 15,960, a relative viscosity of 2.5, an oligomer content of 1.5% or less, and a cyclic dimer content of 0.2% or less.
  • a nylon 6 polymer was obtained.
  • the spinning microporous cross-sectional shape of the above spinning is a triangle
  • the above-mentioned nylon 6 polymer is added with a polymer chip on the line during the melt transportation, and immediately mixed and then directly spun according to the nylon 6 spinning process, and the polymer chip is added in a nylon amount. 65% by weight of the melt.
  • the polymer section was nylon 1212.
  • the obtained product has a number average molecular weight of 2000, an oligomer content of 30%, a cyclic dimer content of 0.1% or less, and a melt viscosity of 5 Pa ⁇ s;
  • the second stage is a pre-polycondensation stage: the product obtained by the ring-opening reaction is subjected to a polycondensation reaction under the conditions of a pressure of 150 Pa and a temperature of 180 ° C, and the pre-polycondensation reaction time is 3 hours; and the molecular weight stabilizer diamine xylene diamine is added at the same time.
  • the obtained prepolymer has a melt molecular weight of 4000, an oligomer content of 2%, wherein the cyclic dimer content is 0.1%, and the melt viscosity is 800 Pa ⁇ s;
  • the nylon 6 polymer of Example 57 was directly spun according to the nylon 6 spinning process immediately after the end of the liquid phase thickening reaction, the spinning temperature was 240 ° C, the spinning speed was 4500 m / min, and the cooling air temperature was 25 ° C. The wind speed was 0.6 m/s and the relative humidity was 60% to obtain a pre-oriented yarn.
  • the spinning microporous cross-sectional shape of the above spinning is a triangle
  • the above-mentioned nylon 6 polymer is added with a polymer chip on the line during the melt transportation, and immediately mixed and then directly spun according to the nylon 6 spinning process, and the polymer chip is added in a nylon amount. 65% by weight of the melt.
  • the polymer section was nylon 1212.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyamides (AREA)

Abstract

本发明涉及一种尼龙6聚合方法及其熔体直纺方法，通过先低温制备聚酰胺6预聚体，预先控制熔体中低聚物含量，然后通过缩聚反应动力学强化的方法，在环状低聚物未大量生成前完成聚合，获得一定分子量的尼龙6聚合物熔体，所得产物中，可萃取物含量≤1.5wt％，环状二聚体含量≤0.2wt％；然后，缩聚反应动力学强化结束后直接熔融纺丝成形。本发明工艺简单，在提高己内酰胺的利用率的同时，还降低了能耗，所获熔体可直接熔融纺丝，易于实现大容量规模化生产，聚合过程中可添加改性剂，实现尼龙6柔性化生产，可应用在服用纤维、工业用丝、工程塑料等领域。

Description

一种尼龙6聚合方法及其熔体直纺方法 技术领域
本发明属技术领域，涉及一种尼龙6聚合方法及其熔体直纺方法。
背景技术
尼龙纤维由于其具有优异的物理机械性能和纺织加工性能，自问世以后，其产量在相当长的一段时间内位居合成纤维家族的第一位，但由于价格与生产成本的限制以及聚酯纤维的快速发展，现为第二大产量的合成纤维。2013年我国锦纶产量为211.28万吨，同比增长12.44％，产量约占合成纤维总产量的6.3％。尼龙纤维具有聚酯纤维无法比拟的优良物理性能，如尼龙纤维的断裂强度较高，耐磨性居纺织通用纤维之冠，吸湿性好，弹性回复率和耐疲劳性能优良，染色性好。尼龙纤维除了服装业用和装饰用外，在其他产业中也有广阔的应用，如其在轮胎帘子布、汽车用纺织品、过滤材料、BCF地毯膨体纱上都开发了新产品。尼龙纤维有很多品种，主要品种是尼龙6和尼龙66纤维，由于历史原因和各国的具体条件不同，各个国家的侧重点也不同，美、英等国以生产尼龙66为主，德国、意大利、日本及东欧各国以尼龙6为主，我国主要生产尼龙6纤维。
己内酰胺连续水解聚合是应用最广泛的尼龙6聚合生产工艺。在尼龙6切片生产中，聚合物达到平衡时，己内酰胺的转化率一般在90％左右，这意味着聚合物中残余有10％左右的己内酰胺与低聚物(其中单体占约75％，低聚物约占25％，低聚物中主要为环状二聚体)，在工业上通常采用热水除去，因此也称为热水可萃取物。在尼龙6熔融纺丝过程中，熔体中不允许有6μm以上的杂质存在，并且希望己内酰胺单体尽可能的少，因为在高速纺丝过程中，纤维的张力大，杂质或气泡的存在会引起应力集中，从而发生断丝现象。环状二聚体的熔融温度达到348℃，远高于尼龙6常规纺丝温度，决定了其无法熔融，也无法在熔融状态下参加开环聚合反应；己内酰胺在纺丝温度下容易挥发，在纤维成型过程中容易形成气泡；因此成为了影响纺丝过程的重要因素。存在熔体中的其他低聚物还会引起相对分子量分布变宽，低分子聚合物的存在不仅影响了纺丝成型过程，还对纤维的力学性能造成了影响。因此在尼龙6纺丝过程中，为了避免出现断丝等不利于纺丝过程的情况，热水可萃取物含量应小于1.5％。
因此目前工业上需对聚酰胺6切片进行萃取后才能进行纺丝，根据FZ/T 51004-2011，聚己内酰胺切片热水可萃取物含量应小于0.5％(优等品)，但该过程需要消耗大量的能量及萃取水，而且还是对原料己内酰胺造成浪费。因此，如何降低已内酰胺聚合过程中所产生的低 聚物，进而实现聚酰胺6的熔体直纺成为了聚酰胺6纤维发展的制约因素之一。因此通过开发新聚合工艺，降低已内酰胺水解聚合过程中所产生的低聚物含量，实现尼龙6熔体直纺成为了产业发展的趋势。
目前降低己内酰胺水解聚合过程中低聚物含量的主要方法是对聚合温度的控制，因为己内酰胺聚合是一个随着温度变化而变化的平衡关系，随着温度的升高，更有利于低聚物生成，尤其是环状低聚物，因此可以通过控制聚合温度来有效控制低聚物含量，即低温聚合。要想确保聚合过程处于液态进行，聚合温度需至少大于聚酰胺6熔点以下10℃，此时的聚合温度仍不能将低聚物控制在可熔体直纺的范围，而且低温聚合还有另外一个缺点，即反应速度较慢，所获的聚合物分子量偏低；而在更低温度下聚合的过程实际上是分为两部分，一部分是熔融聚合过程，一部分是固相聚合过程，固相聚合的过程是为了获得足够分子量的聚合物用以产品的开发，但是目前还没有找到能将低温下形成的固态聚合物变成适合纺丝的有效方法，如果由低温聚合物纺制纤维，则必须先将聚合物熔融，然而，这时随着与时间和温度有关的平衡而又形成低分子化合物，其数量和熔化时的温度相适应，并且总要比低温聚合时要多，这样一来，与正常的聚合法相比较就没有什么优点了。
本发明通过先低温制备聚酰胺6预聚体，预先控制熔体中低聚物含量，然后通过缩聚反应动力学强化的方法，在环状低聚物未大量生成前完成聚合，获得一定分子量的尼龙6聚合物熔体。此方法在高温下反应时间段，可以避免熔体在较高温度下，环状低聚物随着时间的推移大量生成。
发明内容
本发明所要解决的技术问题是提供一种尼龙6聚合方法及其熔体直纺方法。
本发明的一种尼龙6聚合方法，采用分段聚合的方法制备尼龙6，具体制备方法如下：
第一段为开环反应阶段：在温度为150-220℃和压力为0.1-5MPa条件下，将己内酰胺、水和催化剂混合后进行预聚合；此过程为己内酰胺在压力及开环剂水的作用下开环形成氨基己酸，氨基己酸再通过加成反应打开己内酰胺，形成短链段，也使己内酰胺开环率提高，这个过程中所采用的聚合温度较低，由于环状低聚物形成是热力学平衡过程，温度降低有利于降低环状低聚物含量，同时，此阶段所形成均为短链段的尼龙6，尼龙6分子链段呈刚性，端氨基回咬的活化能提高，形成环状低聚物的可能性降低，从而产生的环状低聚物含量也较低；
所获产物数均分子量为1000-2000，低聚物含量10-30％，环状二聚体含量0.1％以下，熔体粘度为1-10Pa·s；
第二段为预缩聚阶段：在压力为10-200Pa和温度为180-220℃条件下，将开环反应所得产物进行缩聚反应；此过程的目的是使第一阶段所获短链段通过缩聚提高分子量，并将大部分单体、水等小分子抽除，此过程需要在压力较低的条件下进行；对于尼龙6来说，当分子量增长到5000左右时，即为分子链缠结点，聚合物熔体粘度会随着分子量的增加而大大增加，此过程为了保证低聚物含量不会大量增加，需保持在较低温度，又必须保证熔体粘度处于较低水平，以方便小分子抽除，因此需将聚合物分子量控制在缠结点附近。
所得预聚物的熔体分子量为4000-6000，低聚物含量在2-8％，其中环状二聚体含量为0.1％，熔体粘度为1-100Pa·s；
第三段为缩聚反应动力学强化阶段：在压力为10-100Pa条件下聚合，聚合温度从180-220℃逐步升至220-280℃；所获熔体分子量为11400-45600，相对粘度为2.0-5.0，低聚物含量在1.5％以下，其中环状二聚体含量为0.2％以下；此过程的目的是将聚合物分子量增加至目标分子量，则需要提高聚合温度，但为了避免熔体在较高温度下低聚物含量随着停留时间的增加而增加，就必须快速抽除小分子，将聚合物分子量快速增粘至目标分子量；为保证小分子能快速脱除以达到快速增粘的目的，需保证熔体粘度处于较低水平；聚合温度从180-220℃逐步升至220-280℃采用的是阶梯升温的方式，原因是随着分子量升高，熔体粘度增大，为了保证熔体粘度处于较低水平，就得升高温度，但综合考虑到高温有利于低聚物的生成，因此采用梯度升温的方法，保证熔体粘度为1000-4000Pa·s；缩聚反应动力学强化结束后即制得尼龙6聚合物。
作为优选的技术方案：
如上所述的一种尼龙6聚合方法，水含量为己内酰胺的1-20wt％，催化剂含量为己内酰胺的1-20wt％。
如上所述的一种尼龙6聚合方法，所述催化剂为氨基酸和/或质子酸，所述质子酸为HCl、H3PO4、H2SO4、HNO3、NH3、[Al(H2O)6]中的一种及以上。
如上所述的一种尼龙6聚合方法，所述氨基酸为脂肪族氨基酸或芳香族氨基酸；所述脂肪族氨基酸的分子式为NH2(CH2)xCOOH，其中x＝1～16；所述芳香族氨基酸为主链或支链上存在苯环，为苯丙氨酸。
如上所述的一种尼龙6聚合方法，所述开环反应时间为3-12h。
如上所述的一种尼龙6聚合方法，所述预缩聚反应时间为1-3h。
如上所述的一种尼龙6聚合方法，所述缩聚反应动力学强化过程时间为10-90min。
如上所述的一种尼龙6聚合方法，所述阶梯升温是指温度从180-220℃升到220-280℃分为2-10个阶段，以实现温度随缩聚反应的进行而逐渐上升。
如上所述的一种尼龙6聚合方法，采用液相增粘釜，实现所述缩聚反应动力学强化过程。
如上所述的一种尼龙6聚合方法，所述开环阶段、所述预缩聚或所述缩聚反应动力学强化阶段，还添加分子量稳定剂，为单元酸、单元胺、多元酸或多元胺中的一种及以上，添加量为己内酰胺的0.01-10wt％；其中：
单元酸，为脂肪族H(CH2)aCOOH，其中，a＝1～16；或芳香族，为苯甲酸；
单元胺，为脂肪族H(CH2)bNH2，其中，b＝1～16；或芳香族，为苯胺；
多元酸，为脂肪族二元酸HOOC(CH2)cCOOH，其中，c＝1-20；或芳香族二元酸，为邻苯二甲酸、间苯二甲酸、对苯二甲酸或萘二甲酸；
多元胺，为脂肪族二元胺H2N(CH2)dNH2，其中，d＝1-20；或芳香族二元胺，为邻苯二胺、间苯二胺、对苯二胺、萘二胺或二甲苯二胺。
如上所述的一种尼龙6聚合方法，所述开环阶段、所述预缩聚或所述缩聚反应动力学强化阶段，还加入内酰胺、内酯或其聚合物，所添加量为己内酰胺的50wt％以下。
如上所述的一种尼龙6聚合方法，所述聚合物为内酰胺和/或内酯的均聚物或共聚物，所述内酰胺为
Figure PCTCN2016080024-appb-000001
所述内酯为
Figure PCTCN2016080024-appb-000002
其中n＝1～10，m＝1～10；所述内酰胺和/或内酯的数均分子量为4000以下。
如上所述的一种尼龙6聚合方法，所述开环阶段、所述预缩聚或所述缩聚反应缩聚反应动力学强化阶段，还添加功能添加剂，为抗氧化剂、抗紫外剂、抗菌剂、阻燃剂、负离子发生材料、荧光材料、碳纳米管或石墨烯，添加量为己内酰胺的0.01-10wt％。
如上所述的一种尼龙6聚合方法，所述抗氧化剂为抗氧化剂1010、抗氧化剂168或抗氧化剂616；抗紫外剂为水杨酸、二苯甲酮系苯并三唑系、二氧化钛、氧化锌、碳酸钙、滑石粉、SEED；抗菌剂为纳米二氧化钛、氧化锌、氧化铁、壳聚糖、纳米银、纳米铜或季铵盐类化合物；阻燃剂为硼酸锌、四溴双酚A、双(六氯环戊二烯)环辛烷、多磷酸铵、十溴二苯醚或1,3,6-三(4,6-二氨基-2-硫基三嗪)己烷与三聚氰酸的混合物；负离子发生材料为奇冰石、电气石、蛋白石或奇才石；荧光材料是以碱土金属的硫化物、铝酸盐作为发光基质，以稀土镧系元素铕、钐、铒或钕，作为激活剂。
如上所述的一种尼龙6聚合方法，所述季铵盐类化合物分子式为
Figure PCTCN2016080024-appb-000003
其中，R1、R2＝C8～C20，R1、R2相同或不同，X-为Cl-、Br-、I-。
如上所述的一种尼龙6聚合方法，所述缩聚反应动力学强化阶段，还添加扩链剂达到快速增粘的效果，扩链剂的添加量为己内酰胺的0.01wt％-1.2wt％；所述扩链剂为双环氧乙烷、 双噁唑酮、双酰基双己内酰胺、磷酸酯或双异氰酸酯；所述的双环氧乙烷的分子式为
Figure PCTCN2016080024-appb-000004
其中R＝C1～C8。
本发明还提供了一种尼龙6聚合物的熔体直纺方法，所述尼龙6聚合物在缩聚反应动力学强化过程结束后，立即按照尼龙6纺丝工艺直接纺丝，纺丝温度为240-280℃，第一导丝盘速度为4000-4500m/min，第二导丝盘速度为5000-6000m/min，拉伸倍数为1.1-1.5倍，冷却风温为15-25℃，风速0.5-1m/s，相对湿度为60％-90％，得到全拉伸丝。
如上所述的一种尼龙6聚合物的熔体直纺方法，所述尼龙6聚合物在缩聚反应动力学强化过程结束后，立即按照尼龙6纺丝工艺直接纺丝，纺丝温度为240-280℃，纺丝速度为700-1500m/min，冷却风温为20-30℃，风速0.3-1m/s，相对湿度为60％-80％，得到未取向丝。
如上所述的一种尼龙6聚合物的熔体直纺方法，所述尼龙6聚合物在缩聚反应动力学强化过程结束后，立即按照尼龙6纺丝工艺直接纺丝，纺丝温度为240-280℃，纺丝速度为4000-4500m/min，冷却风温为15-25℃，风速0.3-0.6m/s，相对湿度为60％-80％，得到预取向丝。
如上所述的一种尼龙6聚合物的熔体直纺方法，所述尼龙6聚合物在缩聚反应动力学强化过程结束后，立即按照尼龙6纺丝工艺直接纺丝，纺丝温度为240-280℃，纺丝速度为4500-6000m/min，冷却风温为15-20℃，风速0.3-0.5m/s，相对湿度为80％-90％，得到高取向丝。
如上所述的一种尼龙6聚合物的熔体直纺方法，所述尼龙6聚合物在缩聚反应动力学强化过程结束后，立即按照尼龙6纺丝工艺直接纺丝得到膨化变形丝，纺丝温度为240-280℃，冷却风温为20-30℃，风速0.3-1m/s，相对湿度为60％-80％，喂入辊温度为60-120℃，拉伸辊温度为100-190℃，喂入速度为300-1000m/min，拉伸速度为1000-3500m/min，拉伸倍数为3.5-5倍，变形热空气温度为190-230℃，空气喷射压力为196kPa-490kPa，卷绕速度为600-3000m/min，冷却空气温度为25℃。
如上所述的一种尼龙6聚合物的熔体直纺方法，所述尼龙6聚合物在缩聚反应动力学强化过程结束后，直接应用于复合纺丝，所述复合纺丝是并列型、皮芯型、海岛型、桔瓣型或多芯型复合纺丝；所述复合纺丝除尼龙6之外另一组分是尼龙6T、尼龙612、尼龙610、尼龙1212、尼龙46、尼龙410、尼龙11、尼龙12、尼龙26、尼龙212、支链尼龙、水溶性聚酯中的一种，所述尼龙6聚合物与另一组分的质量比为3:7-7:3。
如上所述的一种尼龙6聚合物的熔体直纺方法，纺丝的喷丝微孔截面形状是三角形、十字形、多角形、中空纤维、U形、T形、Y形、多边形或工字形。
如上所述的一种尼龙6聚合物的熔体直纺方法，所述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加功能性母粒或色母粒，混合均匀后再按照尼龙6纺丝工艺直接纺丝，添加量为尼龙6聚合物的1-30wt％。
如上所述的一种尼龙6聚合物的熔体直纺方法，所述功能性母粒或色母粒的基体是尼龙、聚酯、聚乙二醇中的一种及以上。
如上所述的一种尼龙6聚合物的熔体直纺方法，尼龙是尼龙6、尼龙6T、尼龙612、尼龙610、尼龙1212、尼龙46、尼龙410、尼龙11、尼龙12、尼龙26、尼龙212、支链尼龙中的一种及以上；聚酯是聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚对苯二甲酸丙二醇酯、水溶性聚酯中的一种及以上；聚乙二醇分子量范围为400-20000，聚乙二醇端基是羟基，或是经过改性的端基为羧基和/或氨基的聚乙二醇。
如上所述的一种尼龙6聚合物的熔体直纺方法，所述功能性母粒中所含功能性助剂是抗氧化剂、抗紫外剂、抗菌剂、阻燃剂、负离子发生材料、荧光材料、碳纳米管或石墨烯，含量为功能性母粒的10-30wt％。
如上所述的一种尼龙6聚合物的熔体直纺方法，所述抗氧化剂为抗氧化剂1010、抗氧化剂168或抗氧化剂616；抗紫外剂为水杨酸、二苯甲酮系苯并三唑系、二氧化钛、氧化锌、碳酸钙、滑石粉、SEED；抗菌剂为纳米二氧化钛、氧化锌、氧化铁、壳聚糖、纳米银、纳米铜或季铵盐类化合物；阻燃剂为硼酸锌、四溴双酚A、双(六氯环戊二烯)环辛烷、多磷酸铵、十溴二苯醚或1,3,6-三(4,6-二氨基-2-硫基三嗪)己烷与三聚氰酸的混合物；负离子发生材料为奇冰石、电气石、蛋白石或奇才石；荧光材料是以碱土金属的硫化物、铝酸盐作为发光基质，以稀土镧系元素铕、钐、铒或钕，作为激活剂。
如上所述的一种尼龙6聚合物的熔体直纺方法，分子式为
Figure PCTCN2016080024-appb-000005
其中，R1、R2＝C8～C20，R1、R2相同或不同；X-为Cl-、Br-、I-。
如上所述的一种尼龙6聚合物的熔体直纺方法，所述色母粒中所用着色剂为酞菁红、酞菁蓝、酞菁绿、耐晒大红、大分子红、大分子黄、永固黄、永固紫、偶氮红、镉红、镉黄、钛白粉、炭黑、氧化铁红、氧化铁黄、颜料红179、颜料蓝60、颜料绿36、颜料黄214、颜料橙43、颜料橙68、颜料棕41、颜料黄184、溶剂紫59、溶剂紫37、溶剂红143、溶剂红181、溶剂蓝94、溶剂蓝132、溶剂绿29、溶剂黄135、溶剂黄167的一种及以上。
如上所述的一种尼龙6聚合物的熔体直纺方法，所述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加聚合物切片，混合均匀后立即按照尼龙6纺丝工艺直接纺丝，所述聚合物切片添加量为尼龙6熔体的5-50wt％。
如上所述的一种尼龙6聚合物的熔体直纺方法，所述聚合物切片是聚酯、尼龙、聚乙二醇中一种及以上。
如上所述的一种尼龙6聚合物的熔体直纺方法，聚酯是聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚对苯二甲酸丙二醇酯、水溶性聚酯中的一种及以上；尼龙是尼龙6、尼龙6T、尼龙612、尼龙610、尼龙1212、尼龙46、尼龙410、尼龙11、尼龙12、尼龙26、尼龙212、支链尼龙中的一种及以上；聚乙二醇分子量范围为400-20000，聚乙二醇端基是羟基，或是经过改性的端基为羧基和/或氨基的聚乙二醇。
本发明还提出一种尼龙6聚合物纺成纤维后织成的面料，将所述尼龙聚合物纺制成的尼龙6纤维，然后通过梭织或针织形成面料，面料是平纹、斜纹、缎纹中的一种，然后进行染色，获得不同规格颜色的布料。
如上所述的面料，面料的染色生产工序为：前处理退浆-热水清洗坯布-升温染色-固色-降温清洗-面料出机防水定型-成品检验-成品打卷。
如上所述的面料，所述前处理退浆温度为60-80℃，退浆时间为6-12h，其退浆助剂配方为：纯碱10-20g/L，去油灵10-15g/L。
如上所述的面料，所述升温染色工艺为始染温度为30-40℃，以1-3℃/min的速率升温，升温至90-95℃再保温40min；染色剂浓度为0.5-2％(omf)，浴比为1:10-20。
如上所述的面料，所述固色工艺为温度为90-95℃，固色时间为20-60min；固色剂浓度为0.5-2％(omf)，浴比为1:10-20。
如上所述的面料，在染色及固色过程中，适当加入一些助剂，所述助剂添加量为5-10g/L，所述助剂为软水剂，为NORM02；匀染剂，为ACID03或ACID16；缓染剂，为硫酸铵。
本发明提出的一种尼龙6聚合方法的装置，料仓的作用是储存己内酰胺，其通过管道与原料加热罐相连，原料加热罐的作用是将己内酰胺熔化；加压开环釜通过管道与原料加热罐相连，加压开环釜的作用是通过加压的方式，促使己内酰胺水解开环，获得环状低聚物含量较低的预聚物；缩聚釜通过管道与加压开环釜相连，缩聚釜的作用是将加压开环釜的产物预缩聚至分子链缠结点附近的分子量，并将大量的未反应的单体抽除，此时熔体粘度较低，因此对于缩聚的条件要求不高；液相增粘釜通过管道与缩聚釜相连，液相增粘釜的作用是将缩聚釜的产物通过高真空缩聚反应动力学强化至目标分子量，并将未反应的单体及水分快速抽除，此时熔体粘度较高，因此对于缩聚的条件要求高；在缩聚釜、液相增粘釜分别与缓冲罐通过管道相连，缓冲罐的作用是收集缩聚釜、液相增粘釜中被抽取出来的小分子，并将其输送到浓缩罐中；浓缩罐与缓冲罐通过管道相连，浓缩罐的作用是将缓冲罐中输送过来的单体浓缩，并重新输送到原料加热罐中，继续参与反应。被送到浓缩器浓缩并属性重新利用；得 到的熔体直接被输送到纺丝组件进行纺丝，随后织造、染整，得到最终产品。
机理说明：
本发明采用低温聚合制备预聚物，实现环状二聚体的有效控制，主要是依靠以下机理：
己内酰胺水解聚合反应过程中所发生的反应均是可逆的平衡反应，形成环状二聚体的反应主要是端氨基咬合反应，其反应可以由以下方程表示：
Pn+C2→Pn+2
其中，正反应是环状二聚体开环加成反应，反应活化能为Ea1＝89.12KJ/mol；逆反应是端氨基咬合反应，反应活化能为Ea2＝102.38KJ/mol，是形成环状二聚体的最主要方式。
温度是影响己内酰胺聚合体系中低聚物含量的最主要因素，下式为阿伦尼乌斯公式：
Figure PCTCN2016080024-appb-000006
取对数后得
lnk＝lnA-Ea/RT
从上可以得到反应速率常数k与温度之间的关系，从式中可以看出，反应活化能越高，反应速率常数对温度的变化越敏感，环状二聚体的加聚反应活化能要小于成环反应活化能，因此，聚合温度升高，有利于环化反应的进行，从而使环状低分子物的含量增加。
有益效果
1、本发明的聚合工艺简单，在提高己内酰胺的利用率的同时，降低了能耗，降低尼龙6生产成本。
2、本发明结合了缩聚反应动力学强化过程，通过缩聚反应动力学强化提高了己内酰胺水解聚合反应速度，提高了生产效率。
3、本发明先在150-220℃条件下，低温预聚合形成预聚物，保证体系中的预聚物具有较高的活性，同时含有较低的环状低聚物，尤其是环状二聚体，然后通过缩聚反应动力学强化的方法，在环状低聚物未大量生成前完成聚合，获得一定分子量的尼龙6聚合物熔体。此方法在高温下反应时间段，可以避免熔体在较高温度下，环状低聚物随着时间的推移大量生成，有效降低环状低聚物含量，所获熔体可萃取物含量≤2％，环状二聚体含量≤0.2％，产物相对粘度为2.0～6.0，可用于熔体直纺的聚酰胺熔体。
4、本发明所述聚合工艺，可在加压开环釜、缩聚釜、液相增粘釜加入改性成分，实现尼龙6功能化柔性生产，利用提高产品附加值。
附图说明
图1为环状二聚体不稳定化处理结构图
图2为尼龙6聚合工艺示意图
1：料仓；2：阀门；3：原料加热罐；4：加压开环釜；5：缩聚釜；6：液相增粘釜；7：缓冲罐；8：浓缩罐
具体实施方式
下面结合具体实施方式，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例1 尼龙6聚合方法
一种尼龙6聚合方法，采用分段聚合的方法制备尼龙6，具体制备方法如下：
第一段为开环反应阶段：在温度为150℃和压力为5MPa条件下，将己内酰胺、水和催化剂混合后进行预聚合，开环反应时间为3h；其中水含量为己内酰胺的1wt％，催化剂含量为己内酰胺的20wt％，催化剂为脂肪族氨基酸，分子式为NH2(CH2)xCOOH，其中x＝1；
所获产物数均分子量为1000，低聚物含量30％，环状二聚体含量0.1％以下，熔体粘度为1Pa·s；
第二段为预缩聚阶段：在压力为10Pa和温度为220℃条件下，将开环反应所得产物进行缩聚反应，预缩聚反应时间为1h；
所得预聚物的熔体分子量为4000，低聚物含量在2％，其中环状二聚体含量为0.1％，熔体粘度为10Pa·s，图1为环状二聚体不稳定化处理结构图；
第三段为缩聚反应动力学强化阶段：在压力为10Pa条件下聚合，聚合温度从220℃逐步升至280℃(分成2个阶段，第一阶段从220℃升至250℃，第二阶段从250℃升至280℃)，缩聚反应动力学强化过程时间为90min；
所获熔体分子量为11400，相对粘度为2.0，低聚物含量在1.5％以下，其中环状二聚体含量为0.2％以下；缩聚反应动力学强化结束后即制得尼龙6聚合物。
实施例2 尼龙6聚合方法
一种尼龙6聚合方法，采用分段聚合的方法制备尼龙6，具体制备方法如下：
第一段为开环反应阶段：在温度为220℃和压力为0.1MPa条件下，将己内酰胺、水和催化剂混合后进行预聚合，开环反应时间为12h；其中水含量为己内酰胺的20wt％，催化剂含量为己内酰胺的1wt％，催化剂为脂肪族氨基酸，分子式为NH2(CH2)xCOOH，其中x＝16；
所获产物数均分子量为1500，低聚物含量20％，环状二聚体含量0.1％以下，熔体粘度为5Pa·s；
第二段为预缩聚阶段：在压力为200Pa和温度为180℃条件下，将开环反应所得产物进行缩聚反应，预缩聚反应时间为3h；
所得预聚物的熔体分子量为5000，低聚物含量在4％，其中环状二聚体含量为0.1％，熔体粘度为50Pa·s；
第三段为缩聚反应动力学强化阶段：在压力为100Pa条件下聚合，聚合温度从180℃逐步升至220℃(分成4个阶段，分别为180℃-190℃-200℃-210℃-220℃)，缩聚反应动力学强化过程时间为10min；
所获熔体分子量为20520，相对粘度为2.8，低聚物含量在1.5％以下，其中环状二聚体含量为0.2％以下；缩聚反应动力学强化结束后即制得尼龙6聚合物。
实施例3 尼龙6聚合方法
一种尼龙6聚合方法，采用分段聚合的方法制备尼龙6，具体制备方法如下：
第一段为开环反应阶段：在温度为180℃和压力为1MPa条件下，将己内酰胺、水和催化剂混合后进行预聚合，开环反应时间为5h；其中水含量为己内酰胺的8wt％，催化剂含量为己内酰胺的15wt％，催化剂为脂肪族氨基酸，分子式为NH2(CH2)xCOOH，其中x＝8；
所获产物数均分子量为2000，低聚物含量10％，环状二聚体含量0.1％以下，熔体粘度为100Pa·s；
第二段为预缩聚阶段：在压力为100Pa和温度为200℃条件下，将开环反应所得产物进行缩聚反应，预缩聚反应时间为1.5h；
所得预聚物的熔体分子量为6000，低聚物含量在2％，其中环状二聚体含量为0.1％，熔体粘度为100Pa·s；
第三段为缩聚反应动力学强化阶段：在压力为50Pa条件下聚合，聚合温度从200℃逐步升至280℃(分成6个阶段，分别为200℃-210℃-220℃-230℃-240℃-260℃-280℃)，缩聚反应动力学强化过程时间为10min；
所获熔体分子量为34200，相对粘度为4.0，低聚物含量在1.5％以下，其中环状二聚体含量为0.2％以下；缩聚反应动力学强化结束后即制得尼龙6聚合物。
实施例4 尼龙6聚合方法
一种尼龙6聚合方法，采用分段聚合的方法制备尼龙6，具体制备方法如下：
第一段为开环反应阶段：在温度为200℃和压力为3MPa条件下，将己内酰胺、水和催化剂混合后进行预聚合，开环反应时间为8h；其中水含量为己内酰胺的15wt％，催化剂含量为己内酰胺的10wt％，催化剂为脂肪族氨基酸，分子式为NH2(CH2)xCOOH，其中x＝10；
所获产物数均分子量为1800，低聚物含量15％，环状二聚体含量0.1％以下，熔体粘度为60Pa·s；
第二段为预缩聚阶段：在压力为150Pa和温度为210℃条件下，将开环反应所得产物进行缩聚反应，预缩聚反应时间为2h；
所得预聚物的熔体分子量为4500，低聚物含量在6％，其中环状二聚体含量为0.1％，熔体粘度为80Pa·s；
第三段为缩聚反应动力学强化阶段：在压力为80Pa条件下聚合，聚合温度从210℃逐步升至280℃(分成5个阶段，分别为210℃-220℃-230℃-240℃-260℃-280℃)，缩聚反应动力学强化过程时间为20min；
所获熔体分子量为13680，相对粘度为2.2，低聚物含量在1.5％以下，其中环状二聚体含量为0.2％以下；缩聚反应动力学强化结束后即制得尼龙6聚合物。
实施例5 尼龙6聚合方法
一种尼龙6聚合方法，采用分段聚合的方法制备尼龙6，具体制备方法如下：
第一段为开环反应阶段：在温度为150℃和压力为5MPa条件下，将己内酰胺、水和催化剂混合后进行预聚合，开环反应时间为10h；其中水含量为己内酰胺的1wt％，催化剂含量为己内酰胺的20wt％，催化剂为苯丙氨酸；
所获产物数均分子量为1200，低聚物含量25％，环状二聚体含量0.1％以下，熔体粘度为6Pa·s；
第二段为预缩聚阶段：在压力为10Pa和温度为220℃条件下，将开环反应所得产物进行缩聚反应，预缩聚反应时间为2h；
所得预聚物的熔体分子量为5500，低聚物含量在5％，其中环状二聚体含量为0.1％，熔体粘度为75Pa·s；
第三段为缩聚反应动力学强化阶段：在压力为10Pa条件下聚合，聚合温度从220℃逐步升至280℃(分成6个阶段，分别为220℃-230℃-240℃-250℃-260℃-270℃-280℃)，缩聚反应动力学强化过程时间为30min；
所获熔体分子量为22800，相对粘度为3.0，低聚物含量在1.5％以下，其中环状二聚体含量为0.2％以下；缩聚反应动力学强化结束后即制得尼龙6聚合物。
实施例6 尼龙6聚合方法
一种尼龙6聚合方法，采用分段聚合的方法制备尼龙6，具体制备方法如下：
第一段为开环反应阶段：在温度为200℃和压力为3MPa条件下，将己内酰胺、水和催化剂混合后进行预聚合，开环反应时间为8h；其中水含量为己内酰胺的15wt％，催化剂含量为己内酰胺的10wt％，催化剂为HCl；同时加入分子量稳定剂H(CH2)aCOOH，其中a＝16，添加量为己内酰胺的0.01wt％；同时加入内酰胺，所添加量为己内酰胺的49wt％；同时加入抗氧化剂1010，添加量为己内酰胺的0.01wt％；同时加入扩链剂双环氧乙烷，分子式为
Figure PCTCN2016080024-appb-000007
其中R＝C1，扩链剂的添加量为己内酰胺的0.01wt％；
所获产物数均分子量为1900，低聚物含量25％，环状二聚体含量0.1％以下，熔体粘度为10Pa·s；
第二段为预缩聚阶段：在压力为150Pa和温度为210℃条件下，将开环反应所得产物进行缩聚反应，预缩聚反应时间为2.5h；
所得预聚物的熔体分子量为5200，低聚物含量在7％，其中环状二聚体含量为0.1％，熔体粘度为90Pa·s；
第三段为缩聚反应动力学强化阶段：在压力为80Pa条件下聚合，聚合温度从210℃逐步升至280℃(分成7个阶段，分别为210℃-220℃-230℃-240℃-250℃-260℃-270℃-280℃)，缩聚反应动力学强化过程时间为40min；
所获熔体分子量为29640，相对粘度为3.6，低聚物含量在1.5％以下，其中环状二聚体含量为0.2％以下；缩聚反应动力学强化结束后即制得尼龙6聚合物。
实施例7 尼龙6聚合方法
一种尼龙6聚合方法，采用分段聚合的方法制备尼龙6，具体制备方法如下：
第一段为开环反应阶段：在温度为200℃和压力为3MPa条件下，将己内酰胺、水和催化剂混合后进行预聚合，开环反应时间为8h；其中水含量为己内酰胺的15wt％，催化剂含量为己内酰胺的10wt％，催化剂为H3PO4；同时加入内酯，所添加量为己内酰胺的40wt％；
所获产物数均分子量为1600，低聚物含量15％，环状二聚体含量0.1％以下，熔体粘度为30Pa·s；
第二段为预缩聚阶段：在压力为150Pa和温度为210℃条件下，将开环反应所得产物进行缩聚反应，预缩聚反应时间为1h；同时加入分子量稳定剂H(CH2)bNH2，其中b＝16，添加量为己内酰胺的2wt％；同时加入抗紫外剂水杨酸，添加量为己内酰胺的10wt％；同时加入扩链剂双环氧乙烷，分子式为
Figure PCTCN2016080024-appb-000008
其中R＝C8，扩链剂的添加量为己内酰胺的1.2wt％；
所得预聚物的熔体分子量为4500，低聚物含量在7％，其中环状二聚体含量为0.1％，熔体粘度为90Pa·s；
第三段为缩聚反应动力学强化阶段：在压力为80Pa条件下聚合，聚合温度从210℃逐步升至280℃(分成7个阶段，分别为210℃-220℃-230℃-240℃-250℃-260℃-270℃-280℃)，缩聚反应动力学强化过程时间为50min；
所获熔体分子量为33060，相对粘度为3.9，低聚物含量在1.5％以下，其中环状二聚体含量为0.2％以下；缩聚反应动力学强化结束后即制得尼龙6聚合物。
实施例8 尼龙6聚合方法
一种尼龙6聚合方法，采用分段聚合的方法制备尼龙6，具体制备方法如下：
第一段为开环反应阶段：在温度为200℃和压力为3MPa条件下，将己内酰胺、水和催化剂混合后进行预聚合，开环反应时间为10h；其中水含量为己内酰胺的15wt％，催化剂含量为己内酰胺的10wt％，催化剂为H2SO4；
所获产物数均分子量为2000，低聚物含量10％，环状二聚体含量0.1％以下，熔体粘度为10Pa·s；
第二段为预缩聚阶段：在压力为150Pa和温度为210℃条件下，将开环反应所得产物进行缩聚反应，预缩聚反应时间为3h；同时加入内酰胺均聚物(n＝1，分子量2000)，所添加量为己内酰胺的30wt％；同时加入扩链剂双噁唑酮，扩链剂的添加量为己内酰胺的0.1wt％；
所得预聚物的熔体分子量为5700，低聚物含量在2％，其中环状二聚体含量为0.1％，熔体粘度为100Pa·s；
第三段为缩聚反应动力学强化阶段：在压力为80Pa条件下聚合，聚合温度从210℃逐步升至280℃(分成7个阶段，分别为210℃-220℃-230℃-240℃-250℃-260℃-270℃-280℃)，缩聚反应动力学强化过程时间为60min；同时加入分子量稳定剂二元酸HOOC(CH2)cCOOH，其中c＝20，添加量为己内酰胺的10wt％；同时加入抗菌剂分子式为
Figure PCTCN2016080024-appb-000009
的季铵盐类化合物，其中，R1、R2＝C8，R1、R2相同，X-为Cl-，添加量为己内酰胺的2wt％；
所获熔体分子量为45600，相对粘度为5.0，低聚物含量在1.5％以下，其中环状二聚体含量为0.2％以下；缩聚反应动力学强化结束后即制得尼龙6聚合物。
实施例9 尼龙6聚合方法
一种尼龙6聚合方法，采用分段聚合的方法制备尼龙6，具体制备方法如下：
第一段为开环反应阶段：在温度为200℃和压力为3MPa条件下，将己内酰胺、水和催化剂混合后进行预聚合，开环反应时间为5h；其中水含量为己内酰胺的15wt％，催化剂含量为己内酰胺的10wt％，催化剂为HNO3和NH3，质量比为2:1；同时加入阻燃剂硼酸锌，添加量为己内酰胺的5wt％
所获产物数均分子量为1500，低聚物含量25％，环状二聚体含量0.1％以下，熔体粘度为8Pa·s；
第二段为预缩聚阶段：在压力为150Pa和温度为210℃条件下，将开环反应所得产物进行缩聚反应，预缩聚反应时间为2h；同时加入扩链剂双酰基双己内酰胺，扩链剂的添加量为己内酰胺的1wt％；
所得预聚物的熔体分子量为4500，低聚物含量在2％，其中环状二聚体含量为0.1％，熔体粘度为10Pa·s；
第三段为缩聚反应动力学强化阶段：采用液相增粘釜，在压力为80Pa条件下聚合，聚合温度从210℃逐步升至280℃(分成7个阶段，分别为210℃-220℃-230℃-240℃-250℃-260℃-270℃-280℃)，缩聚反应动力学强化过程时间为70min；同时加入分子量稳定剂苯甲酸和苯胺(苯甲酸和苯胺质量比2:1)，稳定剂添加量为己内酰胺的4wt％；同时加入内酰胺共聚物(n＝10，分子量3000)，所添加量为己内酰胺的20wt％；
所获熔体分子量为39900，相对粘度为4.5，低聚物含量在1.5％以下，其中环状二聚体含量为0.2％以下；缩聚反应动力学强化结束后即制得尼龙6聚合物。
实施例10 尼龙6聚合方法
一种尼龙6聚合方法，采用分段聚合的方法制备尼龙6，具体制备方法如下：
第一段为开环反应阶段：在温度为200℃和压力为3MPa条件下，将己内酰胺、水和催化剂混合后进行预聚合，开环反应时间为6h；其中水含量为己内酰胺的15wt％，催化剂含量为己内酰胺的10wt％，催化剂为HNO3、NH3和[Al(H2O)6](HNO3、NH3和[Al(H2O)6]质量比为1:1:1)；同时加入内酯均聚物(m＝1，分子量1000)，所添加量为己内酰胺的10wt％；
所获产物数均分子量为2000，低聚物含量30％，环状二聚体含量0.1％以下，熔体粘度为5Pa·s；
第二段为预缩聚阶段：在压力为150Pa和温度为180℃条件下，将开环反应所得产物进行缩聚反应，预缩聚反应时间为3h；同时加入分子量稳定剂二元胺H2N(CH2)dNH2(其中d＝20)和芳香族二元酸邻苯二甲酸(二元胺和邻苯二甲酸的质量比为1:2)，稳定剂添加量为己内酰胺的8wt％；同时加入负离子发生材料奇冰石，添加量为己内酰胺的8wt％；
所得预聚物的熔体分子量为4000，低聚物含量在2％，其中环状二聚体含量为0.1％，熔体粘度为800Pa·s；
第三段为缩聚反应动力学强化阶段：采用液相增粘釜，在压力为80Pa条件下聚合，聚合温度从180℃逐步升至280℃(分成10个阶段，分别为180℃-190℃-200℃-210℃-220℃-230℃-240℃-250℃-260℃-270℃-280℃)，缩聚反应动力学强化过程时间为80min；同时加入扩链剂磷酸酯，扩链剂的添加量为己内酰胺的0.5wt％；
所获熔体分子量为15960，相对粘度为2.5，低聚物含量在1.5％以下，其中环状二聚体含量为0.2％以下；缩聚反应动力学强化结束后即制得尼龙6聚合物。
实施例11 尼龙6聚合方法
一种尼龙6聚合方法，采用分段聚合的方法制备尼龙6，具体制备方法如下：
第一段为开环反应阶段：在温度为200℃和压力为3MPa条件下，将己内酰胺、水和催化剂混合后进行预聚合，开环反应时间为8h；其中水含量为己内酰胺的15wt％，催化剂含量为己内酰胺的10wt％，催化剂为H3PO4；同时加入内酯共聚物(m＝10，分子量3000)，所添加量为己内酰胺的40wt％；
所获产物数均分子量为1800，低聚物含量20％，环状二聚体含量0.1％以下，熔体粘度为90Pa·s；
第二段为预缩聚阶段：在压力为150Pa和温度为210℃条件下，将开环反应所得产物进行缩聚反应，预缩聚反应时间为1h；同时加入分子量稳定剂H(CH2)bNH2，其中b＝16，添加量为己内酰胺的0.01wt％；
所得预聚物的熔体分子量为5000，低聚物含量在5％，其中环状二聚体含量为0.1％，熔体粘度为950Pa·s；
第三段为缩聚反应动力学强化阶段：在压力为80Pa条件下聚合，聚合温度从210℃逐步升至280℃(分成7个阶段，分别为210℃-220℃-230℃-240℃-250℃-260℃-270℃-280℃)，缩聚反应动力学强化过程时间为50min；同时加入以铝酸盐作为发光基质，以稀土镧系元素铕作为激活剂的荧光材料，添加量为己内酰胺的10wt％；同时加入扩链剂双异氰酸酯，扩链剂的添加量为己内酰胺的0.5wt％；
所获熔体分子量为31920，相对粘度为3.8，低聚物含量在1.5％以下，其中环状二聚体含量为0.2％以下；缩聚反应动力学强化结束后即制得尼龙6聚合物。
实施例12 尼龙6聚合物的熔体直纺方法
实施例1所述尼龙6聚合物在缩聚反应动力学强化过程结束后，立即按照尼龙6纺丝工艺直接纺丝，纺丝温度为240℃，第一导丝盘速度为4500m/min，第二导丝盘速度为5000m/min，拉伸倍数为1.5倍，冷却风温为15℃，风速0.5m/s，相对湿度为90％，得到全拉伸丝。
上述纺丝的喷丝微孔截面形状是三角形；
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加功能性母粒或色母粒，混合均匀后再按照尼龙6纺丝工艺直接纺丝，添加量为尼龙6聚合物的1wt％。所述功能性母粒或色母粒的基体是尼龙6。所述功能性母粒中所含功能性助剂是抗氧化剂1010，含量为功能性母粒的30wt％。所述色母粒中所用着色剂为酞菁红。
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加聚合物切片，混合均匀后立即按照尼龙6纺丝工艺直接纺丝，所述聚合物切片添加量为尼龙6熔体的5wt％。所述聚合物切片是聚对苯二甲酸乙二醇酯。
实施例13 尼龙6聚合物的熔体直纺方法
实施例2所述尼龙6聚合物在缩聚反应动力学强化过程结束后，立即按照尼龙6纺丝工艺直接纺丝，纺丝温度为280℃，第一导丝盘速度为4000m/min，第二导丝盘速度为6000m/min，拉伸倍数为1.1倍，冷却风温为25℃，风速1m/s，相对湿度为60％，得到全拉伸丝。
上述纺丝的喷丝微孔截面形状是十字形；
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加功能性母粒或色母粒，混合均匀后再按照尼龙6纺丝工艺直接纺丝，添加量为尼龙6聚合物的30wt％。所述功能性母粒或色母粒的基体是尼龙6T。所述功能性母粒中所含功能性助剂是抗氧化剂168，含量为功能性母粒的10wt％。所述色母粒中所用着色剂为酞菁蓝。
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加聚合物切片，混合均匀后立即按照尼龙6纺丝工艺直接纺丝，所述聚合物切片添加量为尼龙6熔体的50wt％。所述聚合物切片是尼龙6。
实施例14 尼龙6聚合物的熔体直纺方法
实施例3所述尼龙6聚合物在缩聚反应动力学强化过程结束后，立即按照尼龙6纺丝工艺直接纺丝，纺丝温度为260℃，第一导丝盘速度为4300m/min，第二导丝盘速度为5500m/min，拉伸倍数为1.3倍，冷却风温为20℃，风速0.8m/s，相对湿度为70％，得到全拉伸丝。
上述纺丝的喷丝微孔截面形状是多角形；
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加功能性母粒或色母粒，混合均匀后再按照尼龙6纺丝工艺直接纺丝，添加量为尼龙6聚合物的5wt％。所述功能性母粒或色母粒的基体是尼龙612和聚对苯二甲酸乙二醇酯。所述功能性母粒中所含功能性助剂是抗氧化剂616，含量为功能性母粒的15wt％。所述色母粒中所用着色剂为酞菁绿。
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加聚合物切片，混合均匀后立即按照尼龙6纺丝工艺直接纺丝，所述聚合物切片添加量为尼龙6熔体的10wt％。所述聚合物切片是聚乙二醇(聚乙二醇分子量为400，聚乙二醇端基是羟基)。
实施例15 尼龙6聚合物的熔体直纺方法
实施例4所述尼龙6聚合物在缩聚反应动力学强化过程结束后，立即按照尼龙6纺丝工艺直接纺丝，纺丝温度为270℃，第一导丝盘速度为4250m/min，第二导丝盘速度为5000m/min，拉伸倍数为1.4倍，冷却风温为23℃，风速0.8m/s，相对湿度为80％，得到全拉伸丝。
上述纺丝的喷丝微孔截面形状是中空纤维；
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加功能性母粒或色母粒，混合均匀后再按照尼龙6纺丝工艺直接纺丝，添加量为尼龙6聚合物的10wt％。所述功能性母粒或色母粒的基体是尼龙610和聚对苯二甲酸丁二醇酯。所述功能性母粒中所含功能性助剂是抗紫外剂水杨酸，含量为功能性母粒的20wt％。所述色母粒中所用 着色剂为耐晒大红。
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加聚合物切片，混合均匀后立即按照尼龙6纺丝工艺直接纺丝，所述聚合物切片添加量为尼龙6熔体的15wt％。所述聚合物切片是聚对苯二甲酸丁二醇酯和尼龙6T。
实施例16 尼龙6聚合物的熔体直纺方法
实施例5所述尼龙6聚合物在缩聚反应动力学强化过程结束后，立即按照尼龙6纺丝工艺直接纺丝，纺丝温度为240℃，纺丝速度为1500m/min，冷却风温为30℃，风速0.3m/s，相对湿度为60％，得到未取向丝。
上述纺丝的喷丝微孔截面形状是U形；
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加功能性母粒或色母粒，混合均匀后再按照尼龙6纺丝工艺直接纺丝，添加量为尼龙6聚合物的12wt％。所述功能性母粒或色母粒的基体是聚对苯二甲酸丙二醇酯。所述功能性母粒中所含功能性助剂是抗紫外剂二苯甲酮系苯并三唑系，含量为功能性母粒的25wt％。所述色母粒中所用着色剂为大分子红。
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加聚合物切片，混合均匀后立即按照尼龙6纺丝工艺直接纺丝，所述聚合物切片添加量为尼龙6熔体的20wt％。所述聚合物切片是尼龙612和聚乙二醇(分子量为10000，经过改性的端基为羧基的聚乙二醇)。
实施例17 尼龙6聚合物的熔体直纺方法
实施例6所述尼龙6聚合物在缩聚反应动力学强化过程结束后，立即按照尼龙6纺丝工艺直接纺丝，纺丝温度为280℃，纺丝速度为700m/min，冷却风温为20℃，风速1m/s，相对湿度为80％，得到未取向丝。
上述纺丝的喷丝微孔截面形状是T形；
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加功能性母粒或色母粒，混合均匀后再按照尼龙6纺丝工艺直接纺丝，添加量为尼龙6聚合物的1wt％。所述功能性母粒或色母粒的基体是尼龙410和水溶性聚酯。所述功能性母粒中所含功能性助剂是抗紫外剂滑石粉，含量为功能性母粒的30wt％。所述色母粒中所用着色剂为大分子黄。
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加聚 合物切片，混合均匀后立即按照尼龙6纺丝工艺直接纺丝，所述聚合物切片添加量为尼龙6熔体的25wt％。所述聚合物切片是聚对苯二甲酸丙二醇酯。
实施例18 尼龙6聚合物的熔体直纺方法
实施例7所述尼龙6聚合物在缩聚反应动力学强化过程结束后，立即按照尼龙6纺丝工艺直接纺丝，纺丝温度为260℃，纺丝速度为900m/min，冷却风温为25℃，风速0.5m/s，相对湿度为70％，得到未取向丝。
上述纺丝的喷丝微孔截面形状是Y形；
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加功能性母粒或色母粒，混合均匀后再按照尼龙6纺丝工艺直接纺丝，添加量为尼龙6聚合物的30wt％。所述功能性母粒或色母粒的基体是聚乙二醇(分子量为400，聚乙二醇端基是羟基)。所述功能性母粒中所含功能性助剂是抗紫外剂碳酸钙，含量为功能性母粒的10wt％。所述色母粒中所用着色剂为永固黄。
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加聚合物切片，混合均匀后立即按照尼龙6纺丝工艺直接纺丝，所述聚合物切片添加量为尼龙6熔体的30wt％。所述聚合物切片是尼龙612。
实施例19 尼龙6聚合物的熔体直纺方法
实施例8所述尼龙6聚合物在缩聚反应动力学强化过程结束后，立即按照尼龙6纺丝工艺直接纺丝，纺丝温度为270℃，纺丝速度为1000m/min，冷却风温为28℃，风速0.6m/s，相对湿度为65％，得到未取向丝。
上述纺丝的喷丝微孔截面形状是多边形；
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加功能性母粒或色母粒，混合均匀后再按照尼龙6纺丝工艺直接纺丝，添加量为尼龙6聚合物的15wt％。所述功能性母粒或色母粒的基体是尼龙212和聚乙二醇(分子量为20000，聚乙二醇端基是羟基)。所述功能性母粒中所含功能性助剂是抗菌剂纳米二氧化钛，含量为功能性母粒的10wt％。所述色母粒中所用着色剂为颜料红179。
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加聚合物切片，混合均匀后立即按照尼龙6纺丝工艺直接纺丝，所述聚合物切片添加量为尼龙6熔体的35wt％。所述聚合物切片是聚乙二醇(分子量为400经过改性的端基为氨基的聚乙二醇)。
实施例20 尼龙6聚合物的熔体直纺方法
实施例9所述尼龙6聚合物在缩聚反应动力学强化过程结束后，立即按照尼龙6纺丝工艺直接纺丝，纺丝温度为280℃，纺丝速度为4000m/min，冷却风温为15℃，风速0.3m/s，相对湿度为80％，得到预取向丝。
上述纺丝的喷丝微孔截面形状是工字形；
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加功能性母粒或色母粒，混合均匀后再按照尼龙6纺丝工艺直接纺丝，添加量为尼龙6聚合物的20wt％。所述功能性母粒或色母粒的基体是尼龙11。所述功能性母粒中所含功能性助剂是抗菌剂氧化锌，含量为功能性母粒的30wt％。所述色母粒中所用着色剂为颜料蓝60。
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加聚合物切片，混合均匀后立即按照尼龙6纺丝工艺直接纺丝，所述聚合物切片添加量为尼龙6熔体的40wt％。所述聚合物切片是水溶性聚酯。
实施例21 尼龙6聚合物的熔体直纺方法
实施例10所述尼龙6聚合物在缩聚反应动力学强化过程结束后，立即按照尼龙6纺丝工艺直接纺丝，纺丝温度为240℃，纺丝速度为4500m/min，冷却风温为25℃，风速0.6m/s，相对湿度为60％，得到预取向丝。
上述纺丝的喷丝微孔截面形状是三角形；
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加功能性母粒或色母粒，混合均匀后再按照尼龙6纺丝工艺直接纺丝，添加量为尼龙6聚合物的30wt％。所述功能性母粒或色母粒的基体是支链尼龙。所述功能性母粒中所含功能性助剂是抗菌剂氧化铁，含量为功能性母粒的15wt％。所述色母粒中所用着色剂为溶剂紫59。
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加聚合物切片，混合均匀后立即按照尼龙6纺丝工艺直接纺丝，所述聚合物切片添加量为尼龙6熔体的45wt％。所述聚合物切片是尼龙1212。
实施例22 尼龙6聚合物的熔体直纺方法
实施例11所述尼龙6聚合物在缩聚反应动力学强化过程结束后，立即按照尼龙6纺丝工艺直接纺丝，纺丝温度为260℃，纺丝速度为4300m/min，冷却风温为20℃，风速0.4m/s，相对湿度为70％，得到预取向丝。
上述纺丝的喷丝微孔截面形状是十字形；
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加功能性母粒或色母粒，混合均匀后再按照尼龙6纺丝工艺直接纺丝，添加量为尼龙6聚合物的1wt％。所述功能性母粒或色母粒的基体是聚对苯二甲酸乙二醇酯。所述功能性母粒中所含功能性助剂是分子式为
Figure PCTCN2016080024-appb-000010
季铵盐类化合物，其中，R1、R2＝C8，R1、R2相同；X-为Cl-，含量为功能性母粒的20wt％。所述色母粒中所用着色剂为溶剂红181。
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加聚合物切片，混合均匀后立即按照尼龙6纺丝工艺直接纺丝，所述聚合物切片添加量为尼龙6熔体的50wt％。所述聚合物切片是聚对苯二甲酸丙二醇酯和水溶性聚酯。
实施例23 尼龙6聚合物的熔体直纺方法
实施例1所述尼龙6聚合物在缩聚反应动力学强化过程结束后，立即按照尼龙6纺丝工艺直接纺丝，纺丝温度为270℃，纺丝速度为4400m/min，冷却风温为23℃，风速0.5m/s，相对湿度为75％，得到预取向丝。
上述纺丝的喷丝微孔截面形状是多角形；
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加功能性母粒或色母粒，混合均匀后再按照尼龙6纺丝工艺直接纺丝，添加量为尼龙6聚合物的15wt％。所述功能性母粒或色母粒的基体是尼龙1212。所述功能性母粒中所含功能性助剂是分子式为
Figure PCTCN2016080024-appb-000011
季铵盐类化合物，其中，R1、R2＝C20，R1、R2相同；X-为Br-，含量为功能性母粒的25wt％。所述色母粒中所用着色剂为溶剂蓝132。
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加聚合物切片，混合均匀后立即按照尼龙6纺丝工艺直接纺丝，所述聚合物切片添加量为尼龙6熔体的5wt％。所述聚合物切片是聚对苯二甲酸乙二醇酯。
实施例24 尼龙6聚合物的熔体直纺方法
实施例2所述尼龙6聚合物在缩聚反应动力学强化过程结束后，立即按照尼龙6纺丝工艺直接纺丝，纺丝温度为280℃，纺丝速度为4500m/min，冷却风温为15℃，风速0.5m/s，相对湿度为90％，得到高取向丝。
上述纺丝的喷丝微孔截面形状是中空纤维；
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加功能性母粒或色母粒，混合均匀后再按照尼龙6纺丝工艺直接纺丝，添加量为尼龙6聚合物的30wt％。所述功能性母粒或色母粒的基体是聚对苯二甲酸丁二醇酯。所述功能性母粒中所含功能性助剂是阻燃剂硼酸锌，含量为功能性母粒的10wt％。所述色母粒中所用着色剂为溶剂绿29。
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加聚合物切片，混合均匀后立即按照尼龙6纺丝工艺直接纺丝，所述聚合物切片添加量为尼龙6熔体的10wt％。所述聚合物切片是水溶性聚酯。
实施例25 尼龙6聚合物的熔体直纺方法
实施例3所述尼龙6聚合物在缩聚反应动力学强化过程结束后，立即按照尼龙6纺丝工艺直接纺丝，纺丝温度为240℃，纺丝速度为6000m/min，冷却风温为20℃，风速0.3m/s，相对湿度为80％，得到高取向丝。
上述纺丝的喷丝微孔截面形状是U形；
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加功能性母粒或色母粒，混合均匀后再按照尼龙6纺丝工艺直接纺丝，添加量为尼龙6聚合物的1wt％。所述功能性母粒或色母粒的基体是尼龙12。所述功能性母粒中所含功能性助剂是阻燃剂多磷酸铵，含量为功能性母粒的30wt％。所述色母粒中所用着色剂为溶剂黄135。
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加聚合物切片，混合均匀后立即按照尼龙6纺丝工艺直接纺丝，所述聚合物切片添加量为尼龙6熔体的15wt％。所述聚合物切片是尼龙46和尼龙410。
实施例26 尼龙6聚合物的熔体直纺方法
实施例4所述尼龙6聚合物在缩聚反应动力学强化过程结束后，立即按照尼龙6纺丝工艺直接纺丝，纺丝温度为250℃，纺丝速度为4700m/min，冷却风温为18℃，风速0.4m/s，相对湿度为85％，得到高取向丝。
上述纺丝的喷丝微孔截面形状是T形；
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加功能性母粒或色母粒，混合均匀后再按照尼龙6纺丝工艺直接纺丝，添加量为尼龙6聚合物的20wt％。所述功能性母粒或色母粒的基体是尼龙26。所述功能性母粒中所含功能性助剂是1,3,6-三(4,6-二氨基-2-硫基三嗪)己烷与三聚氰酸的混合物，含量为功能性母粒的15wt％。所 述色母粒中所用着色剂为溶剂黄135和颜料红179。
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加聚合物切片，混合均匀后立即按照尼龙6纺丝工艺直接纺丝，所述聚合物切片添加量为尼龙6熔体的20wt％。所述聚合物切片是尼龙尼龙46。
实施例27 尼龙6聚合物的熔体直纺方法
实施例5所述尼龙6聚合物在缩聚反应动力学强化过程结束后，立即按照尼龙6纺丝工艺直接纺丝，纺丝温度为260℃，纺丝速度为4800m/min，冷却风温为16℃，风速0.4m/s，相对湿度为88％，得到高取向丝。
上述纺丝的喷丝微孔截面形状是Y形；
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加功能性母粒或色母粒，混合均匀后再按照尼龙6纺丝工艺直接纺丝，添加量为尼龙6聚合物的25wt％。所述功能性母粒或色母粒的基体是聚对苯二甲酸丙二醇酯。所述功能性母粒中所含功能性助剂是负离子发生材料奇冰石，含量为功能性母粒的10wt％。所述色母粒中所用着色剂为溶剂黄135和溶剂黄167。
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加聚合物切片，混合均匀后立即按照尼龙6纺丝工艺直接纺丝，所述聚合物切片添加量为尼龙6熔体的25wt％。所述聚合物切片是聚乙二醇(分子量为20000，聚乙二醇端基是羟基)。
实施例28 尼龙6聚合物的熔体直纺方法
实施例6所述尼龙6聚合物在缩聚反应动力学强化过程结束后，立即按照尼龙6纺丝工艺直接纺丝得到膨化变形丝，纺丝温度为280℃，冷却风温为20℃，风速0.3m/s，相对湿度为80％，喂入辊温度为60℃，拉伸辊温度为190℃，喂入速度为300m/min，拉伸速度为1000m/min，拉伸倍数为3.5倍，变形热空气温度为230℃，空气喷射压力为490kPa，卷绕速度为600m/min，冷却空气温度为25℃。
上述纺丝的喷丝微孔截面形状是多边形；
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加功能性母粒或色母粒，混合均匀后再按照尼龙6纺丝工艺直接纺丝，添加量为尼龙6聚合物的30wt％。所述功能性母粒或色母粒的基体是聚对苯二甲酸丙二醇酯和水溶性聚酯。所述功能性母粒中所含功能性助剂是负离子发生材料电气石，含量为功能性母粒的30wt％。所述色母粒中所用着色剂为溶剂紫37。
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加聚合物切片，混合均匀后立即按照尼龙6纺丝工艺直接纺丝，所述聚合物切片添加量为尼龙6熔体的30wt％。所述聚合物切片是聚对苯二甲酸丁二醇酯。
实施例29 尼龙6聚合物的熔体直纺方法
实施例7所述尼龙6聚合物在缩聚反应动力学强化过程结束后，立即按照尼龙6纺丝工艺直接纺丝得到膨化变形丝，纺丝温度为240℃，冷却风温为30℃，风速1m/s，相对湿度为60％，喂入辊温度为120℃，拉伸辊温度为100℃，喂入速度为1000m/min，拉伸速度为3500m/min，拉伸倍数为5倍，变形热空气温度为190℃，空气喷射压力为196kPa，卷绕速度为3000m/min，冷却空气温度为25℃。
上述纺丝的喷丝微孔截面形状是工字形；
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加功能性母粒或色母粒，混合均匀后再按照尼龙6纺丝工艺直接纺丝，添加量为尼龙6聚合物的1wt％。所述功能性母粒或色母粒的基体是尼龙46。所述功能性母粒中所含功能性助剂是荧光材料(以碱土金属的硫化物、铝酸盐作为发光基质，以稀土镧系元素铕、钐、铒或钕，作为激活剂)，含量为功能性母粒的10wt％。所述色母粒中所用着色剂为溶剂红143。
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加聚合物切片，混合均匀后立即按照尼龙6纺丝工艺直接纺丝，所述聚合物切片添加量为尼龙6熔体的35wt％。所述聚合物切片是水溶性聚酯。
实施例30 尼龙6聚合物的熔体直纺方法
实施例8所述尼龙6聚合物在缩聚反应动力学强化过程结束后，立即按照尼龙6纺丝工艺直接纺丝得到膨化变形丝，纺丝温度为260℃，冷却风温为25℃，风速0.5m/s，相对湿度为70％，喂入辊温度为80℃，拉伸辊温度为120℃，喂入速度为500m/min，拉伸速度为2000m/min，拉伸倍数为4倍，变形热空气温度为200℃，空气喷射压力为300kPa，卷绕速度为1000m/min，冷却空气温度为25℃。
上述纺丝的喷丝微孔截面形状是三角形；
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加功能性母粒或色母粒，混合均匀后再按照尼龙6纺丝工艺直接纺丝，添加量为尼龙6聚合物的10wt％。所述功能性母粒或色母粒的基体是尼龙6T。所述功能性母粒中所含功能性助剂是负离子发生材料蛋白石，含量为功能性母粒的25wt％。所述色母粒中所用着色剂为溶剂蓝94。
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加聚合物切片，混合均匀后立即按照尼龙6纺丝工艺直接纺丝，所述聚合物切片添加量为尼龙6熔体的40wt％。所述聚合物切片是聚对苯二甲酸丙二醇酯。
实施例31 尼龙6聚合物的熔体直纺方法
实施例9所述尼龙6聚合物在缩聚反应动力学强化过程结束后，立即按照尼龙6纺丝工艺直接纺丝得到膨化变形丝，纺丝温度为270℃，冷却风温为28℃，风速0.8m/s，相对湿度为75％，喂入辊温度为100℃，拉伸辊温度为150℃，喂入速度为800m/min，拉伸速度为3000m/min，拉伸倍数为4.5倍，变形热空气温度为210℃，空气喷射压力为350kPa，卷绕速度为2000m/min，冷却空气温度为25℃。
上述纺丝的喷丝微孔截面形状是十字形；
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加功能性母粒或色母粒，混合均匀后再按照尼龙6纺丝工艺直接纺丝，添加量为尼龙6聚合物的20wt％。所述功能性母粒或色母粒的基体是尼龙212。所述功能性母粒中所含功能性助剂是负离子发生材料奇才石，含量为功能性母粒的20wt％。所述色母粒中所用着色剂为炭黑。
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加聚合物切片，混合均匀后立即按照尼龙6纺丝工艺直接纺丝，所述聚合物切片添加量为尼龙6熔体的45wt％。所述聚合物切片是聚对苯二甲酸丁二醇酯。
实施例32 尼龙6聚合物的熔体直纺方法
实施例10所述尼龙6聚合物在缩聚反应动力学强化过程结束后，直接应用于复合纺丝，所述复合纺丝是并列型，所述复合纺丝除尼龙6之外另一组分是尼龙6T，所述尼龙6聚合物与另一组分的质量比为3:7。
上述纺丝的喷丝微孔截面形状是多角形；
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加功能性母粒或色母粒，混合均匀后再按照尼龙6纺丝工艺直接纺丝，添加量为尼龙6聚合物的1wt％。所述功能性母粒或色母粒的基体是聚对苯二甲酸丙二醇酯。所述功能性母粒中所含功能性助剂是阻燃剂双(六氯环戊二烯)环辛烷，含量为功能性母粒的20wt％。所述色母粒中所用着色剂为颜料黄184。
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加聚合物切片，混合均匀后立即按照尼龙6纺丝工艺直接纺丝，所述聚合物切片添加量为尼龙6 熔体的50wt％。所述聚合物切片是聚对苯二甲酸丁二醇酯。
实施例33 尼龙6聚合物的熔体直纺方法
实施例11所述尼龙6聚合物在缩聚反应动力学强化过程结束后，直接应用于复合纺丝，所述复合纺丝是海岛型；所述复合纺丝除尼龙6之外另一组分是尼龙610，所述尼龙6聚合物与另一组分的质量比为7:3。
上述纺丝的喷丝微孔截面形状是中空纤维；
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加功能性母粒或色母粒，混合均匀后再按照尼龙6纺丝工艺直接纺丝，添加量为尼龙6聚合物的30wt％。所述功能性母粒或色母粒的基体是尼龙610。所述功能性母粒中所含功能性助剂是阻燃剂十溴二苯醚，含量为功能性母粒的20wt％。所述色母粒中所用着色剂为氧化铁红。
上述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加聚合物切片，混合均匀后立即按照尼龙6纺丝工艺直接纺丝，所述聚合物切片添加量为尼龙6熔体的50wt％。所述聚合物切片是水溶性聚酯。
实施例34 尼龙6聚合物纺成纤维后织成的面料
将实施例1所述尼龙聚合物纺制成的尼龙6纤维，然后通过梭织形成面料，面料是平纹，然后进行染色，获得不同规格颜色的布料。
面料的染色生产工序为：前处理退浆-热水清洗坯布-升温染色-固色-降温清洗-面料出机防水定型-成品检验-成品打卷。
所述前处理退浆温度为80℃，退浆时间为6h，其退浆助剂配方为：纯碱10g/L，去油灵15g/L。
所述升温染色工艺为始染温度为40℃，以1℃/min的速率升温，升温至90℃再保温40min；染色剂浓度为2％(omf)，浴比为1:10。
所述固色工艺为温度为90℃，固色时间为60min；固色剂浓度为2％(omf)，浴比为1:10。
在染色及固色过程中，加入助剂，所述助剂添加量为5g/L，所述助剂包括软水剂NORM02、匀染剂ACID03和缓染剂硫酸铵。
实施例35 尼龙6聚合物纺成纤维后织成的面料
将实施例2所述尼龙聚合物纺制成的尼龙6纤维，然后通过针织形成面料，面料是斜纹，然后进行染色，获得不同规格颜色的布料。
面料的染色生产工序为：前处理退浆-热水清洗坯布-升温染色-固色-降温清洗-面料出机防水定型-成品检验-成品打卷。
所述前处理退浆温度为60℃，退浆时间为12h，其退浆助剂配方为：纯碱20g/L，去油灵10g/L。
所述升温染色工艺为始染温度为30℃，以3℃/min的速率升温，升温至95℃再保温40min；染色剂浓度为0.5％(omf)，浴比为1:20。
所述固色工艺为温度为95℃，固色时间为20min；固色剂浓度为0.5％(omf)，浴比为1:20。
在染色及固色过程中，加入助剂，所述助剂添加量为10g/L，所述助剂包括软水剂NORM02、匀染剂ACID16和缓染剂硫酸铵。
实施例36 尼龙6聚合物纺成纤维后织成的面料
将实施例3所述尼龙聚合物纺制成的尼龙6纤维，然后通过梭织形成面料，面料是缎纹，然后进行染色，获得不同规格颜色的布料。
面料的染色生产工序为：前处理退浆-热水清洗坯布-升温染色-固色-降温清洗-面料出机防水定型-成品检验-成品打卷。
所述前处理退浆温度为70℃，退浆时间为8h，其退浆助剂配方为：纯碱15g/L，去油灵12g/L。
所述升温染色工艺为始染温度为35℃，以2℃/min的速率升温，升温至92℃再保温40min；染色剂浓度为0.8％(omf)，浴比为1:15。
所述固色工艺为温度为92℃，固色时间为30min；固色剂浓度为0.8％(omf)，浴比为1:15。
在染色及固色过程中，加入助剂，所述助剂添加量为7g/L，所述助剂包括软水剂NORM02、匀染剂ACID03和缓染剂硫酸铵。
实施例37 尼龙6聚合物纺成纤维后织成的面料
将实施例4所述尼龙聚合物纺制成的尼龙6纤维，然后通过针织形成面料，面料是平纹，然后进行染色，获得不同规格颜色的布料。
面料的染色生产工序为：前处理退浆-热水清洗坯布-升温染色-固色-降温清洗-面料出机防水定型-成品检验-成品打卷。
所述前处理退浆温度为750℃，退浆时间为10h，其退浆助剂配方为：纯碱18g/L，去油 灵13g/L。
所述升温染色工艺为始染温度为38℃，以2℃/min的速率升温，升温至93℃再保温40min；染色剂浓度为1.5％(omf)，浴比为1:18。
所述固色工艺为温度为93℃，固色时间为40min；固色剂浓度为1.5％(omf)，浴比为1:18。
在染色及固色过程中，加入助剂，所述助剂添加量为5-10g/L，所述助剂包括软水剂NORM02、匀染剂ACID16和缓染剂硫酸铵。
实施例38 尼龙6聚合方法的装置
如图2所示，一种尼龙6聚合方法的装置，料仓1的作用是储存己内酰胺，其通过管道与原料加热罐3相连，原料加热罐3的作用是将己内酰胺熔化；加压开环釜4通过管道与原料加热罐3相连，加压开环釜4的作用是通过加压的方式，促使己内酰胺水解开环，获得环状低聚物含量较低的预聚物；缩聚釜5通过管道与加压开环釜4相连，缩聚釜5的作用是将加压开环釜4的产物预缩聚至分子链缠结点附近的分子量，并将大量的未反应的单体抽除，此时熔体粘度较低，因此对于缩聚的条件要求不高；液相增粘釜6通过管道与缩聚釜5相连，液相增粘釜6的作用是将缩聚釜5的产物通过高真空缩聚反应动力学强化至目标分子量，并将未反应的单体及水分快速抽除，此时熔体粘度较高，因此对于缩聚的条件要求高；在缩聚釜5、液相增粘釜6分别与缓冲罐7通过管道相连，缓冲罐7的作用是收集缩聚釜5、液相增粘釜6中被抽取出来的小分子，并将其输送到浓缩罐8中；浓缩罐8与缓冲罐7通过管道相连，浓缩罐8的作用是将缓冲罐7中输送过来的单体浓缩，并重新输送到原料加热罐3中，继续参与反应。被送到浓缩器8浓缩并属性重新利用；得到的熔体直接被输送到纺丝组件进行纺丝，随后织造、染整，得到最终产品。
己内酰胺经过料仓1到与原料加热罐3，己内酰胺熔融后被输送到加压开环釜4，开环结束后所获预聚物被输送至缩聚釜5进行真空缩聚，所获聚合物被输送至液相增粘釜6进行高真空缩聚，得到的熔体直接被输送到纺丝组件进行纺丝，随后织造、染整，得到最终产品。在5、6中被抽出的己内酰胺将被送到浓缩器8浓缩并属性重新利用。
实施例39 尼龙6聚合方法
一种尼龙6聚合方法，采用分段聚合的方法制备尼龙6，具体制备方法如下：
第一段为开环反应阶段：在温度为200℃和压力为3MPa条件下，将己内酰胺、水和催化剂混合后进行预聚合，开环反应时间为6h；其中水含量为己内酰胺的15wt％，催化剂含量 为己内酰胺的10wt％，催化剂为HNO3、NH3和[Al(H2O)6](HNO3、NH3和[Al(H2O)6]质量比为2:1:1)；同时加入内酯均聚物(m＝1，分子量1000)，所添加量为己内酰胺的10wt％；
所获产物数均分子量为2000，低聚物含量30％，环状二聚体含量0.1％以下，熔体粘度为5Pa·s；
第二段为预缩聚阶段：在压力为150Pa和温度为180℃条件下，将开环反应所得产物进行缩聚反应，预缩聚反应时间为3h；同时加入分子量稳定剂二元胺H2N(CH2)dNH2(其中d＝1)和芳香族二元酸对苯二甲酸(二元胺和对苯二甲酸的质量比为1:1)，稳定剂添加量为己内酰胺的8wt％；同时加入碳纳米管，添加量为己内酰胺的8wt％；
所得预聚物的熔体分子量为4000，低聚物含量在2％，其中环状二聚体含量为0.1％，熔体粘度为800Pa·s；
第三段为液相增粘阶段：采用液相增粘釜，在压力为80Pa条件下聚合，聚合温度从180℃逐步升至280℃(分成10个阶段，分别为180℃-190℃-200℃-210℃-220℃-230℃-240℃-250℃-260℃-270℃-280℃)，液相增粘反应时间为80min；同时加入扩链剂磷酸酯，扩链剂的添加量为己内酰胺的0.5wt％；
所获熔体分子量为15960，相对粘度为2.5，低聚物含量在1.5％以下，其中环状二聚体含量为0.2％以下；液相增粘结束后即制得尼龙6聚合物。
实施例40 尼龙6聚合物的熔体直纺方法
实施例39所述尼龙6聚合物在液相增粘反应结束后，立即按照尼龙6纺丝工艺直接纺丝，纺丝温度为250℃，纺丝速度为4500m/min，冷却风温为25℃，风速0.6m/s，相对湿度为70％，得到预取向丝。
上述纺丝的喷丝微孔截面形状是U形；
上述尼龙6聚合物在液相增粘反应结束后，在熔体输送过程中，在线添加功能性母粒或色母粒，混合均匀后再按照尼龙6纺丝工艺直接纺丝，添加量为尼龙6聚合物的30wt％。所述功能性母粒或色母粒的基体是支链尼龙。所述功能性母粒中所含功能性助剂是碳纳米管，含量为功能性母粒的15wt％。所述色母粒中所用着色剂为颜料棕41。
上述尼龙6聚合物在液相增粘反应结束后，在熔体输送过程中，在线添加聚合物切片，混合均匀后立即按照尼龙6纺丝工艺直接纺丝，所述聚合物切片添加量为尼龙6熔体的45wt％。所述聚合物切片是尼龙1212。
实施例41 尼龙6聚合方法
一种尼龙6聚合方法，采用分段聚合的方法制备尼龙6，具体制备方法如下：
第一段为开环反应阶段：在温度为210℃和压力为2MPa条件下，将己内酰胺、水和催化剂混合后进行预聚合，开环反应时间为6h；其中水含量为己内酰胺的15wt％，催化剂含量为己内酰胺的10wt％，催化剂为HNO3、NH3和[Al(H2O)6](HNO3、NH3和[Al(H2O)6]质量比为1:1:2)；同时加入内酯均聚物(m＝1，分子量1000)，所添加量为己内酰胺的10wt％；
所获产物数均分子量为2000，低聚物含量30％，环状二聚体含量0.1％以下，熔体粘度为5Pa·s；
第二段为预缩聚阶段：在压力为100Pa和温度为190℃条件下，将开环反应所得产物进行缩聚反应，预缩聚反应时间为3h；同时加入分子量稳定剂二元胺邻苯二胺和芳香族二元酸间苯二甲酸(邻苯二胺和间苯二甲酸的质量比为1:2)，稳定剂添加量为己内酰胺的8wt％；同时加入石墨烯，添加量为己内酰胺的6wt％；
所得预聚物的熔体分子量为4000，低聚物含量在2％，其中环状二聚体含量为0.1％，熔体粘度为800Pa·s；
第三段为液相增粘阶段：采用液相增粘釜，在压力为80Pa条件下聚合，聚合温度从180℃逐步升至280℃(分成10个阶段，分别为180℃-190℃-200℃-210℃-220℃-230℃-240℃-250℃-260℃-270℃-280℃)，液相增粘反应时间为80min；同时加入扩链剂磷酸酯，扩链剂的添加量为己内酰胺的0.5wt％；
所获熔体分子量为15960，相对粘度为2.5，低聚物含量在1.5％以下，其中环状二聚体含量为0.2％以下；液相增粘结束后即制得尼龙6聚合物。
实施例42 尼龙6聚合物的熔体直纺方法
实施例41所述尼龙6聚合物在液相增粘反应结束后，立即按照尼龙6纺丝工艺直接纺丝，纺丝温度为270℃，纺丝速度为4500m/min，冷却风温为25℃，风速0.6m/s，相对湿度为75％，得到预取向丝。
上述纺丝的喷丝微孔截面形状是U形；
上述尼龙6聚合物在液相增粘反应结束后，在熔体输送过程中，在线添加功能性母粒或色母粒，混合均匀后再按照尼龙6纺丝工艺直接纺丝，添加量为尼龙6聚合物的30wt％。所述功能性母粒或色母粒的基体是支链尼龙。所述功能性母粒中所含功能性助剂是石墨烯，含量为功能性母粒的15wt％。所述色母粒中所用着色剂为颜料黄184。
上述尼龙6聚合物在液相增粘反应结束后，在熔体输送过程中，在线添加聚合物切片，混合均匀后立即按照尼龙6纺丝工艺直接纺丝，所述聚合物切片添加量为尼龙6熔体的 45wt％。所述聚合物切片是尼龙1212。
实施例43 尼龙6聚合方法
一种尼龙6聚合方法，采用分段聚合的方法制备尼龙6，具体制备方法如下：
第一段为开环反应阶段：在温度为260℃和压力为2MPa条件下，将己内酰胺、水和催化剂混合后进行预聚合，开环反应时间为8h；其中水含量为己内酰胺的15wt％，催化剂含量为己内酰胺的10wt％，催化剂为HCl；同时加入分子量稳定剂H(CH2)aCOOH，其中a＝1，添加量为己内酰胺的0.01wt％；同时加入内酰胺，所添加量为己内酰胺的49wt％；同时加入抗氧化剂1010，添加量为己内酰胺的0.01wt％；同时加入扩链剂双环氧乙烷，分子式为
Figure PCTCN2016080024-appb-000012
其中R＝C1，扩链剂的添加量为己内酰胺的0.02wt％；
所获产物数均分子量为1900，低聚物含量25％，环状二聚体含量0.1％以下，熔体粘度为10Pa·s；
第二段为预缩聚阶段：在压力为160Pa和温度为200℃条件下，将开环反应所得产物进行缩聚反应，预缩聚反应时间为2.5h；
所得预聚物的熔体分子量为5200，低聚物含量在7％，其中环状二聚体含量为0.1％，熔体粘度为90Pa·s；
第三段为液相增粘阶段：在压力为80Pa条件下聚合，聚合温度从210℃逐步升至280℃(分成7个阶段，分别为210℃-220℃-230℃-240℃-250℃-260℃-270℃-280℃)，液相增粘反应时间为40min；
所获熔体分子量为29640，相对粘度为3.6，低聚物含量在1.5％以下，其中环状二聚体含量为0.2％以下；液相增粘结束后即制得尼龙6聚合物。
实施例44 尼龙6聚合物的熔体直纺方法
实施例43所述尼龙6聚合物在液相增粘反应结束后，立即按照尼龙6纺丝工艺直接纺丝，纺丝温度为280℃，纺丝速度为700m/min，冷却风温为20℃，风速1m/s，相对湿度为80％，得到未取向丝。
上述纺丝的喷丝微孔截面形状是T形；
上述尼龙6聚合物在液相增粘反应结束后，在熔体输送过程中，在线添加功能性母粒或色母粒，混合均匀后再按照尼龙6纺丝工艺直接纺丝，添加量为尼龙6聚合物的1wt％。所述功能性母粒或色母粒的基体是尼龙410和水溶性聚酯。所述功能性母粒中所含功能性助剂是 抗紫外剂滑石粉，含量为功能性母粒的30wt％。所述色母粒中所用着色剂为永固紫。
上述尼龙6聚合物在液相增粘反应结束后，在熔体输送过程中，在线添加聚合物切片，混合均匀后立即按照尼龙6纺丝工艺直接纺丝，所述聚合物切片添加量为尼龙6熔体的25wt％。所述聚合物切片是聚对苯二甲酸丙二醇酯。
实施例45 尼龙6聚合方法
一种尼龙6聚合方法，采用分段聚合的方法制备尼龙6，具体制备方法如下：
第一段为开环反应阶段：在温度为210℃和压力为1MPa条件下，将己内酰胺、水和催化剂混合后进行预聚合，开环反应时间为8h；其中水含量为己内酰胺的15wt％，催化剂含量为己内酰胺的10wt％，催化剂为H3PO4；同时加入内酯，所添加量为己内酰胺的40wt％；
所获产物数均分子量为1600，低聚物含量15％，环状二聚体含量0.1％以下，熔体粘度为30Pa·s；
第二段为预缩聚阶段：在压力为150Pa和温度为210℃条件下，将开环反应所得产物进行缩聚反应，预缩聚反应时间为1h；同时加入分子量稳定剂H(CH2)bNH2，其中b＝1，添加量为己内酰胺的2wt％；同时加入抗紫外剂水杨酸，添加量为己内酰胺的10wt％；同时加入扩链剂双环氧乙烷，分子式为
Figure PCTCN2016080024-appb-000013
其中R＝C8，扩链剂的添加量为己内酰胺的1.2wt％；
所得预聚物的熔体分子量为4500，低聚物含量在7％，其中环状二聚体含量为0.1％，熔体粘度为90Pa·s；
第三段为液相增粘阶段：在压力为80Pa条件下聚合，聚合温度从210℃逐步升至280℃(分成7个阶段，分别为210℃-220℃-230℃-240℃-250℃-260℃-270℃-280℃)，液相增粘反应时间为50min；
所获熔体分子量为33060，相对粘度为3.9，低聚物含量在1.5％以下，其中环状二聚体含量为0.2％以下；液相增粘结束后即制得尼龙6聚合物。
实施例46 尼龙6聚合物的熔体直纺方法
实施例45所述尼龙6聚合物在液相增粘反应结束后，立即按照尼龙6纺丝工艺直接纺丝，纺丝温度为260℃，纺丝速度为900m/min，冷却风温为25℃，风速0.5m/s，相对湿度为70％，得到未取向丝。
上述纺丝的喷丝微孔截面形状是Y形；
上述尼龙6聚合物在液相增粘反应结束后，在熔体输送过程中，在线添加功能性母粒或色母粒，混合均匀后再按照尼龙6纺丝工艺直接纺丝，添加量为尼龙6聚合物的30wt％。所述功能性母粒或色母粒的基体是聚乙二醇(分子量为400，聚乙二醇端基是羟基)。所述功能性母粒中所含功能性助剂是抗紫外剂碳酸钙，含量为功能性母粒的10wt％。所述色母粒中所用着色剂为偶氮红和镉红，偶氮红和镉红的质量比为1:1。
上述尼龙6聚合物在液相增粘反应结束后，在熔体输送过程中，在线添加聚合物切片，混合均匀后立即按照尼龙6纺丝工艺直接纺丝，所述聚合物切片添加量为尼龙6熔体的30wt％。所述聚合物切片是尼龙612。
实施例47 尼龙6聚合方法
一种尼龙6聚合方法，采用分段聚合的方法制备尼龙6，具体制备方法如下：
第一段为开环反应阶段：在温度为150℃和压力为5MPa条件下，将己内酰胺、水和催化剂混合后进行预聚合，开环反应时间为10h；其中水含量为己内酰胺的15wt％，催化剂含量为己内酰胺的10wt％，催化剂为H2SO4；
所获产物数均分子量为2000，低聚物含量10％，环状二聚体含量0.1％以下，熔体粘度为10Pa·s；
第二段为预缩聚阶段：在压力为150Pa和温度为210℃条件下，将开环反应所得产物进行缩聚反应，预缩聚反应时间为3h；同时加入内酰胺均聚物(n＝1，分子量2000)，所添加量为己内酰胺的30wt％；同时加入扩链剂双噁唑酮，扩链剂的添加量为己内酰胺的0.1wt％；
所得预聚物的熔体分子量为5700，低聚物含量在2％，其中环状二聚体含量为0.1％，熔体粘度为100Pa·s；
第三段为液相增粘阶段：在压力为80Pa条件下聚合，聚合温度从210℃逐步升至280℃(分成7个阶段，分别为210℃-220℃-230℃-240℃-250℃-260℃-270℃-280℃)，液相增粘反应时间为60min；同时加入分子量稳定剂二元酸HOOC(CH2)cCOOH，其中c＝1，添加量为己内酰胺的10wt％；同时加入抗菌剂分子式为
Figure PCTCN2016080024-appb-000014
的季铵盐类化合物，其中，R1、R2＝C8，R1、R2相同，X-为Cl-，添加量为己内酰胺的2wt％；
所获熔体分子量为45600，相对粘度为5.0，低聚物含量在1.5％以下，其中环状二聚体含量为0.2％以下；液相增粘结束后即制得尼龙6聚合物。
实施例48 尼龙6聚合物的熔体直纺方法
实施例47所述尼龙6聚合物在液相增粘反应结束后，立即按照尼龙6纺丝工艺直接纺丝，纺丝温度为270℃，纺丝速度为1000m/min，冷却风温为28℃，风速0.6m/s，相对湿度为65％，得到未取向丝。
上述纺丝的喷丝微孔截面形状是多边形；
上述尼龙6聚合物在液相增粘反应结束后，在熔体输送过程中，在线添加功能性母粒或色母粒，混合均匀后再按照尼龙6纺丝工艺直接纺丝，添加量为尼龙6聚合物的15wt％。所述功能性母粒或色母粒的基体是尼龙212和聚乙二醇(分子量为20000，聚乙二醇端基是羟基)。所述功能性母粒中所含功能性助剂是抗菌剂纳米二氧化钛，含量为功能性母粒的10wt％。所述色母粒中所用着色剂为镉黄和钛白粉，镉黄和钛白粉的质量比为2:1。
上述尼龙6聚合物在液相增粘反应结束后，在熔体输送过程中，在线添加聚合物切片，混合均匀后立即按照尼龙6纺丝工艺直接纺丝，所述聚合物切片添加量为尼龙6熔体的35wt％。所述聚合物切片是聚乙二醇(分子量为400经过改性的端基为氨基的聚乙二醇)。
实施例49 尼龙6聚合方法
一种尼龙6聚合方法，采用分段聚合的方法制备尼龙6，具体制备方法如下：
第一段为开环反应阶段：在温度为210℃和压力为2MPa条件下，将己内酰胺、水和催化剂混合后进行预聚合，开环反应时间为6h；其中水含量为己内酰胺的15wt％，催化剂含量为己内酰胺的10wt％，催化剂为HNO3、NH3和[Al(H2O)6](HNO3、NH3和[Al(H2O)6]质量比为1:2:1)；同时加入内酯均聚物(m＝1，分子量1000)，所添加量为己内酰胺的10wt％；
所获产物数均分子量为2000，低聚物含量30％，环状二聚体含量0.1％以下，熔体粘度为5Pa·s；
第二段为预缩聚阶段：在压力为150Pa和温度为180℃条件下，将开环反应所得产物进行缩聚反应，预缩聚反应时间为3h；同时加入分子量稳定剂二元胺间苯二胺和芳香族二元酸萘二甲酸(二元胺和萘二甲酸的质量比为1:2)，稳定剂添加量为己内酰胺的8wt％；同时加入负离子发生材料奇冰石，添加量为己内酰胺的8wt％；
所得预聚物的熔体分子量为4000，低聚物含量在2％，其中环状二聚体含量为0.1％，熔体粘度为800Pa·s；
第三段为液相增粘阶段：采用液相增粘釜，在压力为80Pa条件下聚合，聚合温度从180℃逐步升至280℃(分成10个阶段，分别为180℃-190℃-200℃-210℃-220℃-230℃-240℃-250℃-260℃-270℃-280℃)，液相增粘反应时间为80min；同时加入扩链剂磷酸酯，扩链剂的添加量为己内酰胺的0.5wt％；
所获熔体分子量为15960，相对粘度为2.5，低聚物含量在1.5％以下，其中环状二聚体含量为0.2％以下；液相增粘结束后即制得尼龙6聚合物。
实施例50 尼龙6聚合物的熔体直纺方法
实施例49所述尼龙6聚合物在液相增粘反应结束后，立即按照尼龙6纺丝工艺直接纺丝，纺丝温度为240℃，纺丝速度为4500m/min，冷却风温为25℃，风速0.6m/s，相对湿度为60％，得到预取向丝。
上述纺丝的喷丝微孔截面形状是三角形；
上述尼龙6聚合物在液相增粘反应结束后，在熔体输送过程中，在线添加功能性母粒或色母粒，混合均匀后再按照尼龙6纺丝工艺直接纺丝，添加量为尼龙6聚合物的30wt％。所述功能性母粒或色母粒的基体是支链尼龙。所述功能性母粒中所含功能性助剂是抗菌剂氧化铁，含量为功能性母粒的15wt％。所述色母粒中所用着色剂为氧化铁黄、颜料绿36、颜料黄214，氧化铁黄、颜料绿36和颜料黄214的质量比为2:1:1。
上述尼龙6聚合物在液相增粘反应结束后，在熔体输送过程中，在线添加聚合物切片，混合均匀后立即按照尼龙6纺丝工艺直接纺丝，所述聚合物切片添加量为尼龙6熔体的45wt％。所述聚合物切片是尼龙1212。
实施例51 尼龙6聚合方法
一种尼龙6聚合方法，采用分段聚合的方法制备尼龙6，具体制备方法如下：
第一段为开环反应阶段：在温度为150℃和压力为0.8MPa条件下，将己内酰胺、水和催化剂混合后进行预聚合，开环反应时间为6h；其中水含量为己内酰胺的15wt％，催化剂含量为己内酰胺的10wt％，催化剂为HNO3、NH3和[Al(H2O)6](HNO3、NH3和[Al(H2O)6]质量比为1:1:2)；同时加入内酯均聚物(m＝1，分子量1000)，所添加量为己内酰胺的10wt％；
所获产物数均分子量为2000，低聚物含量30％，环状二聚体含量0.1％以下，熔体粘度为5Pa·s；
第二段为预缩聚阶段：在压力为150Pa和温度为180℃条件下，将开环反应所得产物进行缩聚反应，预缩聚反应时间为3h；同时加入分子量稳定剂二元胺H2N(CH2)dNH2(其中d＝10)和芳香族二元酸间苯二甲酸(二元胺和间苯二甲酸的质量比为1:2)，稳定剂添加量为己内酰胺的8wt％；同时加入负离子发生材料奇冰石，添加量为己内酰胺的8wt％；
所得预聚物的熔体分子量为4000，低聚物含量在2％，其中环状二聚体含量为0.1％，熔体粘度为800Pa·s；
第三段为液相增粘阶段：采用液相增粘釜，在压力为80Pa条件下聚合，聚合温度从180℃逐步升至280℃(分成10个阶段，分别为180℃-190℃-200℃-210℃-220℃-230℃-240℃-250℃-260℃-270℃-280℃)，液相增粘反应时间为80min；同时加入扩链剂磷酸酯，扩链剂的添加量为己内酰胺的0.5wt％；
所获熔体分子量为15960，相对粘度为2.5，低聚物含量在1.5％以下，其中环状二聚体含量为0.2％以下；液相增粘结束后即制得尼龙6聚合物。
实施例52 尼龙6聚合物的熔体直纺方法
实施例51所述尼龙6聚合物在液相增粘反应结束后，直接应用于复合纺丝，所述复合纺丝是并列型，所述复合纺丝除尼龙6之外另一组分是尼龙6T，所述尼龙6聚合物与另一组分的质量比为3:7。
上述纺丝的喷丝微孔截面形状是多角形；
上述尼龙6聚合物在液相增粘反应结束后，在熔体输送过程中，在线添加功能性母粒或色母粒，混合均匀后再按照尼龙6纺丝工艺直接纺丝，添加量为尼龙6聚合物的1wt％。所述功能性母粒或色母粒的基体是聚对苯二甲酸丙二醇酯。所述功能性母粒中所含功能性助剂是阻燃剂双(六氯环戊二烯)环辛烷，含量为功能性母粒的20wt％。所述色母粒中所用着色剂为颜料橙43和颜料橙68，颜料橙43和颜料橙68的质量比为1:1。
上述尼龙6聚合物在液相增粘反应结束后，在熔体输送过程中，在线添加聚合物切片，混合均匀后立即按照尼龙6纺丝工艺直接纺丝，所述聚合物切片添加量为尼龙6熔体的50wt％。所述聚合物切片是聚对苯二甲酸丁二醇酯。
实施例53 尼龙6聚合方法
一种尼龙6聚合方法，采用分段聚合的方法制备尼龙6，具体制备方法如下：
第一段为开环反应阶段：在温度为150℃和压力为0.8MPa条件下，将己内酰胺、水和催化剂混合后进行预聚合，开环反应时间为6h；其中水含量为己内酰胺的15wt％，催化剂含量为己内酰胺的10wt％，催化剂为HNO3、NH3和[Al(H2O)6](HNO3、NH3和[Al(H2O)6]质量比为1:1:2)；同时加入内酯均聚物(m＝1，分子量1000)，所添加量为己内酰胺的10wt％；
所获产物数均分子量为2000，低聚物含量30％，环状二聚体含量0.1％以下，熔体粘度为5Pa·s；
第二段为预缩聚阶段：在压力为150Pa和温度为180℃条件下，将开环反应所得产物进行缩聚反应，预缩聚反应时间为3h；同时加入分子量稳定剂二元胺对苯二胺和芳香族二元酸 间苯二甲酸(二元胺和间苯二甲酸的质量比为1:2)，稳定剂添加量为己内酰胺的8wt％；同时加入负离子发生材料奇冰石，添加量为己内酰胺的8wt％；
所得预聚物的熔体分子量为4000，低聚物含量在2％，其中环状二聚体含量为0.1％，熔体粘度为800Pa·s；
第三段为液相增粘阶段：采用液相增粘釜，在压力为80Pa条件下聚合，聚合温度从180℃逐步升至280℃(分成10个阶段，分别为180℃-190℃-200℃-210℃-220℃-230℃-240℃-250℃-260℃-270℃-280℃)，液相增粘反应时间为80min；同时加入扩链剂磷酸酯，扩链剂的添加量为己内酰胺的0.5wt％；
所获熔体分子量为15960，相对粘度为2.5，低聚物含量在1.5％以下，其中环状二聚体含量为0.2％以下；液相增粘结束后即制得尼龙6聚合物。
实施例54 尼龙6聚合物的熔体直纺方法
实施例53所述尼龙6聚合物在液相增粘反应结束后，直接应用于复合纺丝，所述复合纺丝是并列型，所述复合纺丝除尼龙6之外另一组分是尼龙6T，所述尼龙6聚合物与另一组分的质量比为3:7。
上述纺丝的喷丝微孔截面形状是多角形；
上述尼龙6聚合物在液相增粘反应结束后，在熔体输送过程中，在线添加功能性母粒或色母粒，混合均匀后再按照尼龙6纺丝工艺直接纺丝，添加量为尼龙6聚合物的1wt％。所述功能性母粒或色母粒的基体是聚对苯二甲酸丙二醇酯。所述功能性母粒中所含功能性助剂是阻燃剂双(六氯环戊二烯)环辛烷，含量为功能性母粒的20wt％。所述色母粒中所用着色剂为颜料橙43。
上述尼龙6聚合物在液相增粘反应结束后，在熔体输送过程中，在线添加聚合物切片，混合均匀后立即按照尼龙6纺丝工艺直接纺丝，所述聚合物切片添加量为尼龙6熔体的50wt％。所述聚合物切片是聚对苯二甲酸丁二醇酯。
实施例55 尼龙6聚合方法
一种尼龙6聚合方法，采用分段聚合的方法制备尼龙6，具体制备方法如下：
第一段为开环反应阶段：在温度为210℃和压力为2MPa条件下，将己内酰胺、水和催化剂混合后进行预聚合，开环反应时间为6h；其中水含量为己内酰胺的15wt％，催化剂含量为己内酰胺的10wt％，催化剂为HNO3、NH3和[Al(H2O)6](HNO3、NH3和[Al(H2O)6]质量比为1:2:1)；同时加入内酯均聚物(m＝1，分子量1000)，所添加量为己内酰胺的10wt％；
所获产物数均分子量为2000，低聚物含量30％，环状二聚体含量0.1％以下，熔体粘度为5Pa·s；
第二段为预缩聚阶段：在压力为150Pa和温度为180℃条件下，将开环反应所得产物进行缩聚反应，预缩聚反应时间为3h；同时加入分子量稳定剂二元胺萘二胺和芳香族二元酸萘二甲酸(二元胺和萘二甲酸的质量比为1:2)，稳定剂添加量为己内酰胺的8wt％；同时加入负离子发生材料奇冰石，添加量为己内酰胺的8wt％；
所得预聚物的熔体分子量为4000，低聚物含量在2％，其中环状二聚体含量为0.1％，熔体粘度为800Pa·s；
第三段为液相增粘阶段：采用液相增粘釜，在压力为80Pa条件下聚合，聚合温度从180℃逐步升至280℃(分成10个阶段，分别为180℃-190℃-200℃-210℃-220℃-230℃-240℃-250℃-260℃-270℃-280℃)，液相增粘反应时间为80min；同时加入扩链剂磷酸酯，扩链剂的添加量为己内酰胺的0.5wt％；
所获熔体分子量为15960，相对粘度为2.5，低聚物含量在1.5％以下，其中环状二聚体含量为0.2％以下；液相增粘结束后即制得尼龙6聚合物。
实施例56 尼龙6聚合物的熔体直纺方法
实施例55所述尼龙6聚合物在液相增粘反应结束后，立即按照尼龙6纺丝工艺直接纺丝，纺丝温度为240℃，纺丝速度为4500m/min，冷却风温为25℃，风速0.6m/s，相对湿度为60％，得到预取向丝。
上述纺丝的喷丝微孔截面形状是三角形；
上述尼龙6聚合物在液相增粘反应结束后，在熔体输送过程中，在线添加功能性母粒或色母粒，混合均匀后再按照尼龙6纺丝工艺直接纺丝，添加量为尼龙6聚合物的30wt％。所述功能性母粒或色母粒的基体是支链尼龙。所述功能性母粒中所含功能性助剂是抗菌剂氧化铁，含量为功能性母粒的15wt％。所述色母粒中所用着色剂为氧化铁黄。
上述尼龙6聚合物在液相增粘反应结束后，在熔体输送过程中，在线添加聚合物切片，混合均匀后立即按照尼龙6纺丝工艺直接纺丝，所述聚合物切片添加量为尼龙6熔体的45wt％。所述聚合物切片是尼龙1212。
实施例57 尼龙6聚合方法
一种尼龙6聚合方法，采用分段聚合的方法制备尼龙6，具体制备方法如下：
第一段为开环反应阶段：在温度为210℃和压力为2MPa条件下，将己内酰胺、水和催化剂混合后进行预聚合，开环反应时间为6h；其中水含量为己内酰胺的15wt％，催化剂含量为己内酰胺的10wt％，催化剂为HNO3、NH3和[Al(H2O)6](HNO3、NH3和[Al(H2O)6]质量比为1:2:1)；同时加入内酯均聚物(m＝1，分子量1000)，所添加量为己内酰胺的10wt％；
所获产物数均分子量为2000，低聚物含量30％，环状二聚体含量0.1％以下，熔体粘度为5Pa·s；
第二段为预缩聚阶段：在压力为150Pa和温度为180℃条件下，将开环反应所得产物进行缩聚反应，预缩聚反应时间为3h；同时加入分子量稳定剂二元胺二甲苯二胺和芳香族二元酸萘二甲酸(二元胺和萘二甲酸的质量比为1:2)，稳定剂添加量为己内酰胺的8wt％；同时加入负离子发生材料奇冰石，添加量为己内酰胺的8wt％；
所得预聚物的熔体分子量为4000，低聚物含量在2％，其中环状二聚体含量为0.1％，熔体粘度为800Pa·s；
第三段为液相增粘阶段：采用液相增粘釜，在压力为80Pa条件下聚合，聚合温度从180℃逐步升至280℃(分成10个阶段，分别为180℃-190℃-200℃-210℃-220℃-230℃-240℃-250℃-260℃-270℃-280℃)，液相增粘反应时间为80min；同时加入扩链剂磷酸酯，扩链剂的添加量为己内酰胺的0.5wt％；
所获熔体分子量为15960，相对粘度为2.5，低聚物含量在1.5％以下，其中环状二聚体含量为0.2％以下；液相增粘结束后即制得尼龙6聚合物。
实施例58 尼龙6聚合物的熔体直纺方法
实施例57所述尼龙6聚合物在液相增粘反应结束后，立即按照尼龙6纺丝工艺直接纺丝，纺丝温度为240℃，纺丝速度为4500m/min，冷却风温为25℃，风速0.6m/s，相对湿度为60％，得到预取向丝。
上述纺丝的喷丝微孔截面形状是三角形；
上述尼龙6聚合物在液相增粘反应结束后，在熔体输送过程中，在线添加功能性母粒或色母粒，混合均匀后再按照尼龙6纺丝工艺直接纺丝，添加量为尼龙6聚合物的30wt％。所述功能性母粒或色母粒的基体是支链尼龙。所述功能性母粒中所含功能性助剂是抗菌剂氧化铁，含量为功能性母粒的15wt％。所述色母粒中所用着色剂为颜料黄214。
上述尼龙6聚合物在液相增粘反应结束后，在熔体输送过程中，在线添加聚合物切片，混合均匀后立即按照尼龙6纺丝工艺直接纺丝，所述聚合物切片添加量为尼龙6熔体的45wt％。所述聚合物切片是尼龙1212。

Claims (40)

  1. 一种尼龙6聚合方法，其特征是：采用分段聚合的方法制备尼龙6，具体制备方法如下：
    第一段为开环反应阶段：在温度为150-220℃和压力为0.1-5MPa条件下，将己内酰胺、水和催化剂混合后进行预聚合；
    所获产物数均分子量为1000-2000，低聚物含量10-30％，环状二聚体含量0.1％以下，熔体粘度为1-10Pa·s；
    第二段为预缩聚阶段：在压力为10-200Pa和温度为180-220℃条件下，将开环反应所得产物进行缩聚反应；
    所得预聚物的熔体分子量为4000-6000，低聚物含量在2-8％，其中环状二聚体含量为0.1％，熔体粘度为1-100Pa·s；
    第三段为缩聚反应动力学强化阶段：在压力为10-100Pa条件下聚合，聚合温度从180-220℃逐步升至220-280℃；所获熔体分子量为11400-45600，相对粘度为2.0-5.0，低聚物含量在1.5％以下，其中环状二聚体含量为0.2％以下；为保证小分子能快速脱除以达到快速增粘的目的，聚合温度从180-220℃逐步升至220-280℃采用的是阶梯升温的方式，保证熔体粘度为1000-4000Pa·s；缩聚反应动力学强化结束后即制得尼龙6聚合物。
  2. 根据权利要求1所述的一种尼龙6聚合方法，其特征在于，水含量为己内酰胺的1-20wt％，催化剂含量为己内酰胺的1-20wt％。
  3. 根据权利要求1所述的一种尼龙6聚合方法，其特征在于，所述催化剂为氨基酸和/或质子酸，所述质子酸为HCl、H3PO4、H2SO4、HNO3、NH3、[Al(H2O)6]中的一种及以上。
  4. 根据权利要求3所述的一种尼龙6聚合方法，其特征在于，所述氨基酸为脂肪族氨基酸或芳香族氨基酸；所述脂肪族氨基酸的分子式为NH2(CH2)xCOOH，其中x＝1～16；所述芳香族氨基酸为主链或支链上存在苯环，为苯丙氨酸。
  5. 根据权利要求1所述的一种尼龙6聚合方法，其特征在于，所述开环反应时间为3-12h。
  6. 根据权利要求1所述的一种尼龙6聚合方法，其特征在于，所述预缩聚反应时间为1-3h。
  7. 根据权利要求1所述的一种尼龙6聚合方法，其特征在于，所述缩聚反应动力学强化过程时间为10-90min。
  8. 根据权利要求1所述的一种尼龙6聚合方法，其特征在于，所述阶梯升温是指温度从180-220℃升到220-280℃分为2-10个阶段，以实现温度随缩聚反应的进行而逐渐上升。
  9. 根据权利要求1所述的一种尼龙6聚合方法，其特征在于，采用液相增粘釜，实现所述缩聚反应动力学强化过程。
  10. 根据权利要求1所述的一种尼龙6聚合方法，其特征在于，所述开环阶段、所述预缩聚 或所述缩聚反应动力学强化阶段，还添加分子量稳定剂，为单元酸、单元胺、多元酸或多元胺中的一种及以上，添加量为己内酰胺的0.01-10wt％；其中：
    单元酸，为脂肪族H(CH2)aCOOH，其中，a＝1～16；或芳香族，为苯甲酸；
    单元胺，为脂肪族H(CH2)bNH2，其中，b＝1～16；或芳香族，为苯胺；
    多元酸，为脂肪族二元酸HOOC(CH2)cCOOH，其中，c＝1-20；或芳香族二元酸，为邻苯二甲酸、间苯二甲酸、对苯二甲酸或萘二甲酸；
    多元胺，为脂肪族二元胺H2N(CH2)dNH2，其中，d＝1-20；或芳香族二元胺，为邻苯二胺、间苯二胺、对苯二胺、萘二胺或二甲苯二胺。
  11. 根据权利要求1所述的一种尼龙6聚合方法，其特征在于，所述开环阶段、所述预缩聚或所述缩聚反应动力学强化阶段，还加入内酰胺、内酯或其聚合物，所添加量为己内酰胺的50wt％以下。
  12. 根据权利要求11所述的一种尼龙6聚合方法，其特征在于，所述聚合物为内酰胺和/或内酯的均聚物或共聚物，所述内酰胺为
    Figure PCTCN2016080024-appb-100001
    所述内酯为
    Figure PCTCN2016080024-appb-100002
    其中n＝1～10，m＝1～10；所述内酰胺和/或内酯的均聚物或共聚物数均分子量为4000以下。
  13. 根据权利要求1所述的一种尼龙6聚合方法，其特征在于，所述开环阶段、所述预缩聚或所述缩聚反应动力学强化阶段，还添加功能添加剂，为抗氧化剂、抗紫外剂、抗菌剂、阻燃剂、负离子发生材料、荧光材料、碳纳米管或石墨烯，添加量为己内酰胺的0.01-10wt％。
  14. 根据权利要求13所述的一种尼龙6聚合方法，其特征在于，所述抗氧化剂为抗氧化剂1010、抗氧化剂168或抗氧化剂616；抗紫外剂为水杨酸、二苯甲酮系苯并三唑系、二氧化钛、氧化锌、碳酸钙、滑石粉或SEED；抗菌剂为纳米二氧化钛、氧化锌、氧化铁、壳聚糖、纳米银、纳米铜或季铵盐类化合物；阻燃剂为硼酸锌、四溴双酚A、双(六氯环戊二烯)环辛烷、多磷酸铵、十溴二苯醚或1,3,6-三(4,6-二氨基-2-硫基三嗪)己烷与三聚氰酸的混合物；负离子发生材料为奇冰石、电气石、蛋白石或奇才石；荧光材料以碱土金属的硫化物、铝酸盐作为发光基质，以稀土镧系元素铕、钐、铒或钕，作为激活剂。
  15. 根据权利要求14所述的一种尼龙6聚合方法，其特征在于，所述季铵盐类化合物分子式为
    Figure PCTCN2016080024-appb-100003
    其中，R1、R2＝C8～C20，R1、R2相同或不同，X-为Cl-、Br-、I-。
  16. 根据权利要求1所述的一种尼龙6聚合方法，其特征在于，所述缩聚反应动力学强化阶段，还添加扩链剂达到快速增粘的效果，扩链剂的添加量为己内酰胺的0.01wt％-1.2wt％；所述扩链剂为双环氧乙烷、双噁唑酮、双酰基双己内酰胺、磷酸酯或双异氰酸酯；所述的 双环氧乙烷的分子式为
    Figure PCTCN2016080024-appb-100004
    其中R＝C1～C8。
  17. 如权利要求1所述的聚合方法所得尼龙6聚合物的熔体直纺方法，其特征是：所述尼龙6聚合物在缩聚反应动力学强化过程结束后，立即按照尼龙6纺丝工艺直接纺丝，纺丝温度为240-280℃，第一导丝盘速度为4000-4500m/min，第二导丝盘速度为5000-6000m/min，拉伸倍数为1.1-1.5倍，冷却风温为15-25℃，风速0.5-1m/s，相对湿度为60％-90％，得到全拉伸丝。
  18. 如权利要求1所述的聚合方法所得尼龙6聚合物的熔体直纺方法，其特征是：所述尼龙6聚合物在缩聚反应动力学强化过程结束后，立即按照尼龙6纺丝工艺直接纺丝，纺丝温度为240-280℃，纺丝速度为700-1500m/min，冷却风温为20-30℃，风速0.3-1m/s，相对湿度为60％-80％，得到未取向丝。
  19. 如权利要求1所述的聚合方法所得尼龙6聚合物的熔体直纺方法，其特征是：所述尼龙6聚合物在缩聚反应动力学强化过程结束后，立即按照尼龙6纺丝工艺直接纺丝，纺丝温度为240-280℃，纺丝速度为4000-4500m/min，冷却风温为15-25℃，风速0.3-0.6m/s，相对湿度为60％-80％，得到预取向丝。
  20. 如权利要求1所述的聚合方法所得尼龙6聚合物的熔体直纺方法，其特征是：所述尼龙6聚合物在缩聚反应动力学强化过程结束后，立即按照尼龙6纺丝工艺直接纺丝，纺丝温度为240-280℃，纺丝速度为4500-6000m/min，冷却风温为15-20℃，风速0.3-0.5m/s，相对湿度为80％-90％，得到高取向丝。
  21. 如权利要求1所述的聚合方法所得尼龙6聚合物的熔体直纺方法，其特征是：所述尼龙6聚合物在缩聚反应动力学强化过程结束后，立即按照尼龙6纺丝工艺直接纺丝得到膨化变形丝，纺丝温度为240-280℃，冷却风温为20-30℃，风速0.3-1m/s，相对湿度为60％-80％，喂入辊温度为60-120℃，拉伸辊温度为100-190℃，喂入速度为300-1000m/min，拉伸速度为1000-3500m/min，拉伸倍数为3.5-5倍，变形热空气温度为190-230℃，空气喷射压力为196kPa-490kPa，卷绕速度为600-3000m/min，冷却空气温度为25℃。
  22. 如权利要求1所述的聚合方法所得尼龙6聚合物的熔体直纺方法，其特征是：所述尼龙6聚合物在缩聚反应动力学强化过程结束后，直接应用于复合纺丝，所述复合纺丝是并列型、皮芯型、海岛型、桔瓣型或多芯型复合纺丝；所述复合纺丝除尼龙6之外另一组分是尼龙6T、尼龙612、尼龙610、尼龙1212、尼龙46、尼龙410、尼龙11、尼龙12、尼龙26、尼龙212、支链尼龙、水溶性聚酯中的一种，所述尼龙6聚合物与另一组分的质量比为3:7-7:3。
  23. 如权利要求17～21中任一项所述的熔体直纺方法，其特征是：纺丝的喷丝微孔截面形状是三角形、十字形、多角形、中空纤维、U形、T形、Y形、多边形或工字形。
  24. 如权利要求17～22中任一项所述的熔体直纺方法，其特征是：所述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加功能性母粒或色母粒，混合均匀后再按照尼龙6纺丝工艺直接纺丝，添加量为尼龙6聚合物的1-30wt％。
  25. 根据权利要求24中所述的熔体直纺方法，其特征在于，所述功能性母粒或色母粒的基体是尼龙、聚酯、聚乙二醇中的一种及以上。
  26. 根据权利要求25中所述的熔体直纺方法，其特征在于，尼龙是尼龙6、尼龙6T、尼龙612、尼龙610、尼龙1212、尼龙46、尼龙410、尼龙11、尼龙12、尼龙26、尼龙212、支链尼龙中的一种及以上；聚酯是聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚对苯二甲酸丙二醇酯、水溶性聚酯中的一种及以上；聚乙二醇分子量范围为400-20000，聚乙二醇端基是羟基，或是经过改性的端基为羧基和/或氨基的聚乙二醇。
  27. 根据权利要求24中所述的熔体直纺方法，其特征在于，所述功能性母粒中所含功能性助剂是抗氧化剂、抗紫外剂、抗菌剂、阻燃剂、负离子发生材料、荧光材料、碳纳米管或石墨烯，含量为功能性母粒的10-30wt％。
  28. 根据权利要求27中所述的熔体直纺方法，其特征在于，所述抗氧化剂为抗氧化剂1010、抗氧化剂168或抗氧化剂616；抗紫外剂为水杨酸、二苯甲酮系苯并三唑系、二氧化钛、氧化锌、碳酸钙、滑石粉、SEED；抗菌剂为纳米二氧化钛、氧化锌、氧化铁、壳聚糖、纳米银、纳米铜或季铵盐类化合物；阻燃剂为硼酸锌、四溴双酚A、双(六氯环戊二烯)环辛烷、多磷酸铵、十溴二苯醚或1,3,6-三(4,6-二氨基-2-硫基三嗪)己烷与三聚氰酸的混合物；负离子发生材料为奇冰石、电气石、蛋白石或奇才石；荧光材料是以碱土金属的硫化物、铝酸盐作为发光基质，以稀土镧系元素铕、钐、铒或钕，作为激活剂。
  29. 根据权利要求28中所述的熔体直纺方法，其特征在于，所述季铵盐类化合物分子式为
    Figure PCTCN2016080024-appb-100005
    其中，R1、R2＝C8～C20，R1、R2相同或不同；X-为Cl-、Br-、I-。
  30. 根据权利要求24中所述的熔体直纺方法，其特征在于，所述色母粒中所用着色剂为酞菁红、酞菁蓝、酞菁绿、耐晒大红、大分子红、大分子黄、永固黄、永固紫、偶氮红、镉红、镉黄、钛白粉、炭黑、氧化铁红、氧化铁黄、颜料红179、颜料蓝60、颜料绿36、颜料黄214、颜料橙43、颜料橙68、颜料棕41、颜料黄184、溶剂紫59、溶剂紫37、溶剂红143、溶剂红181、溶剂蓝94、溶剂蓝132、溶剂绿29、溶剂黄135、溶剂黄167的一种及以上。
  31. 如权利要求17～22中任一项所述的熔体直纺方法，其特征是：所述尼龙6聚合物在缩聚反应动力学强化过程结束后，在熔体输送过程中，在线添加聚合物切片，混合均匀后立即按照尼龙6纺丝工艺直接纺丝，所述聚合物切片添加量为尼龙6熔体的5-50wt％。
  32. 根据权利要求31中所述的熔体直纺方法，其特征在于，所述聚合物切片是聚酯、尼龙、聚乙二醇中一种及以上。
  33. 根据权利要求31中所述的熔体直纺方法，其特征在于，聚酯是聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚对苯二甲酸丙二醇酯、水溶性聚酯中的一种及以上；尼龙是尼龙6、尼龙6T、尼龙612、尼龙610、尼龙1212、尼龙46、尼龙410、尼龙11、尼龙12、尼龙26、尼龙212、支链尼龙中的一种及以上；聚乙二醇分子量范围为400-20000，聚乙二醇端基是羟基，或是经过改性的端基为羧基和/或氨基的聚乙二醇。
  34. 如权利要求1所述的一种尼龙6聚合方法所获得的尼龙6聚合物纺成纤维后织成的面料，其特征是：将所述尼龙聚合物纺制成的尼龙6纤维，然后通过梭织或针织形成面料，面料是平纹、斜纹、缎纹中的一种，然后进行染色，获得不同规格颜色的布料。
  35. 根据权利要求34所述的面料，其特征在于，面料的染色生产工序为：前处理退浆-热水清洗坯布-升温染色-固色-降温清洗-面料出机防水定型-成品检验-成品打卷。
  36. 根据权利要求35所述的面料，其特征在于，所述前处理退浆温度为60-80℃，退浆时间为6-12h，其退浆助剂配方为：纯碱10-20g/L，去油灵10-15g/L。
  37. 根据权利要求35所述的面料，其特征在于，所述升温染色工艺为始染温度为30-40℃，以1-3℃/min的速率升温，升温至90-95℃再保温40min；染色剂浓度为0.5-2％(omf)，浴比为1:10-20。
  38. 根据权利要求35所述的面料，其特征在于，所述固色工艺为温度为90-95℃，固色时间为20-60min；固色剂浓度为0.5-2％(omf)，浴比为1:10-20。
  39. 根据权利要求34所述的面料，其特征在于，在染色及固色过程中，加入助剂，所述助剂添加量为5-10g/L，所述助剂包括软水剂、匀染剂和缓染剂；软水剂，为NORM02；匀染剂，为ACID03或ACID16；缓染剂，为硫酸铵。
  40. 如权利要求1所述的一种尼龙6聚合方法的装置，其特征是：料仓(1)通过管道与原料加热罐(3)相连，加压开环釜(4)通过管道与原料加热罐(3)相连，缩聚釜(5)通过管道与加压开环釜(4)相连，液相增粘釜(6)通过管道与缩聚釜(5)相连，缩聚釜(5)、液相增粘釜(6)分别与缓冲罐(7)通过管道相连，浓缩罐(8)与缓冲罐(7)通过管道相连。
PCT/CN2016/080024 2016-02-01 2016-04-22 一种尼龙6聚合方法及其熔体直纺方法 WO2017133085A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP16888909.5A EP3412704A4 (en) 2016-02-01 2016-04-22 METHOD FOR POLYMERIZING NYLON 6, AND METHOD FOR DIRECT FUSION MIXING THEREOF

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201610071571.3 2016-02-01
CN201610071571.3A CN105669969B (zh) 2016-02-01 2016-02-01 一种尼龙6聚合方法及其熔体直纺方法

Publications (1)

Publication Number Publication Date
WO2017133085A1 true WO2017133085A1 (zh) 2017-08-10

Family

ID=56303295

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2016/080024 WO2017133085A1 (zh) 2016-02-01 2016-04-22 一种尼龙6聚合方法及其熔体直纺方法

Country Status (3)

Country Link
EP (1) EP3412704A4 (zh)
CN (1) CN105669969B (zh)
WO (1) WO2017133085A1 (zh)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111155193A (zh) * 2020-01-20 2020-05-15 福建中锦新材料有限公司 一种成纤聚合物的合成方法
CN111424328A (zh) * 2020-03-12 2020-07-17 浙江恒澜科技有限公司 一种包含气相抽提、液相萃取的尼龙熔体直纺方法
CN111621995A (zh) * 2018-03-02 2020-09-04 苏州棠华纳米科技有限公司 一种染料组合物的制备方法
CN113215678A (zh) * 2021-06-15 2021-08-06 闽江学院 一种荧光透明锦纶长丝的制备方法
CN114775096A (zh) * 2022-03-24 2022-07-22 浙江嘉华特种尼龙有限公司 一种采用固相缩聚直纺技术生产再生锦纶6纤维的方法

Families Citing this family (51)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105669969B (zh) * 2016-02-01 2018-02-09 东华大学 一种尼龙6聚合方法及其熔体直纺方法
CN105887230A (zh) * 2016-06-17 2016-08-24 优纤科技（丹东）有限公司 一种锦纶56短纤及其熔体直纺制备方法
TWI612074B (zh) * 2016-08-04 2018-01-21 博祥國際股份有限公司 含有胜肽的聚己內醯胺材料的製備方法及含有胜肽的聚己內醯胺材料
CN107778477B (zh) * 2016-08-30 2020-05-12 江苏瑞美福实业有限公司 一种低分子量聚己内酰胺的制备方法
CN108532026B (zh) * 2016-12-12 2022-03-22 东丽纤维研究所（中国）有限公司 一种芯鞘复合纤维及其制造方法和纺织品
CN106637448B (zh) * 2016-12-13 2018-12-11 苏州金纬化纤工程技术有限公司 一种化纤锦纶长丝fdy电气控制装置
CN106637496B (zh) * 2016-12-27 2019-04-19 宁波三邦超细纤维有限公司 抗uv超细旦锦纶水溶性涤纶复合纤维及制备方法
CN106676672B (zh) * 2016-12-27 2019-04-19 宁波三邦超细纤维有限公司 超细旦锦纶水溶性涤纶复合纤维及制备方法
CN106637501B (zh) * 2016-12-27 2019-05-24 宁波三邦超细纤维有限公司 有色超细旦锦纶水溶性涤纶复合纤维及制备方法
CN106702531B (zh) * 2016-12-27 2019-05-24 宁波三邦超细纤维有限公司 阻燃超细旦锦纶水溶性涤纶复合纤维及制备方法
CN106637476B (zh) * 2016-12-27 2019-05-24 宁波三邦超细纤维有限公司 抗菌超细旦锦纶水溶性涤纶复合纤维及制备方法
CN106906534B (zh) * 2017-03-07 2019-02-05 杭州高烯科技有限公司 一种高强高模量石墨烯/尼龙6纤维及制备方法
CN106866957B (zh) * 2017-03-09 2019-06-07 长乐力恒锦纶科技有限公司 一种纳米铜离子差异化锦纶切片的制备方法
CN106958048B (zh) * 2017-03-21 2019-04-30 长乐力恒锦纶科技有限公司 一种高亮度锦纶6纤维及其制备方法
CN107151828A (zh) * 2017-04-21 2017-09-12 长兴博美纺织有限公司 一种锦纶欧根纱的制备方法
CN107151827A (zh) * 2017-04-21 2017-09-12 长兴博美纺织有限公司 一种应用于夏季女士时装的锦纶纤维的制备方法
CN107419356A (zh) * 2017-05-19 2017-12-01 广州傲群刷业有限公司 一种用于安全毛刷的黄色阻燃尼龙丝及其制备方法
CN107385545B (zh) * 2017-06-26 2019-10-29 杭州师范大学 一种氧化石墨烯改性的共聚酯酰胺及其纤维的制备方法与应用
CN107142551B (zh) * 2017-06-27 2018-10-23 江苏苏能新材料科技有限公司 一种抗菌聚酰胺超细纤维及其反应挤出制备方法
CN107142537A (zh) * 2017-07-07 2017-09-08 江苏海阳化纤有限公司 一种颜色纤维用色材及其制备方法和应用
CN107177897A (zh) * 2017-07-07 2017-09-19 江苏海阳化纤有限公司 一种尼龙颜色纤维及其制备方法
CN107723828A (zh) * 2017-10-13 2018-02-23 江苏双良低碳产业技术研究院有限公司 一种高分散性石墨烯/尼龙6复合纤维的制备方法及纺丝方法
CN107698754B (zh) * 2017-11-01 2020-05-01 湖南斯沃德化工有限公司 一种氧化石墨烯改性聚酰胺-6的制备方法
CN108047709B (zh) * 2017-12-29 2020-04-07 福建华彩新材料有限公司 一种石墨烯抗菌母粒、纤维及其制备方法
CN108559074B (zh) * 2018-03-26 2020-09-25 中国石油化工股份有限公司 一种支化尼龙6的连续聚合工艺及其产品
CN108560074A (zh) * 2018-05-24 2018-09-21 奚正华 一种耐老化锦纶的制备方法
CN108676353A (zh) * 2018-05-24 2018-10-19 东阳市特意新材料科技有限公司 一种耐高温聚酰胺塑料及其制备方法
CN108676354A (zh) * 2018-05-24 2018-10-19 东阳市特意新材料科技有限公司 一种阻燃抗熔滴聚酰胺薄膜的制备方法
CN108676356A (zh) * 2018-05-24 2018-10-19 东阳市特意新材料科技有限公司 一种耐老化尼龙弹性体及其制备方法
CN108842270A (zh) * 2018-08-30 2018-11-20 佛山市南海区佳妍内衣有限公司 能对温度微调节的三维立体结构面料
CN109355727A (zh) * 2018-10-17 2019-02-19 浙江方圆聚合纤有限公司 一种高效光催化抗菌锦纶6纤维及其制备方法
CN109898330B (zh) * 2018-10-18 2020-05-26 天津工业大学 一种改性聚己内酰胺碳纤维水性上浆剂的制备方法
CN109294224A (zh) * 2018-10-29 2019-02-01 江苏亿超工程塑料有限公司 一种聚酰胺复合材料及其制备方法
CN109629033A (zh) * 2018-12-25 2019-04-16 南通东屹高新纤维科技有限公司 一种超消光新型尼龙56吸湿快干纤维的制作工艺
CN109811423B (zh) * 2018-12-25 2021-10-26 中国纺织科学研究院有限公司 连续聚合熔体直纺功能聚酰胺纤维的生产方法及该功能聚酰胺纤维
CN109778331A (zh) * 2018-12-29 2019-05-21 浙江恒逸锦纶有限公司 一种锦纶聚合用二氧化钛悬浮液及其制备方法
CN109880079A (zh) * 2019-03-27 2019-06-14 江苏弘盛新材料股份有限公司 一种抗静电抗菌尼龙6及其制备方法
CN110079879A (zh) * 2019-04-29 2019-08-02 吴江精美峰实业有限公司 一种海岛纤维及用于制备海岛纤维的方法和复合纺丝组件
CN110387597B (zh) * 2019-06-19 2021-10-26 东华大学 一种基于一步法牵伸工艺的高强尼龙6长丝及其制备方法
CN110818893A (zh) * 2019-09-26 2020-02-21 江阴市强力化纤有限公司 一种抗菌尼龙6切片聚合生产方法
CN110776732A (zh) * 2019-09-27 2020-02-11 中广核俊尔(浙江)新材料有限公司 一种耐水煮色母及其制备方法与应用
CN110965147B (zh) * 2019-12-05 2022-04-22 中国纺织科学研究院有限公司 一种聚酯制品的制备方法及聚酯制品
CN111055612A (zh) * 2019-12-31 2020-04-24 深圳市宏翔新材料发展有限公司 一种毛笔的制备方法
CN111574709B (zh) * 2020-03-05 2022-11-15 浙江恒逸石化研究院有限公司 一种尼龙6熔体多级脱挥装置
CN111304771B (zh) * 2020-03-12 2022-09-13 浙江恒逸石化研究院有限公司 一种共聚改性低熔点尼龙纤维的熔融直纺方法
CN111575825B (zh) * 2020-03-20 2022-11-11 浙江恒逸石化研究院有限公司 一种基于熔体直纺技术制备功能化尼龙6纤维的方法
CN111394831B (zh) * 2020-03-20 2022-08-23 浙江恒逸石化研究院有限公司 一种熔体直纺制备涤锦复合纤维的方法
CN112064137B (zh) * 2020-08-05 2022-02-08 南通九野智能科技有限公司 聚酰胺6及聚酰胺6的石墨烯改性物的熔体直纺纤维的制备方法
CN112094406A (zh) * 2020-08-31 2020-12-18 聊城鲁西聚酰胺新材料科技有限公司 一种尼龙6生产工艺及其系统与产品
CN113215679B (zh) * 2021-04-30 2022-06-17 东华大学 一种吸光发热聚酰胺基弹性纤维的制备方法
CN114836979A (zh) * 2022-05-27 2022-08-02 四川鑫敬业化纤织带有限公司 一种尼龙阻燃抗红外迷彩织带生产工艺

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4310659A (en) * 1980-04-21 1982-01-12 Allied Corporation Two-stage hydrolysis process for the preparation of nylon 6
CN102358780A (zh) * 2011-08-03 2012-02-22 浙江华建尼龙有限公司 用己内酰胺制造大有光尼龙6切片的生产方法
CN104499076A (zh) * 2014-12-12 2015-04-08 广东新会美达锦纶股份有限公司 一种阻燃聚酰胺6纤维的制备方法
CN104562271A (zh) * 2013-10-28 2015-04-29 上海凯赛生物技术研发中心有限公司 尼龙纤维及其制备方法
CN105669969A (zh) * 2016-02-01 2016-06-15 东华大学 一种尼龙6聚合方法及其熔体直纺方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19519819A1 (de) * 1995-05-31 1996-12-05 Bayer Ag Verfahren zur Wiederverwertung von wäßrigen Extraktlösungen, die bei der Herstellung von PA 6 oder Copolyamiden anfallen
DE10124580A1 (de) * 2001-05-21 2002-12-05 Bayer Ag Verfahren zur Behandlung von Oligoamiden und zur Herstellung von Polyamid
DE10155242A1 (de) * 2001-11-09 2003-05-22 Bayer Ag Herstellung von Polyamid
EP2046863A2 (de) * 2006-05-04 2009-04-15 Uhde Inventa-Fischer AG Verfahren zur kontinuierlichen herstellung von polyamid-granulat

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4310659A (en) * 1980-04-21 1982-01-12 Allied Corporation Two-stage hydrolysis process for the preparation of nylon 6
CN102358780A (zh) * 2011-08-03 2012-02-22 浙江华建尼龙有限公司 用己内酰胺制造大有光尼龙6切片的生产方法
CN104562271A (zh) * 2013-10-28 2015-04-29 上海凯赛生物技术研发中心有限公司 尼龙纤维及其制备方法
CN104499076A (zh) * 2014-12-12 2015-04-08 广东新会美达锦纶股份有限公司 一种阻燃聚酰胺6纤维的制备方法
CN105669969A (zh) * 2016-02-01 2016-06-15 东华大学 一种尼龙6聚合方法及其熔体直纺方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3412704A4 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111621995A (zh) * 2018-03-02 2020-09-04 苏州棠华纳米科技有限公司 一种染料组合物的制备方法
CN111621995B (zh) * 2018-03-02 2022-09-06 苏州棠华纳米科技有限公司 一种染料组合物的制备方法
CN111155193A (zh) * 2020-01-20 2020-05-15 福建中锦新材料有限公司 一种成纤聚合物的合成方法
CN111424328A (zh) * 2020-03-12 2020-07-17 浙江恒澜科技有限公司 一种包含气相抽提、液相萃取的尼龙熔体直纺方法
CN111424328B (zh) * 2020-03-12 2022-12-06 浙江恒逸石化研究院有限公司 一种包含气相抽提、液相萃取的尼龙熔体直纺方法
CN113215678A (zh) * 2021-06-15 2021-08-06 闽江学院 一种荧光透明锦纶长丝的制备方法
CN114775096A (zh) * 2022-03-24 2022-07-22 浙江嘉华特种尼龙有限公司 一种采用固相缩聚直纺技术生产再生锦纶6纤维的方法

Also Published As

Publication number Publication date
EP3412704A4 (en) 2019-12-04
EP3412704A1 (en) 2018-12-12
CN105669969B (zh) 2018-02-09
CN105669969A (zh) 2016-06-15

Similar Documents

Publication Publication Date Title
WO2017133085A1 (zh) 一种尼龙6聚合方法及其熔体直纺方法
CN109957856B (zh) 一种并列复合纤维及其制备方法
CN110117835B (zh) 尼龙纤维及其制备方法
TWI613229B (zh) 聚醯胺組合物及方法
WO2021148039A1 (zh) 一种共聚聚酰胺56/66聚合物及其制备方法与应用
CN111918990B (zh) 聚酰胺纤维及机织针织物、和聚酰胺纤维的制造方法
JP5807456B2 (ja) ポリアミド４１０繊維およびそれからなる繊維構造体
CN109930230A (zh) 一种共聚酰胺工业丝及其制备方法
JP5450695B2 (ja) 形状記憶性ポリアミド生地の製造方法、形状記憶性ポリアミド生地および形状記憶性衣類
CN107815741A (zh) 一种间位芳纶长丝制备方法
WO2019114277A1 (zh) 一步纺弹力复合丝及其制备方法
CN111691001A (zh) 一种离子液体增塑聚酰胺56工业丝的制备方法
CN111040152B (zh) 一种基于预聚体的聚酰胺酯的制备方法及聚酰胺酯纤维的制备方法
CN111979591B (zh) 一种高强度高耐热细单纤尼龙66纤维及其制备方法
JP6379643B2 (ja) 改質ポリエステル繊維及びその混用品
EP1689801A2 (en) Modified polyethylene, terephthalate for low temperature dyeability, controlled shrinkage characteristcs and improved tensile properties
TW201728794A (zh) 可高溫染色的聚醯胺纖維
US3923749A (en) Polymerization of caprolactam
CN117364274B (zh) 全生物基高强度尼龙510纤维及其制备方法和应用
CN115536838B (zh) 一种共聚酰胺树脂、纤维及其制备方法与应用
CN116065411B (zh) 一种高耐日晒尼龙印花面料
JPH0441714A (ja) ポリウレタンウレア弾性繊維
CN117926568A (zh) 一种超低旦锦纶复合面料及其生产工艺
JP2011058133A (ja) 産業繊維構造体
CN115449069A (zh) 一种共聚酰胺树脂、共聚酰胺纤维及其制备方法和应用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16888909

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2016888909

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2016888909

Country of ref document: EP

Effective date: 20180903