WO2022048664A1 - 一种生物基聚酰胺短纤维聚纺牵定一体化成型制备方法及设备 - Google Patents

一种生物基聚酰胺短纤维聚纺牵定一体化成型制备方法及设备 Download PDF

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WO2022048664A1
WO2022048664A1 PCT/CN2021/116659 CN2021116659W WO2022048664A1 WO 2022048664 A1 WO2022048664 A1 WO 2022048664A1 CN 2021116659 W CN2021116659 W CN 2021116659W WO 2022048664 A1 WO2022048664 A1 WO 2022048664A1
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drafting
temperature
spinning
polyamide
setting
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PCT/CN2021/116659
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English (en)
French (fr)
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郝新敏
郭亚飞
梁高勇
闫金龙
乔荣荣
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军事科学院系统工程研究院军需工程技术研究所
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Publication of WO2022048664A1 publication Critical patent/WO2022048664A1/zh

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    • 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
    • D01D5/26—Formation of staple fibres
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/02—Heat treatment
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/098—Melt spinning methods with simultaneous stretching
    • 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
    • D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static 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

Definitions

  • the invention relates to a preparation method and equipment for integral molding of bio-based polyamide staple fibers, which belong to the field of fiber material preparation.
  • Polyamide fibers also known as nylon and nylon, are a large class of synthetic fibers that were first developed and industrialized in the world. It has a development history of more than 80 years and is one of the important polymer materials in modern industry.
  • the repeating unit (monomer) of polyamide (PA) has an amide group as a characteristic feature. Due to its high breaking strength, wear resistance, fatigue resistance, light weight and softness, breathability and moisture absorption, and good elasticity, it is widely used in military products, rubber, etc. Skeleton materials, ropes, nets, cables, tarpaulins, industrial filter cloths, as well as silk for high-end sewing threads, silk for T-shirts, umbrella fabrics, sports textiles and other fields have good market prospects.
  • the traditional direct spinning method is to directly send the polymerized polymer melt to the spinning machine for spinning, and then prepare fibers through the processes of bundling, drafting, and shaping. Although the process is short and the cost is low, until now, polyamide
  • the direct spinning technology of quasi-fiber is not yet mature, and the product performance is unstable. With the rise of bio-based materials, bio-based polyamide fibers have gradually become the focus. my country urgently needs to develop products with good product quality and low production cost that are suitable for bio-based polyamides. Direct spinning method of fibers.
  • the purpose of the present invention is to provide a preparation method and equipment for the integrated molding of bio-based polyamide staple fiber poly-spinning and drawing.
  • the invention provides a bio-based polyamide staple fiber poly-spinning and drawing integrated molding equipment, including a salt solution preparation device system, a polymerization reaction device system, a spinning and drawing device system and a bundle cutting device system connected in sequence;
  • the salt solution preparation device system includes a refined salt storage tank, a salt solution preparation tank, and a salt solution intermediate tank connected in sequence;
  • the polymerization reaction device system includes a concentration tank, a U-shaped reactor, a flasher, a front polymerizer and a rear polymerizer connected in sequence; the salt solution intermediate tank is connected with the inlet of the concentration tank;
  • the spinning and drawing device system includes a spinning box, an oiling device, a winding device, a drafting device, a tension heat setting device, and a cooling and oiling device connected in sequence;
  • a blowing device is provided for cooling the melt stream produced by the spinning box that flows through it;
  • the drafting device includes a first drafting machine, a second drafting machine and a third drafting machine which are connected in sequence
  • the first drafting machine, the second drafting machine and the third drafting machine are all provided with temperature control devices, and the third drafting machine is connected to a tension heat setting device for cooling and oiling. device;
  • the bundled cutting device system includes a bundled device, a wire stacking device, a crimping device, a relaxation heat setting device, a drying device, a cutting device and a packing device which are connected in sequence.
  • the drafting device is specifically divided and combined according to the performance requirements of the prepared product, the first drafting machine is used for normal temperature drafting, the second drafting machine is used for low temperature drafting, and the third drafting machine is used for low temperature drafting.
  • the first drafting machine, the second drafting machine and the third drafting machine may all be at least 1
  • the drafting machines are connected in sequence; more specifically, the number of the third drafting machine is 3 drafting machines are connected for three-stage drafting;
  • the temperature control method of the temperature control device may specifically be at least one of water bath temperature control, hot plate temperature control and steam temperature control.
  • the fiber forming process using the above-mentioned equipment is as follows: the spinning box produces a thin stream of melt; the thin stream of melt flows through the spinning shaft; The thin flow of the melt in the silk tunnel is cooled and blown to make it cool and solidify into a thread; the thread is oiled by the oiling device, and after being wound by the winding device, it is drawn by the drafting device and set by the tension heat-setting device; Cooling and oiling, bundling, stacking, crimping, relaxation heat setting and drying are carried out through the cooling and oiling device, bundling device, wire stacking device, crimping device, relaxation heat setting device, drying device, cutting device, and packaging device , cutting and packaging steps to complete the preparation of bio-based polyamide staple fibers.
  • the present invention also provides a method for preparing bio-based polyamide staple fibers by integral molding of the above-mentioned equipment, comprising the following steps:
  • salt solution preparation process the polyamide dry salt in described refined salt storage tank is injected into described salt solution preparation tank and is mixed with polyamide salt solution solution, and it is stored in described salt solution intermediate tank;
  • the polyamide salt solution in the salt solution intermediate tank is concentrated in the concentration tank and then enters the U-shaped reactor to carry out a prepolymerization reaction, and after the prepolymerization reaction, the rapid decompression is carried out in the flasher, Then enter into the front polymerizer and the back polymerizer in turn, respectively carry out the prepolymerization reaction and the postpolymerization reaction to obtain a polyamide polymer;
  • Bundle cutting process the drawn tow is bundled by the bundle device, stacked by the wire stacking device, crimped by the crimping device, relaxed and thermally shaped by the relaxation heat setting device, and dried by the drying device. After drying, the cutting device and the packaging device are sequentially cut and packaged to obtain the bio-based polyamide staple fiber.
  • the mass percentage of the polyamide salt solution in step 1) may be 20% to 80%, and the pH value is 7.25 to 7.95.
  • step 1) also includes the step of modifying the polyamide by adding an auxiliary agent to the salt solution preparation tank.
  • the auxiliary agent includes at least one of a molecular weight regulator, a flame retardant, an antistatic agent, an antibacterial finishing agent, an anti-ultraviolet finishing agent, and a matting agent;
  • the added amount of the auxiliary agent is 0.10% to 5.50% of the mass of the polyamide 56 dry salt.
  • control pressure of the concentration tank in step 2) is 25-35kPa; the material outlet temperature is 105-130°C.
  • the U-shaped reactor in step 2) adopts the following conditions for prepolymerization in three-stage heating: R1 section inlet material temperature: 150 ⁇ 220 °C, R2 section outlet material temperature: 170 ⁇ 260 °C, R3 The temperature of the material at the outlet of the section: 170 ⁇ 260°C, and the pressure of the reactor is controlled to be stable at 1.70 ⁇ 1.80MPa.
  • the pressure in the reactor is released in the flasher in step 2), and the temperature of the material at the outlet of the flasher rises to 180-290°C.
  • the conditions of the pre-polymerization reaction in step 2) are as follows: the liquid level is stabilized at 30-50%, the material outlet temperature is 220-285°C, and the time is 20-120min.
  • the conditions of the post-polymerization reaction in step 2) are as follows: the liquid level is stabilized at 30-50%, the vacuum degree is 50-80kPa, the material outlet temperature is 220-290°C, the time is 10-60min, and the increase Pressure pump pressure: 10 ⁇ 15MPa.
  • step 3 the polyamide polymer melt described in step 3) is sprayed through a spinneret to obtain a thin stream of melt as follows: the temperature of the spinning box is: the temperature of the first zone of the spinning box is 270-290 °C, the temperature of the second zone is 270 ⁇ 290°C, the temperature of the third zone is 270 ⁇ 290°C, the temperature of the metering pump is 270 ⁇ 290°C, the temperature of the spinning assembly is 270 ⁇ 290°C; the speed of the metering pump is 12 ⁇ 18rpm/min in the spinning box,
  • the polyamide polymer melt is distributed through pipelines and delivered to each spinneret with equal residence time and pressure drop, and the number of spinneret holes is 500-5000; Specifically, it can be 2000m/min, 1000 ⁇ 2000m/min, 2000 ⁇ 3000m/min or 1500 ⁇ 2500m/min.
  • the melt thin stream is cooled and formed by a blowing device, and the blowing device can be a side blowing device or a ring blowing device, and the conditions are as follows: the wind speed can be 0.30-0.50m/min; the wind temperature can be 20 ⁇ 25°C; wind pressure can be 400 ⁇ 500Pa; wind speed can be 0.50m/min, 0.30 ⁇ 0.50m/min, 0.50 ⁇ 0.80m/min or 0.40 ⁇ 0.70m/min; wind temperature can be 25°C, 21 ⁇ 25°C, 25 ⁇ 26°C or 23 ⁇ 26°C; wind pressure can be 440Pa, 420 ⁇ 440Pa, 440 ⁇ 480Pa or 430 ⁇ 470Pa;
  • the oil concentration of the oiling can be 1-10%.
  • the drafting process includes sequentially performing normal temperature drafting through the first drafting machine, low-temperature drafting by the second drafting machine, and hot drafting by the third drafting machine; wherein
  • the drafting can be one-stage drafting, two-stage drafting or multi-stage drafting, and after the drafting, the fibers are bundled through a tension heat-setting device and a cooling and oiling device;
  • the drawing temperature may be 15-30°C, and the drawing ratio may be 1.01-1.85 times;
  • the drafting temperature can be 5-20° C., and the drafting ratio can be 1.01-1.15 times;
  • the drawing temperature can be 60-210°C, and the drawing ratio can be 1.01-6.0 times;
  • the tension heat setting temperature can range from 98 to 230°C according to the difference between normal temperature, low temperature and thermal drawing temperature, specifically 150°C, 170°C, 190°C, 210°C, 230°C, 150 ⁇ 170°C, 150°C. ⁇ 190°C or 150 ⁇ 230°C;
  • the oil concentration can be 2% to 6%
  • the tension heat setting selects different setting processes according to the performance requirements of preparing fibers, and the tension heat setting heating method includes at least one of dry hot air setting, contact heating setting, steam wet heat setting and bath setting.
  • the liquid used in the setting of the bath liquid is water or glycerin.
  • the parameters of the crimping device described in step 4) the pressure of the pressure reducing valve of the main pressure cylinder is 1-3 bar, the pressure of the pressure-reducing valve of the back pressure cylinder is 1 bar, the crimping temperature can be 60-90 °C, and the speed can be 900-1000 m /min, specifically 300m/min, 300-320m/min or 300-340m/min, the number of curls can be 10-30, specifically 15, 10-15, 15-30 or 12-25 .
  • the relaxation heat setting heating method in step 4) includes dry hot air setting and/or contact heating setting, the relaxation heat setting temperature can be 95 ⁇ 190°C, and the residence time is 3 ⁇ 15min.
  • the present invention further provides the bio-based polyamide staple fibers prepared by the above method.
  • the performance parameters of the bio-based polyamide staple fiber of the present invention are as follows: the breaking strength is 4.0-8.0 cN/dtex, and the limiting oxygen index is 28.0-36.0%.
  • Figure 1 is a schematic diagram of the connection of the bio-based polyamide 56 short fiber poly-spinning and traction integrated molding equipment of the present invention.
  • Fig. 2 is a flow chart of the bio-based polyamide 56 short fiber poly-spinning and pinning integrated molding preparation process flow chart of the present invention.
  • Fig. 3 is the process flow diagram of the existing production of polyamide 66 fibers
  • 1 Refined salt storage tank 2 Salt liquid preparation tank; 3 Salt liquid intermediate tank; 4 Concentration tank; 5U type reactor; 6 Flash evaporator; 7 Prepolymerizer; Spinning shaft; 12 oiling device; 13 winding device; 14 first drafting machine; 15 second drafting machine; 16 third drafting machine; 20 wire stacking device; 21 crimping device; 22 relaxation heat setting device; 23 drying device; 24 cutting device; 25 packing device.
  • the limiting oxygen index is tested according to GB/T5454-1997;
  • DSC Differential scanning calorimeter
  • the bio-based polyamide staple fiber equipment of the present invention includes a salt solution preparation device system, a polymerization reaction device system, a spinning pulling device system and a cluster cutting device system connected in sequence;
  • the salt solution preparation device system includes a refined salt storage tank 1, a salt solution preparation tank 2, and a salt solution intermediate tank 3 connected in sequence;
  • the polymerization reaction device system comprises a concentration tank 4, a U-shaped reactor 5, a flasher 6, a front polymerizer 7 and a rear polymerizer 8 connected in sequence; the salt liquid intermediate tank 3 is connected with the inlet of the concentration tank 4;
  • the spinning and drafting device system includes a spinning box 9, an oiling device 12, a winding device 13, and a drafting device (a first drafting machine 14, a second drafting machine 15, a third drafting machine 14, a second drafting machine 15, and a third drafting machine connected in sequence).
  • the first drafting machine 14, the second drafting machine 15 and the third drafting machine 16 are all provided with temperature control devices, and the drafting devices can be divided and combined according to the performance requirements of the prepared products (such as
  • the drawing can be one-stage drafting, two-stage drafting or multi-stage drafting, specifically, for example, the first drafting machine 14, the second drafting machine 15 and the third drafting machine 16 can all be connected in sequence from 1 to 3 units; For example, the number of the third drafting machines 16 is three connected to perform secondary drafting, as shown in Figure 3.
  • the temperature control method of the temperature control device is water bath temperature control, hot plate temperature control and steam temperature control At least one of), tension heat setting device 17; cooling and oiling device 18; wherein, the spinning shaft 11 in the spinning box 9 is provided with a thin stream of melt produced by the spinning box 9 that flows through it.
  • the bundle cutting device system includes a bundle device 19 , a wire stacking device 20 , a crimping device 21 , a relaxation heat setting device 22 , a drying device 23 , a cutting device 24 and a packaging device 25 , which are connected in sequence.
  • Example 1 Integrated molding preparation of bio-based polyamide 56 short fibers
  • Bio-based polyamide 56 staple fibers are prepared by integrated molding using the device shown in Figure 1 and the process flow shown in Figure 2. The specific steps are as follows:
  • a polyamide 56 salt solution with a mass percentage concentration of 60% was prepared. Inject the prepared polyamide 56 salt solution into the salt solution intermediate tank 2, adjust the pH value to 7.85, and then enter the concentration tank 4, the pressure of the concentration tank 4 is 30kPa, the material outlet temperature: 120 ° C; the R1 section of the U-shaped reactor 5 Inlet material temperature control Inlet temperature: 217°C, R2 section outlet temperature: 224°C, R3 section outlet temperature: 245°C, U-type reactor 5 pressure 1.75MPa, and the prepolymer is obtained after the reaction;
  • the prepolymer enters the flasher 6, and the temperature of the material at the outlet is controlled to rise to 277°C.
  • the prepolymer enters the prepolymerizer 7 for prepolymerization reaction, the liquid level is controlled to 45%, the material outlet temperature is 278°C, and the time is 20min;
  • the post-polymerization reaction is carried out in the device 8, the liquid level is controlled to 45%, the vacuum degree: 65kPa, the material outlet temperature is 280°C, the time is 10min, the pressure of the booster pump: 12MPa, and the polyamide 56 polymer is obtained after the reaction; polyamide 56 polymer Enter the spinning box 9 for spinning.
  • the temperature of the spinning box 9 is: 285°C in the first zone, 285°C in the second zone, 285°C in the third zone, 285°C for the metering pump, 13rpm/min for the metering pump, and 285°C for the spinning assembly , the number of spinneret holes is 2300, the spinning speed is 2000m/min, the side blowing speed is 0.50m/min; the wind temperature is 25°C, the side blowing pressure is 440Pa; Commercially available in Takemoto, Japan), after winding and oiling, the fibers were successively drawn at a normal temperature of 20°C, and the drafting ratio was 1.55 times; the first-stage low-temperature drafting temperature was 5°C, and the drafting ratio was 1.03 times; The first pull ratio is 3.57, the second pull ratio is 1.12, the temperature of the first roll is 80 °C, the temperature of the second roll is 150 °C, the temperature of the third roll is 170 °C, and the temperature of the control hot plate is 1
  • the fibers After setting, the fibers are cooled and oiled, the concentration of oil is 3%, and then bundled. After bundled, three pieces of fiber are stacked into one piece and then crimped.
  • the pressure of the main pressure cylinder pressure reducing valve is 2 bar, and the pressure of the back pressure cylinder pressure reducing valve is 1 bar.
  • the temperature can be 60°C, the speed can be 1000m/min, the number of crimps can be 15, and then under the condition of a hot plate temperature of 150°C for 10 minutes, contact heating, relaxation and heat-setting, and finally drying, cutting, and packaging to obtain polyamide 56 short fibers. .
  • the polyamide 56 staple fiber is recorded as 1#, and its performance test results are shown in Table 1.
  • a polyamide 56 salt solution with a mass percentage concentration of 60% was prepared.
  • the prepared polyamide 56 salt solution was injected into the salt solution intermediate tank 3, and 0.50% of the dry salt mass of polyamide 56 was added with titanium dioxide as a matting agent, and the pH value was adjusted to 7.85 to modify the polyamide 56.
  • the rest of the process is exactly the same as that of Example 1 of the present invention.
  • the polyamide 56 staple fiber was obtained, denoted as 2#, and its performance test results are shown in Table 1.
  • the device shown in Figure 1 is used, and the polyamide 56/66 staple fiber is prepared by integrated molding according to the process flow shown in Figure 2.
  • the specific steps are as follows:
  • a polyamide 56/66 salt solution with a mass percentage concentration of 65% is prepared, wherein. Inject the prepared polyamide 56/66 salt solution into the salt solution intermediate tank, adjust the pH value to 7.82, and then enter the concentration tank, the pressure of the concentration tank is 30kPa, the material outlet temperature: 120°C; the R1 section inlet material of the U-shaped reactor Temperature control inlet temperature: 217°C, R2 section outlet temperature: 224°C, R3 section outlet temperature: 245°C, U-type reactor pressure 1.8MPa, and the prepolymer is obtained after the reaction;
  • the prepolymer enters the flasher 6, and the temperature of the material at the outlet is controlled to rise to 277°C.
  • the prepolymer enters the prepolymerizer 7 for prepolymerization reaction, the liquid level is controlled to 45%, the material outlet temperature is 278°C, and the time is 20min;
  • the post-polymerization reaction is carried out in the device 8, the liquid level is controlled to 45%, the vacuum degree: 65kPa, the material outlet temperature is 280°C, the time is 10min, the pressure of the booster pump: 12MPa, and the polyamide 56/66 polymer is obtained after the reaction; polyamide 56 The /66 polymer enters the spinning box 9 for spinning.
  • the temperature of the spinning box 9 is: 286 °C in the first zone, 288 °C in the second zone, 287 °C in the third zone, 287 °C in the metering pump, 12.4 rpm/min in the metering pump speed, spinning
  • the assembly temperature is 287°C, the number of spinneret holes is 2300, the spinning rate is 2400m/min, the side blowing speed is 0.40m/min; the air temperature is 20°C, the side blowing pressure is 480Pa; the concentration of oil is 6% (winding
  • the oiling agent is F5103, commercially available from Takemoto, Japan), and after winding and oiling, the fibers are successively subjected to a first-level normal temperature drafting temperature of 20 °C, and a drafting ratio of 1.32 times; a low-temperature drafting temperature of 5 °C, and a drafting ratio of 1.02 times;
  • the first-drawing ratio of the two-stage hot drawing is 3.34
  • the fibers After setting, the fibers are cooled and oiled, the concentration of oil is 3%, and then bundled. After bundled, three pieces of fiber are stacked into one piece and then crimped.
  • the pressure of the main pressure cylinder pressure reducing valve is 2 bar, and the pressure of the back pressure cylinder pressure reducing valve is 1 bar.
  • the temperature can be 60°C
  • the speed can be 1000m/min
  • the number of crimps can be 15, and then under the condition of a hot plate temperature of 160°C for 10 minutes, contact heating to relax and heat-setting, and finally, after drying, cutting and packaging, polyamide 56/66 is obtained. short fibre.
  • Polyamide 56/66 staple fiber is recorded as 3#, and its performance test results are shown in Table 1.
  • the preparation mass percentage concentration of 55% polyamide 510 salt solution According to the preparation mass percentage concentration of 55% polyamide 510 salt solution. Inject the prepared polyamide 510 salt solution into the salt solution intermediate tank 2, adjust the pH value to 7.45, and then enter the concentration tank 4, the pressure of the concentration tank 4 is 25kPa, the material outlet temperature: 100 ° C; the R1 section of the U-shaped reactor 5 Inlet material temperature control Inlet temperature: 170 °C, R2 section outlet temperature: 180 °C, R3 section outlet temperature: 185 °C, U-type reactor 5 pressure 1.78MPa, after the reaction, the prepolymer is obtained; the prepolymer enters the flasher 6, The temperature of the material at the outlet was controlled to rise to 185°C, the prepolymer entered the prepolymerizer 7 for prepolymerization, the liquid level was controlled to 45%, the temperature at the material outlet was 215°C, and the time was 60min; the prepolymer entered the backpolymerizer 8 for postpolymerization
  • the fibers After setting, the fibers are cooled and oiled, the concentration of oil is 3%, and then bundled. After bundled, three pieces of fiber are stacked into one piece and then crimped.
  • the pressure of the pressure reducing valve of the main pressure cylinder is 2 bar, and the pressure of the pressure reducing valve of the back pressure cylinder is 1 bar.
  • the temperature can be 50°C
  • the speed can be 900m/min
  • the number of crimps is 15, and then contact heating under the condition of 130°C hot plate for 12min to relax and heat-set, and finally, after drying, cutting and packaging, polyamide 510 short fibers are obtained. .
  • Polyamide 510 staple fiber is recorded as 4#, and its performance test results are shown in Table 1.
  • the configuration of the polyamide 56 salt solution, the polymerization reaction and the melt-spinning process are all the same as those in Example 1 of the present invention, and the thermal drafting temperature in the post-spinning process is changed to study the changes in fiber properties.
  • the undrawn fiber is recorded as 5#.
  • Hot drawing and setting process in post-spinning process two-stage hot-drawing, one-drawing ratio (drawing 2.0, 2.5, 3.0, 3.4 respectively); two-drawing ratio 1.05; one-roll temperature of the drafting box 80°C; two-roll temperature 150 °C; three-roll temperature 170 °C; dry hot air tension setting is carried out under the condition of hot plate temperature 170 °C after drawing.
  • the polyamide 56 staple fibers prepared in this comparative example are denoted as 5# to 9#.
  • the melting point of the undrawn yarn was 252.2°C, and the melting point slightly increased after the fiber was drawn.
  • the draw ratio is increased to 3.0, the Tm rises to 230.1°C.
  • the crystallinity of the fibers increased rapidly, and when the drafting ratio was greater than 2.5, the crystallinity increased slowly.
  • the undrawn yarn has no orientation. After drawing, the crystallization and sonic orientation increase with the increase of the draw ratio, and the breaking strength increases slowly with the increase of the draw ratio.
  • the first-drawing ratio of the second-stage hot-drawing is 3.0; the second-drawing ratio is 1.05; the temperature of the first roll of the drafting box is 80 °C; the temperature of the second roll is 150 °C; the temperature of the third roll is 170 °C; Under the condition of plate temperature (150 ⁇ 230°C, interval 20°C), dry hot air tension setting is carried out.
  • the polyamide 56 staple fibers prepared in this example are denoted as 11#-15#.
  • the crystal orientation of the polyamide 56 fibers set at different temperatures increased from 76.04 to 82.09, as shown in Table 3.
  • the crystallinity of the fibers after heat-setting generally tends to increase, but the crystallinity is the highest when the heat-setting temperature is 150-170 °C;
  • the crystal orientation of nylon 56 fibers increased, and the breaking strength increased.
  • the temperature continued to rise to 230 °C the crystal orientation decreased and the breaking strength decreased. This may be due to the strong damage of fibers in high temperature treatment.
  • the configuration of the polyamide 56 salt solution, the polymerization reaction and the melt spinning process are all the same as the parameter settings of Example 1 of the present invention.
  • Drawing process the same process is set parameters with reference to Example 1 of the present invention, in the test, it is found that after the tow is converged, a fuse phenomenon occurs occasionally on the winding barrel, and the appearance of the output fiber appears woolly, and the test performance strength is low only 0.84 cN/dtex, unable to meet application standards.
  • the process of drafting at normal temperature and low temperature is added in the present invention to rapidly cool down the fiber and ensure the smooth progress of subsequent processes; Therefore, the crystallization is difficult and imperfect, which is helpful for subsequent high-stretching and short fibers with excellent performance.
  • Polyamide 56 salt solution preparation and polymerization are prepared according to the content of Example 1;
  • Polyamide 56 polymer enters spinning box for spinning, spinning box temperature: 285°C in the first zone, 285°C in the second zone, 285°C in the third zone, metering pump temperature 285°C, metering pump speed 13rpm/min, number of spinneret holes 2300 pieces, the spinning assembly temperature is 285°C, the spinning speed is 2000m/min, the side blowing speed is 0.50m/min; the air temperature is 25°C, the side blowing pressure is 440Pa; F5103, commercially available from Takemoto, Japan), bundled, the fibers were wound and oiled and then subjected to secondary drafting, the first draft ratio was 3.57, the second draft ratio was 1.12, the temperature of the first roll was 80 °C, the temperature of the second roll was 150 °C, and the temperature of the third roll was 170 °C , Control the temperature of the hot plate to 170 °C for dry hot air tension setting.
  • the pressure of the pressure reducing valve of the main pressure cylinder is 2bar
  • the pressure of the pressure reducing valve of the back pressure cylinder is 1bar
  • the crimping temperature can be 60°C
  • the speed can be 900m/min
  • the number of crimping can be 15.
  • a hot plate temperature 150° C. for 10 minutes, contact heating, relaxation, and heat-setting, and finally drying, cutting, and packaging to obtain polyamide 56 short fibers.
  • the fiber prepared in this comparative example has a breaking strength of 3.23 cN/dtex, an elongation at break of 54.3%, and a limiting oxygen index of 23%.
  • the polyamide 56 short fibers prepared by the present invention have higher breaking strength and limiting oxygen index, indicating that the process of the present invention can improve the mechanical properties and flame retardant properties of polyamide fibers.
  • the technological process of the present invention is changed, (1) due to the slow cooling rate of the bio-based polyamide fiber, the first bundling and then the drawing easily lead to the melting of the silk, which reduces the product performance; (2) the normal temperature drafting and low temperature drafting are added in the drafting process. Step, the fiber is rapidly cooled, so that the polymer molecular chain does not have enough time to arrange and stack, resulting in difficult and imperfect crystallization. In the case of unstable performance, on the other hand, it helps to improve the fiber properties.
  • the normal temperature drafting and low temperature drafting help the subsequent high-fold drafting, so as to obtain short fibers with excellent performance; (3) Change the drafting of bio-based polyamide fibers
  • Process and heat-setting temperature conditions, adjusting the process equipment for bio-based polyamides can improve the crystallinity, orientation, mechanical properties, flame retardancy, etc. of the fibers.
  • the equipment of the present invention is a continuous production device, and it is a continuous and integrated production process from the configuration of the brine solution to the cutting of fibers, which abandons the traditional intermittent production, effectively saves the production cost and improves the work efficiency.

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Abstract

一种生物基聚酰胺短纤维聚纺牵定一体化成型制备方法及设备。本发明设备包括依次连接的盐液调配装置系统、聚合反应装置系统、纺丝牵定装置系统和集束切断装置系统；其中，纺丝牵定装置系统中的牵伸装置包括依次连接的第一牵伸机（14）、第二牵伸机（15）和第三牵伸机（16），牵伸机上均设有控温装置，第三牵伸机后连接紧张热定型装置（17）和冷却上油装置（18）。该聚酰胺纤维聚纺牵定一体化成型制备方法采用先牵伸定型后集束，并且在牵伸过程加入常温牵伸、低温牵伸步骤，使成型丝束快速冷却，有助于改善纤维产品性能。该一体化成型制备方法及设备有效节约了生产成本，提高了生产效率，并且得到性能稳定的生物基聚酰胺短纤维。

Description

一种生物基聚酰胺短纤维聚纺牵定一体化成型制备方法及设备 技术领域
本发明涉及一种生物基聚酰胺短纤维聚纺牵定一体成型制备方法及设备，属于纤维材料制备领域。
背景技术
聚酰胺纤维又称尼龙、锦纶是世界上最早发展并实现工业化生产的一大类合成纤维。迄今已有80多年的发展历史，是现代工业重要的聚合物材料之一。聚酰胺(PA)的重复单元(单体)具有酰胺基团作为特征性特征，由于其断裂强度高、耐磨、耐疲劳、轻质柔软、透气吸湿、弹性好等特点，在军工产品、橡胶骨架材料、绳、网、索类、篷布、工业滤布以及在高档缝纫线用丝、T恤衫用丝、雨伞面料、运动纺织品等领域拥有良好的市场前景。
目前市场占有量最大的聚酰胺6和聚酰胺66的生产原料主要来源于石油化工产品，面对世界化石资源的日益匮乏、全球环境的不断恶化，寻找清洁能源以替代石油化工产品，已是各国工业发展的重点关注方向。生物基聚酰胺是利用微生物发酵淀粉制备出戊二胺，进而与己二酸聚合纺丝制备了生物基聚酰胺纤维，具有绿色、环境友好、原料可再生以及可生物降解的特性，有助于解决当前全球经济社会发展所面临的严重的资源和能源短缺，以及环境污染等问题，是当今世界各国纺织纤维发展竞争的热点。
传统直接纺丝法是将聚合后的聚合物熔体直接送至纺丝机进行纺丝，然后经过集束、牵伸、定型等工序制备纤维，虽然工序短，成本低，但是直到现在，聚酰类纤维直接纺丝技术尚未成熟，产品性能不稳定，而随着生物基材料的兴起，生物基聚酰胺纤维逐渐成为焦点，我国急需开发产品质量好、生产成本低的适用于生物基类聚酰胺纤维的直接纺丝方法。
发明公开
本发明的目的是提供一种生物基聚酰胺短纤维聚纺牵定一体化成型的制备方法及设备。
本发明提供的一种生物基聚酰胺短纤维聚纺牵定一体化成型的设备，包括依次连接的盐液调配装置系统、聚合反应装置系统、纺丝牵定装置系统和集束切断 装置系统；
所述盐液调配装置系统包括依次连接的精盐储罐、盐液调配罐、盐液中间罐；
所述聚合反应装置系统包括依次连接的浓缩槽、U型反应器、闪蒸器、前聚合器和后聚合器；所述盐液中间罐与所述浓缩槽的入口相连接；
所述纺丝牵定装置系统包括依次连接的纺丝箱、上油装置、卷绕装置、牵伸装置、紧张热定型装置、冷却上油装置；其中，所述纺丝箱的纺丝甬道旁设有对其内流经的所述纺丝箱产出的熔体细流进行冷却的吹风装置；所述牵伸装置包括依次连接的第一牵伸机、第二牵伸机和第三牵伸机，所述第一牵伸机、所述第二牵伸机和所述第三牵伸机上均设有控温装置，所述第三牵伸机后连接紧张热定型装置、冷却上油装置；
所述集束切断装置系统包括依次连接的集束装置、叠丝装置、卷曲装置、松弛热定型装置、烘干装置、切断装置和打包装置。
本发明中，所述牵伸装置具体根据制备产品性能要求不同拆分组合，所述第一牵伸机进行常温牵伸、所述第二牵伸机进行低温牵伸、所述第三牵伸机进行热牵伸；如根据牵伸为一级牵伸、二级牵伸或多级牵伸，具体如第一牵伸机、第二牵伸机和第三牵伸机可均为至少1台牵伸机依次连接；更具体如第三牵伸机数量为3台牵伸机连接，以进行三级牵伸；
所述控温装置的控温方式具体可为水浴控温、热板控温和蒸汽控温中的至少一种。
本发明中，采用上述的设备进行纤维成型加工过程如下：所述纺丝箱产出熔体细流；所述熔体细流流经所述纺丝甬道；所述吹风装置对流经所述纺丝甬道的熔体细流进行冷却吹风，使其冷却凝固成为丝条；丝条经过上油装置上油，卷绕装置卷绕后，经过牵伸装置牵伸、紧张热定型装置定型；然后依次经所述冷却上油装置、集束装置、叠丝装置、卷曲装置、松弛热定型装置、烘干装置、切断装置、打包装置进行冷却上油、集束、叠丝、卷曲、松弛热定型、烘干、切断、打包步骤完成生物基聚酰胺短纤的制备。
本发明还提供了一种利用上述设备一体化成型制备生物基聚酰胺短纤维的方法，包括如下步骤：
1)盐液配制过程：将所述精盐储罐中的聚酰胺干盐注入所述盐液调配罐配 制成聚酰胺盐水溶液，并将其存储于所述盐液中间罐；
2)聚合过程：所述盐液中间罐中聚酰胺盐水溶液经所述浓缩槽浓缩后进入所述U型反应器中进行预聚反应，预聚反应后在所述闪蒸器中进行快速解压，再依次进入所述前聚合器和所述后聚合器中，分别进行前聚合反应和后聚合反应，得到聚酰胺聚合物；
3)纺丝牵定过程：将所述聚酰胺聚合物熔体经所述纺丝箱的喷丝板喷出熔体细流，熔体细流流经所述纺丝甬道，经所述吹风装置冷却凝固成为丝条，所述丝条经所述上油装置上油、卷绕装置卷绕、牵伸装置牵伸，紧张热定型装置定型，冷却上油装置冷却上油后得到牵伸丝束；
4)集束切断过程：所述牵伸丝束依次经所述集束装置集束、所述叠丝装置叠丝、所述卷曲装置卷曲、所述松弛热定型装置松弛热定型、所述烘干装置烘干，最后经所述切断装置和打包装置依次切断、打包，即得到所述生物基聚酰胺短纤维。
上述的方法中，步骤1)所述聚酰胺盐水溶液的质量百分含量可为20％～80％，pH值7.25～7.95。
上述的方法中，步骤1)中还包括通过所述盐液调配罐添加助剂对所述聚酰胺进行改性的步骤。
上述的方法中，所述助剂包括分子量调节剂、阻燃剂、抗静电剂、抗菌整理剂、抗紫外线整理剂、消光剂中的至少一种；
所述助剂加入量为所述聚酰胺56干盐质量的0.10％～5.50％。
上述的方法中，步骤2)所述浓缩槽控制压力：25～35kPa；物料出口温度105～130℃。
上述的方法中，步骤2)所述U型反应器采用三段加热中进行预聚反应的条件如下：R1段入口物料温度：150～220℃，R2段出口物料温度：170～260℃，R3段出口物料温度：170～260℃，控制反应器压力稳定在1.70～1.80MPa。
上述的方法中，步骤2)所述闪蒸器中释放反应器内的压力，所述闪蒸器出口物料温度升至180～290℃。
上述的方法中，步骤2)所述前聚合反应的条件如下：液位稳定在30～50％，物料出口温度为220℃～285℃，时间为20～120min。
上述的方法中，步骤2)所述后聚合反应的条件如下：液位稳定在 30～50％，真空度：50～80kPa，物料出口温度为220℃～290℃，时间为10～60min，增压泵压力：10～15MPa。
上述的方法中，步骤3)中所述聚酰胺聚合物熔体经喷丝板喷出得到熔体细流的过程如下：所述纺丝箱温度为：纺丝箱体一区温度270～290℃，二区温度270～290℃，三区温度270～290℃，计量泵温度270～290℃，纺丝组件温度为270～290℃；计量泵转速12～18rpm/min在纺丝箱体内，所述聚酰胺聚合物熔体通过管路分配，以相等的停留时间和压力降输送到每一个喷丝口，喷丝头孔数500～5000根；纺丝速率可为1000～3000m/min，具体可为2000m/min、1000～2000m/min、2000～3000m/min或1500～2500m/min。
上述的方法中，所述熔体细流经吹风装置冷却成型，所述吹风装置可为侧吹风装置或环吹风装置，其条件如下：风速可为0.30～0.50m/min；风温可为20～25℃；风压可为400～500Pa；风速具体可为0.50m/min、0.30～0.50m/min、0.50～0.80m/min或0.40～0.70m/min；风温具体可为25℃、21～25℃、25～26℃或23～26℃；风压具体可为440Pa、420～440Pa、440～480Pa或430～470Pa；
所述上油的油剂浓度可为1～10％。
上述的方法中，所述牵伸过程包括依次经所述第一牵伸机进行常温牵伸、所述第二牵伸机进行低温牵伸、所述第三牵伸机进行热牵伸；其中所述牵伸可为一级牵伸、二级牵伸或多级牵伸，牵伸后纤维经过紧张热定型装置、冷却上油装置后集束；
所述常温牵伸中牵伸温度可为15～30℃，牵伸的倍率可为1.01～1.85倍；
所述低温牵伸中牵伸温度可为5～20℃，牵伸的倍率可为1.01～1.15倍；
所述热牵伸中牵伸温度可为60～210℃，牵伸的倍率可为1.01～6.0倍；
所述紧张热定型温度根据常温、低温、热牵伸温度的不同，范围可为98～230℃，具体可为150℃、170℃、190℃、210℃、230℃、150～170℃、150～190℃或150～230℃；
所述冷却上油装置，油剂浓度可为2％～6％；
所述紧张热定型根据制备纤维性能要求选择不同定型工艺，所述紧张热定型加热方式包括干热空气定型、接触加热定型、水蒸气湿热定型和浴液定型中的至少一种。所述浴液定型采用的液体为水或甘油。
上述的方法中，步骤4)中所述卷曲装置参数：主压气缸减压阀压力 1～3bar、背压气缸减压阀压力1bar，卷曲温度可为60～90℃，速率可为900～1000m/min，具体可300m/min、300～320m/min或300～340m/min，卷曲数可为10～30个，具体可为15个、10～15个、15～30个或12～25个。
上述的方法中，步骤4)中所述松弛热定型加热方式包括干热空气定型和/或接触加热定型，所述松弛热定型的温度可为95～190℃，停留时间为3～15min。
本发明进一步提供了上述的方法制备得到的生物基聚酰胺短纤维。
本发明所述生物基聚酰胺短纤维的性能参数如下：断裂强度4.0～8.0cN/dtex，极限氧指数28.0～36.0％。
附图说明
图1为本发明生物基聚酰胺56短纤维聚纺牵定一体化成型设备的连接示意图。
图2为本发明生物基聚酰胺56短纤维聚纺牵定一体化成型制备工艺流程图。
图3为现有生产聚酰胺66纤维的工艺流程图
图1、图3中各个标记如下：
1精盐储罐；2盐液调配罐；3盐液中间罐；4浓缩槽；5U型反应器；6闪蒸器；7前聚合器；8后聚合器；9纺丝箱；10吹风装置；11纺丝甬道；12上油装置；13卷绕装置；14第一牵伸机；15第二牵伸机；16第三牵伸机；17紧张热定型装置；18冷却上油装置19集束装置；20叠丝装置；21卷曲装置；22松弛热定型装置；23烘干装置；24切断装置；25打包装置。
实施发明的最佳方式
下述实施例中的实验方法，如无特别说明，均为常规方法
下述实施例中，1、线密度根据GB/T14335-2008测试；
2、断裂强度和断裂伸长率(％)根据GB/T14337-2008测试；
3、极限氧指数根据GB/T5454-1997测试；
4、差示扫描量热仪(DSC)测试纤维的熔点、结晶度；
5、回潮率：根据GB/T6503-2008测试。
如图1所示，为本发明生物基聚酰胺短纤维设备。它包括依次连接的盐液调 配装置系统、聚合反应装置系统、纺丝牵定装置系统和集束切断装置系统；
盐液调配装置系统包括依次连接的精盐储罐1、盐液调配罐2、盐液中间罐3；
聚合反应装置系统包括依次连接的浓缩槽4、U型反应器5、闪蒸器6、前聚合器7和后聚合器8；盐液中间罐3与浓缩槽4的入口相连接；
纺丝牵定装置系统包括依次连接的纺丝箱9、上油装置12、卷绕装置13、牵伸装置(由依次连接的第一牵伸机14、第二牵伸机15、第三牵伸机16组成，第一牵伸机14、第二牵伸机15和第三牵伸机16上均设有控温装置，牵伸装置可以根据制备产品性能要求不同拆分组合(如根据牵伸为一级牵伸、二级牵伸或多级牵伸，具体如第一牵伸机14、第二牵伸机15和第三牵伸机16可均为1～3台依次连接；本例具体如第三牵伸机16数量为3台连接，以进行二级牵伸，如图3所示。)，控温装置的控温方式为水浴控温、热板控温和蒸汽控温中的至少一种)、紧张热定型装置17；冷却上油装置18；其中，纺丝箱9中纺丝甬道11旁设有对其内流经的纺丝箱9产出的熔体细流进行冷却的吹风装置10；
集束切断装置系统包括依次连接的集束装置19、叠丝装置20、卷曲装置21、松弛热定型装置22、烘干装置23、切断装置24和打包装置25。
实施例1、生物基聚酰胺56短纤维的一体化成型制备
采用如图1中所示装置，并按照如图2所示的工艺流程进行一体化成型制备生物基聚酰胺56短纤维，具体步骤如：
配制质量百分浓度为60％的聚酰胺56盐水溶液。将已制备好的聚酰胺56盐水溶液注入盐液中间罐2，调节pH值为7.85，然后进入浓缩槽4，浓缩槽4压力30kPa，物料出口温度：120℃；U型反应器5的R1段入口物料温度控制入口温度：217℃，R2段出口温度：224℃，R3段出口温度：245℃，U型反应器5压力1.75MPa，反应后得到预聚体；
预聚体进入闪蒸器6，控制出口物料温度升至277℃，预聚体进入前聚合器7中进行前聚合反应，控制液位45％，物料出口温度278℃，时间为20min；进入后聚合器8中进行后聚合反应，控制液位45％，真空度：65kPa，物料出口温度为280℃，时间10min，增压泵压力：12MPa，反应后得到聚酰胺56聚合物；聚酰胺56聚合物进入纺丝箱9进行纺丝，纺丝箱9温度：一区285℃，二区285℃，三区 285℃，计量泵温度285℃，计量泵转速13rpm/min，纺丝组件温度为285℃，喷丝头孔数2300根，纺丝速率2000m/min，侧吹风速为0.50m/min；风温为25℃，侧吹风压为440Pa；油剂浓度5％(卷绕油剂为F5103，商购于日本竹本)，卷绕上油后纤维依次进行一级常温牵伸温度20℃，牵伸倍率1.55倍；一级低温牵伸温度5℃，牵伸倍率1.03倍；二级热牵伸的一牵倍率3.57，二牵倍率1.12、一辊温度80℃，二辊温度150℃，三辊温度170℃，控制热板温度170℃进行干热空气紧张定型。定型后纤维冷却上油，油剂浓度3％，再集束，集束后将纤维三片丝叠成一片后进行卷曲，卷曲主压气缸减压阀压力2bar，背压气缸减压阀压力1bar，卷曲温度可为60℃，速率可为1000m/min、卷曲数15个，然后在热板温度150℃条件下10min接触加热松弛热定型，最后经烘干、切断、打包，即得到聚酰胺56短纤维。
聚酰胺56短纤记为1#，其性能测试结果如表1所示。
实施例2、
配制质量百分浓度为60％的聚酰胺56盐水溶液。将已制备好的聚酰胺56盐水溶液注入盐液中间罐3，同时加入聚酰胺56干盐质量的0.50％消光剂二氧化钛，调节pH值为7.85，将聚酰胺56改性。其余工艺与本发明实施例1完全相同。得到聚酰胺56短纤，记为2#，其性能测试结果如表1所示。
实施例3
采用如图1中所示装置，并按照如图2所示的工艺流程进行一体化成型制备聚酰胺56/66短纤维，具体步骤如：
按照聚酰胺56干盐与聚酰胺66干盐质量比为9:1，配制质量百分浓度为65％的聚酰胺56/66盐水溶液，其中。将已制备好的聚酰胺56/66盐水溶液注入盐液中间罐，调节pH值为7.82，然后进入浓缩槽，浓缩槽压力30kPa，物料出口温度：120℃；U型反应器的R1段入口物料温度控制入口温度：217℃，R2段出口温度：224℃，R3段出口温度：245℃，U型反应器压力1.8MPa，反应后得到预聚体；
预聚体进入闪蒸器6，控制出口物料温度升至277℃，预聚体进入前聚合器7中进行前聚合反应，控制液位45％，物料出口温度278℃，时间为20min；进入后聚合器8中进行后聚合反应，控制液位45％，真空度：65kPa，物料出口温度为280℃，时间10min，增压泵压力：12MPa，反应后得到聚酰胺56/66聚合物；聚酰胺56/66聚合物进入纺丝箱9进行纺丝，纺丝箱9温度：一区286℃，二区 288℃，三区287℃，计量泵温度287℃，计量泵转速12.4rpm/min，纺丝组件温度为287℃，喷丝头孔数2300根，纺丝速率2400m/min，侧吹风速为0.40m/min；风温为20℃，侧吹风压为480Pa；油剂浓度6％(卷绕油剂为F5103，商购于日本竹本)，卷绕上油后纤维依次进行一级常温牵伸温度20℃，牵伸倍率1.32倍；一级低温牵伸温度5℃，牵伸倍率1.02倍；二级热牵伸的一牵倍率3.34，二牵倍率1.12、一辊温度90℃，二辊温度160℃，三辊温度175℃，控制热板温度175℃进行干热空气紧张定型。定型后纤维冷却上油，油剂浓度3％，再集束，集束后将纤维三片丝叠成一片后进行卷曲，卷曲主压气缸减压阀压力2bar，背压气缸减压阀压力1bar，卷曲温度可为60℃，速率可为1000m/min、卷曲数15个，然后在热板温度160℃条件下10min接触加热松弛热定型，最后经烘干、切断、打包，即得到聚酰胺56/66短纤维。
聚酰胺56/66短纤记为3#，其性能测试结果如表1所示。
实施例4、生物基聚酰胺510短纤维的一体化成型制备
采用如图1中所示装置，并按照如图2所示的工艺流程进行一体化成型制备聚酰胺510短纤维，具体步骤如：
按照配制质量百分浓度为55％的聚酰胺510盐水溶液。将已制备好的聚酰胺510盐水溶液注入盐液中间罐2，调节pH值为7.45，然后进入浓缩槽4，浓缩槽4压力25kPa，物料出口温度：100℃；U型反应器5的R1段入口物料温度控制入口温度：170℃，R2段出口温度：180℃，R3段出口温度：185℃，U型反应器5压力1.78MPa，反应后得到预聚体；预聚体进入闪蒸器6，控制出口物料温度升至185℃，预聚体进入前聚合器7中进行前聚合反应，控制液位45％，物料出口温度215℃，时间为60min；进入后聚合器8中进行后聚合反应，控制液位45％，真空度：60kPa，物料出口温度为215℃，时间20min，增压泵压力：14MPa，反应后得到聚酰胺510聚合物；聚酰胺510聚合物进入纺丝箱9进行纺丝，纺丝箱9温度：一区245℃，二区245℃，三区245℃，计量泵温度245℃，计量泵转速15rpm/min，纺丝组件温度为245℃，喷丝头孔数2000根，纺丝速率900m/min，侧吹风速为0.50m/min；风温为22℃，侧吹风压为430Pa；油剂浓度3％(卷绕油剂为F5103，商购于日本竹本)，卷绕上油后纤维依次进行一级常温牵伸温度18℃，牵伸倍率1.15倍；一级低温牵伸温度8℃，牵伸倍率1.04倍；二级热牵伸一牵倍率2.83，二牵倍率1.07、一辊温度60℃，二辊温度120℃，三辊温度 150℃，控制热板温度150℃进行干热空气紧张定型。定型后纤维冷却上油，油剂浓度3％，再集束，集束后将纤维三片丝叠成一片后进行卷曲，卷曲主压气缸减压阀压力2bar，背压气缸减压阀压力1bar，卷曲温度可为50℃，速率可为900m/min、卷曲数15个，然后在热板温度130℃条件下12min接触加热松弛热定型，最后经烘干、切断、打包，即得到聚酰胺510短纤维。
聚酰胺510短纤记为4#，其性能测试结果如表1所示。
表1聚酰胺短纤维测试数据
Figure PCTCN2021116659-appb-000001
实施例5、
聚酰胺56盐水溶液配置、聚合反应以及熔融纺丝过程均与本发明实施例1完全相同，改变后纺工艺中热牵伸温度，研究纤维性能变化。未牵伸纤维记为5#。
后纺工艺中热牵伸定型工艺：二级热牵伸，一牵倍率(分别牵伸2.0、2.5、3.0、3.4)；二牵倍率1.05；牵伸箱一辊温度80℃；二辊温度150℃；三辊温度170℃；牵伸后在热板温度170℃的条件下进行干热空气紧张定型。本对比例制备的聚酰胺56短纤记为5#～9#。
纤维熔点、熔融焓、结晶度、取向、力学性能测试结果如表2所示。
未牵伸丝的熔点在252.2℃，纤维拉伸后，熔点有微弱的升高。当牵伸倍数增加到3.0时，T m升到230.1℃。牵伸后，纤维的结晶度迅速增加，牵伸倍数大于2.5后，结晶度增加缓慢。未牵伸丝无取向，牵伸后，结晶和声速取向都随着牵伸倍数的增加而增加，断裂强度随着牵伸倍数的增加缓慢增加。
表2 PA56纤维熔点、熔融焓、结晶度、取向、力学性能测试结果
Figure PCTCN2021116659-appb-000002
Figure PCTCN2021116659-appb-000003
测试牵伸工艺前后纤维物理性能，随着牵伸倍数增加，纤维的结晶和声速取向都增加，机械性能中，断裂强度缓慢增加。
实施例6、
聚酰胺56盐水溶液配置、聚合反应以及熔融纺丝过程均与本发明实施例1完全相同，改变后纺热牵伸定型工艺中定型温度，研究纤维性能变化。未定型纤维记为10#。
后纺热牵伸定型工艺：二级热牵伸的一牵倍率3.0；二牵倍率1.05；牵伸箱一辊温度80℃；二辊温度150℃；三辊温度170℃；牵伸后控制热板温度(150～230℃，间隔20℃)的条件下进行干热空气紧张定型。本实施例制备的聚酰胺56短纤记为11#～15#。
在150～230℃范围内不同温度的热定型过程中，不同温度定型聚酰胺56纤维的晶体取向从76.04增加到82.09，如表3所示。
表3热定型温度对纤维结构的影响
Figure PCTCN2021116659-appb-000004
升高温度有利于聚合物分子链排列的更加规整，形成更加完整的结晶结构，因此热定型后纤维结晶度总体呈增长趋势，但是在热定型温度在150～170℃条件下，结晶度最高；在150～210℃范围内不同温度的热定型过程中，锦纶56纤维的晶体取向有所增加，断裂强度成增长趋势，当温度继续升高至230℃，晶区取向减小，断裂强度降低，这可能是由于高温处理纤维强力损伤。
对比例1、
聚酰胺56盐水溶液配置、聚合反应以及熔融纺丝过程均与本发明实施例1的参数设定完全相同，当纤维冷却成丝条上油后，按照传统纺丝加工进行，直接进行集束、牵伸工艺，同样工艺参照本发明实施例1设定参数，试验中发现丝束汇聚后在卷绕桶上偶尔出现熔丝现象，并且产出的纤维外观出现毛丝、测试性能强度低仅为0.84cN/dtex，无法达到应用标准。
这可能是因为聚酰胺56的冷却结晶温度低，结晶速率慢。在纺丝时，纤维没有完全冷却就开始卷绕，多层纤维叠加，纤维内部热量无法散失，不仅出现熔丝现象，而且影响产品性能，但是如果直接将初生纤维温度冷却到10℃以下，则纤维可能发生脆损，因此，聚酰胺56初生纤维需要依次进行常温牵伸、低温牵伸、热牵伸后再进行后续工艺流程。本发明增加常温牵伸、低温牵伸工艺一方面使纤维快速降温，保证后续工序顺利进行；另一方面由于聚合物分子链折叠进入晶格的速度跟不上温度的下降速度，分子链没有充足的时间排布与堆砌，因而结晶困难、不完善，有助于后续高倍牵伸，得到性能优异的短纤维。
对比例2、
常规工艺制备生物基聚酰胺56：
采用现有聚酰胺66生产流程，制备聚酰胺56短纤维，具体步骤如：
聚酰胺56盐液配制、聚合按照实施例1内容制备；
聚酰胺56聚合物进入纺丝箱纺丝，纺丝箱温度：一区285℃，二区285℃，三区285℃，计量泵温度285℃，计量泵转速13rpm/min，喷丝头孔数2300根，纺丝组件温度为285℃，纺丝速率2000m/min，侧吹风速为0.50m/min；风温为25℃，侧吹风压为440Pa；油剂浓度5％(卷绕油剂为F5103，商购于日本竹本)，集束，卷绕上油后纤维进行二级牵伸，一牵倍率3.57，二牵倍率1.12、一辊温度80℃，二辊温度150℃，三辊温度170℃，控制热板温度170℃进行干热空气紧张定型。再将纤维三片丝叠成一片后进行卷曲，卷曲主压气缸减压阀压力2bar，背压气缸减压阀压力1bar，卷曲温度可为60℃，速率可为900m/min、卷曲数15个，然后在热板温度150℃条件下10min接触加热松弛热定型，最后经烘干、切断、打包，即得到聚酰胺56短纤维。
本对比例制备的纤维断裂强度3.23cN/dtex，断裂伸长率54.3％，极限氧指数23％。
由上述数据可知，通过与对比例2相比，本发明制备的聚酰胺56短纤维断裂 强度和极限氧指数更高，说明本发明工艺可以改善聚酰胺类纤维的力学性能及阻燃性能。
工业应用
本发明工艺流程改变，(1)由于生物基聚酰胺纤维冷却速率较慢，先集束后牵伸容易导致融丝，使产品性能下降；(2)在牵伸过程加入常温牵伸、低温牵伸步骤，纤维快速冷却，使聚合物分子链没有充足的时间排布与堆砌，导致结晶困难、不完善，一方面避免了由于纤维冷却速率慢，集束后直接牵伸纤维芯皮层差异大，成品纤维性能不稳定等情况，另一方面有助于改善纤维性能，常温牵伸和低温牵伸有助于后续高倍牵伸，从而得到性能优异的短纤维；(3)改变生物基聚酰胺纤维的牵伸工艺和热定型温度条件，针对生物基聚酰胺调整工艺设备可以改善纤维的结晶度、取向度、力学性能、阻燃性等。
本发明的设备装置是连续生产装置，从盐水溶液配置开始一直到切断纤维是连续一体化生产过程，摒弃了传统的间歇式生产，有效的节约了生产成本，提高了工作效率。

Claims (12)

  1. 一种生物基聚酰胺短纤维聚纺牵定一体化成型的设备，其特征在于：该设备包括依次连接的盐液调配装置系统、聚合反应装置系统、纺丝牵定装置系统和集束切断装置系统；
    所述盐液调配装置系统包括依次连接的精盐储罐、盐液调配罐、盐液中间罐；
    所述聚合反应装置系统包括依次连接的浓缩槽、U型反应器、闪蒸器、前聚合器和后聚合器；所述盐液中间罐与所述浓缩槽的入口相连接；
    所述纺丝牵定装置系统包括依次连接的纺丝箱、上油装置、卷绕装置、牵伸装置；其中，所述纺丝箱的纺丝甬道旁设有对其内流经的所述纺丝箱产出的熔体细流进行冷却的吹风装置；所述牵伸装置包括依次连接的第一牵伸机、第二牵伸机和第三牵伸机，所述第一牵伸机、所述第二牵伸机和第三牵伸机上均设有控温装置，所述第三牵伸机后连接紧张热定型装置、冷却上油装置；
    所述集束切断装置系统包括依次连接的集束装置、叠丝装置、卷曲装置、松弛热定型装置、烘干装置、切断装置和打包装置。
  2. 一种利用权利要求1所述设备一体化成型制备生物基聚酰胺短纤维的方法，包括如下步骤：
    1)盐液调配过程：将所述精盐储罐中的聚酰胺干盐注入所述盐液调配罐配制成聚酰胺盐水溶液，并将其存储于所述盐液中间罐；
    2)聚合过程：所述盐液中间罐中聚酰胺盐水溶液经所述浓缩槽浓缩后进入所述U型反应器中进行预聚反应，预聚反应后在所述闪蒸器中进行快速解压，再依次进入所述前聚合器和所述后聚合器中，分别进行前聚合反应和后聚合反应，得到聚酰胺聚合物；
    3)纺丝牵定过程：将所述生物基聚酰胺聚合物熔体经所述纺丝箱的喷丝板喷出熔体细流，熔体细流流经所述纺丝甬道，并经所述吹风装置冷却凝固成为丝条，所述丝条经所述上油装置上油、卷绕装置卷绕、牵伸装置牵伸、紧张热定型装置定型、冷却上油装置冷却上油后得到牵伸丝束；
    所述牵伸的过程包括依次经所述第一牵伸机进行常温牵伸、所述第二牵伸机进行低温牵伸、所述第三牵伸机进行热牵伸；其中所述牵伸为一级牵伸、二级牵伸或多级牵伸，牵伸后纤维经过紧张热定型装置、冷却上油装置后集束；
    所述常温牵伸中牵伸温度为15～30℃，牵伸的倍率为1.01～1.85倍；
    所述低温牵伸中牵伸温度为5～20℃，牵伸的倍率为1.01～1.5倍；
    所述热牵伸中牵伸温度为60～210℃，牵伸的倍率为1.01～6.0倍；
    所述紧张热定型根据常温、低温、热牵伸温度的不同，温度范围为98～230℃；
    4)集束切断过程：所述牵伸丝束依次经所述集束装置集束、所述叠丝装置叠丝、然后经所述卷曲装置卷曲、所述松弛热定型装置松弛热定型、所述烘干装置烘干，最后经所述切断装置和打包装置依次切断、打包，即得到所述生物基聚酰胺短纤维。
  3. 根据权利要求2所述的方法，其特征在于：所述聚酰胺盐水溶液的质量百分含量为20％～80％，盐液pH值7.25～7.95；
    所述浓缩槽控制压力：25～35kPa；物料出口温度105～130℃。
  4. 根据权利要求2所述的方法，其特征在于：步骤1)中还包括通过所述盐液调配罐添加助剂对所述聚酰胺进行改性的步骤。
  5. 根据权利要求4所述的方法，其特征在于：所述助剂包括分子量调节剂、阻燃剂、抗静电剂、抗菌整理剂、抗紫外线整理剂、消光剂中的至少一种；
    所述助剂加入量为所述聚酰胺56干盐质量的0.10％～5.50％。
  6. 根据权利要求2所述的方法，其特征在于：所述U型反应器采用三段加热进行预聚反应的条件如下：R1段入口物料温度：150～220℃，R2段出口物料温度：170～260℃，R3段出口物料温度：170～260℃，控制反应器压力稳定在1.7～1.8MPa；
    所述闪蒸器中释放反应器内的压力，所述闪蒸器出口物料温度升至180～290℃。
  7. 根据权利要求2所述的方法，其特征在于：所述前聚合反应的条件如下：液位稳定在30～50％，物料出口温度为220℃～285℃，时间为20～120min；
    所述后聚合反应的条件如下：液位稳定在30～50％，真空度：50～80kPa，物料出口温度为220℃～290℃，时间为10～60min，增压泵压力：10～15MPa。
  8. 根据权利要求2所述的方法，其特征在于：步骤3)中所述聚酰胺聚合物熔体经喷丝板喷出得到熔体细流的过程如下：所述纺丝箱温度为：纺丝箱体一区温度270～290℃，二区温度270～290℃，三区温度270～290℃，计量泵温度 270～290℃，纺丝组件温度为270～290℃；计量泵转速12～18rpm/min在所述纺丝箱体内，所述聚酰胺聚合物熔体通过管路分配，以相等的停留时间和压力降输送到每一个喷丝口，喷丝头孔数500～5000根；纺丝速率可为1000～3000m/min。
  9. 根据权利要求2所述的方法，其特征在于：步骤3)中所述熔体细流经吹风装置冷却成型，所述吹风装置为侧吹风装置或环吹风装置，其条件如下：风速可为0.30～0.50m/min；风温可为20～25℃；风压可为400～500Pa；
    所述上油的油剂浓度为1～10％。
  10. 根据权利要求2所述的方法，其特征在于：所述紧张热定型，根据制备纤维性能要求选择不同定型工艺；所述紧张热定型加热方式包括干热空气定型、接触加热定型、水蒸气湿热定型和浴液定型中的至少一种。
  11. 根据权利要求2所述的方法，其特征在于：所述卷曲装置参数：主压气缸减压阀压力1～3bar、背压气缸减压阀压力1bar，卷曲温度为60～90℃，速率为900～1000m/min，卷曲数为10～30个；
    所述松弛热定型加热方式包括干热空气定型和/或接触加热定型，所述松弛热定型的温度为95～190℃，停留时间为3～15min。
  12. 权利要求2-8中任一项所述的方法制备得到的生物基聚酰胺短纤维；
    所述生物基聚酰胺短纤维的性能参数如下：断裂强度4.0～8.0cN/dtex，极限氧指数28.0～36.0％。
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