CN114921868A - Preparation method of nano biochar modified melt direct spinning superfine denier polyester fibers - Google Patents

Preparation method of nano biochar modified melt direct spinning superfine denier polyester fibers Download PDF

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CN114921868A
CN114921868A CN202210589285.1A CN202210589285A CN114921868A CN 114921868 A CN114921868 A CN 114921868A CN 202210589285 A CN202210589285 A CN 202210589285A CN 114921868 A CN114921868 A CN 114921868A
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biomass charcoal
superfine denier
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CN114921868B (en
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王华平
陈向玲
吉鹏
王朝生
谢锐敏
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Donghua University
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/318—Preparation characterised by the starting materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/336—Preparation characterised by gaseous activating agents
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

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Abstract

The invention relates to a preparation method of a nano biochar modified melt direct spinning superfine denier polyester fiber, which comprises the steps of adding a modified and modified nano biomass carbon material (the average particle size is 2-6 nm) after the polyester esterification reaction is finished, then carrying out polycondensation reaction, and spinning a polyester melt after the polycondensation reaction to obtain the nano biochar modified melt direct spinning superfine denier polyester fiber; the modified nano biomass charcoal material is prepared by mixing a nano biomass charcoal material with an aqueous solution of bis (dioctyloxy pyrophosphate) ethylene titanate or an aqueous solution of a chelate of bis (dioctyloxy pyrophosphate) ethylene titanate and triethanolamine, and then carrying out hydrothermal activation at 150-250 ℃. The invention has simple and convenient process, reasonable preparation flow and extremely high market popularization value; the method solves the problem of dispersibility of the nano biomass carbon in the polyester, is suitable for preparing melt direct spinning superfine denier fibers, and improves the replacement period of the spinneret plate filter component.

Description

Preparation method of nano biochar modified melt direct-spun superfine denier polyester fiber
Technical Field
The invention belongs to the technical field of melt direct spinning superfine denier polyester fibers, and relates to a preparation method of a nano biochar modified melt direct spinning superfine denier polyester fiber.
Background
The polyester fiber is the leading variety of chemical fiber in China, and accounts for 75 percent of the total amount of chemical fiber in China. The functional fine denier is the general trend of the chemical fiber technology development. The ultra-fine denier fiber has no unified standard internationally, and the fiber within 1.0dtex is generally changed into the fine denier/ultra-fine denier fiber in China, so that the ultra-fine denier fiber has high specific surface area, and very many small micropores exist among the filaments and between layers, thereby showing extremely strong cleaning function and good air permeability. The fabric made of the material has soft hand feeling, is comfortable to wear, has good drapability, is dry and fine, and is a key raw material for the fields of high-grade clothing fabrics, home textiles, automotive interiors and the like.
China is a big agricultural country, the yield of wastes from agriculture and forestry is high, only the agricultural straw production amount in China is about 8-10 hundred million tons, and most of China adopts incineration treatment, so that not only is the environmental pollution caused, but also the resources are greatly wasted, and the resource utilization of agricultural wastes is urgent. In recent years, with the rise of the biochar industry, researchers are gradually applying biochar to the field of polyester chemical fiber textile. The biomass carbon is generally added by master batches in a melt spinning system: grinding biomass charcoal into nano-scale powder, adding a dispersing agent, melt blending with polyester, polyamide and the like to prepare high-concentration bamboo charcoal master batch, and then melt blending with polyester and polyamide chips for spinning or composite spinning to prepare functional polyester and polyamide fibers. For example, in patent application CN103014907A, bamboo charcoal particles are surface-treated with silicon, then mixed with manganese phenate under stirring, and then mixed with polyester chips to prepare polyester masterbatch, and blended and spun to prepare functional polyester fiber. The application laid-open patent CN101857977A discloses a preparation method of tea carbon fiber, which is to simply blend nano-scale tea carbon powder, resin, auxiliary agent, colorant and adhesive to prepare master batch, and then blend the master batch and slices to spin to prepare negative ion fiber. Patent CN103820879 describes a hydrophilic polyester fiber containing coffee carbon and a preparation method thereof, wherein nano-scale silicon dioxide powder is attached to the surface pores of the nano-scale coffee carbon powder to prepare composite powder, and then the composite powder is prepared into master batch and slices to carry out blended spinning and alkali washing to prepare the functional polyester fiber. In patent CN102828274 and patent CN10382087, etc., biomass charcoal is directly added into resin matrix to be blended to prepare master batch, and then blended with resin slice to spin. The prior art is comprehensively analyzed, and the biomass carbon modified polyester fiber is basically prepared by directly mixing biomass carbon powder with a resin matrix or simply performing surface treatment on the biomass carbon powder by using a silane coupling agent, and preparing the functional polyester fiber by using a master batch adding mode, but modifying the melt direct spinning fiber by using the method is not seen. The modified polyester fiber prepared by the method cannot meet the preparation requirement of fine denier or superfine denier fiber due to the dispersion of the biochar powder.
Compared with the conventional fine denier filament preparation system, the superfine denier polyester filament yarn is thinner, the nozzle stretching ratio is larger, the requirements on the quantity and the size of impurity particles in the melt are tighter, the molecular weight is moderate and the distribution is small, the melt is uniform, the impurities are less, and the melt flowability is good. At the same time, the filtration accuracy requirements of the filter and the spin pack are also very high, and all particles exceeding the diameter of the microfibers must be filtered. Because the nano biomass charcoal has small grain size and high surface energy, agglomeration is easy to occur, even if the silane coupling agent is adopted to coat the nano biomass charcoal, the dispersibility is increased, and the agglomeration effect is reduced, but because the silane coupling agent and the nano biomass charcoal have pure physical action and are directly coated on the surface of the nano biomass charcoal, the grain size of the nano biomass charcoal is increased to a certain extent, so that the nano biomass charcoal is difficult to be used for preparing the superfine denier polyester fibers; moreover, silane coupling agents are hydrolyzed in the presence of water, cannot be added during polyester polymerization, and are not suitable for melt direct spinning. In patent CN102864507 (method for manufacturing melt direct spinning superfine denier porous differential polyester fiber and product thereof), pentaerythritol is added in esterification stage for micro modification to increase fluidity of polyester melt; secondly, the melt is subjected to multi-stage filtration by adding filter sand, metal mesh, cup sand and the like of the spinning assembly, so that the purity of the melt is improved; finally, the porous superfine fiber is prepared by adopting circular blowing and uniform cooling. The invention mainly develops the superfine denier fiber from the aspects of melt quality control and spinning process design without carrying out functional modification on the superfine denier fiber. In patent CN114108120 (a melt direct-spun porous superfine denier polyester fiber and a preparation method thereof), sodium borohydride is added during the polymerization process to eliminate the network structure formed by p-carboxybenzaldehyde in the polyester during the polyester synthesis process, thereby improving the filtration performance of the polyester melt and ensuring the quality of the porous superfine polyester fiber. The method also starts from improving the quality of the polyester melt, and does not modify the function of the polyester fiber. In patent CN111286804 (preparation method of dope dyed melt direct spinning super black polyester fiber), after esterification of polyester, black color paste composed of carbon black and carbon nanotubes is added into the esterified product, and then polycondensation reaction is performed. The patent does not mention fiber spinning techniques and fibers produced. Patent CN108060468 (a melt direct spinning preparation method of extinction PET fiber) adopts modified titanium dioxide and polyester chips to prepare master batches, and then prepares extinction PET fiber through online addition, the method is a master batch addition method, the mixing of the master batches and the polyester chips depends on the shearing action of double screws, the dispersion effect of the titanium dioxide is relatively limited, and the prepared fiber titer is 3.2-4.0 dtex, which cannot meet the requirement of fine denier application. By combining the patent and literature technologies, the biomass charcoal is not found to be used for modifying and preparing melt direct spinning superfine denier polyester fiber,
therefore, the development of the melt direct spinning superfine denier polyester fiber modified by the nano biomass carbon has very important application value.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a preparation method of a nano biochar modified melt direct-spun superfine denier polyester fiber.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a process for preparing the superfine polyester fibres directly spun from the modified fused mass of nano biochar includes such steps as esterifying polyester, adding modified nano biochar, and polycondensing. Spinning the polyester melt after polycondensation reaction to prepare nano biochar modified melt direct-spun superfine denier polyester fiber; after esterification, adding (dioctyloxy pyrophosphate ester) ethylene titanate or a chelate of bis (dioctyloxy pyrophosphate ester) ethylene titanate and triethanolamine, and performing polycondensation reaction with polyester by using unsaturated bonds in the chelate in the polycondensation process to join a polyester macromolecular chain. The addition in the esterification stage can affect the transesterification reaction of terephthalic acid and ethylene glycol, and has great influence on the quality of polyester melt. After polycondensation, polyester already forms macromolecular chains, the melt viscosity is higher, the adding reaction is limited at the moment, and the polyester cannot be uniformly connected into the macromolecular chains of the polyester;
the average particle size of the modified nano biomass charcoal material is 2-6 nm;
the modified nano biomass charcoal material is prepared by mixing a nano biomass charcoal material with a modifier solution and then carrying out hydrothermal activation;
the modifier solution is an aqueous solution of bis (dioctyloxy pyrophosphate) ethylene titanate or an aqueous solution of a chelate of bis (dioctyloxy pyrophosphate) ethylene titanate and triethanolamine;
the temperature of the hydrothermal activation is 150-250 ℃. When the temperature of the hydrothermal activation is lower than 150 ℃, the pressure of water vapor is small, and the generated activation energy can not effectively etch the surface of the biomass carbon; the temperature is higher than 250 ℃, the stability of the chelate of the (dioctyloxy pyrophosphate) ethylene titanate or the bis (dioctyloxy pyrophosphate) ethylene titanate and triethanolamine is easily influenced, therefore, the temperature range is set to be 150-250 ℃, the biomass charcoal can be fully activated and effectively etched, and the stability of the chelate of the (dioctyloxy pyrophosphate) ethylene titanate or the bis (dioctyloxy pyrophosphate) ethylene titanate and triethanolamine can be ensured.
As a preferred technical scheme:
the preparation method of the nano biochar modified melt direct spinning superfine denier polyester fiber specifically comprises the following steps of:
(1) heating the biomass raw material to 400-600 ℃ at a speed of 5-15 ℃/min in a nitrogen atmosphere, and preserving heat for 1-2 hours to obtain a biomass charcoal material;
(2) crushing, grinding, filtering and secondarily grinding the biomass charcoal material in a crusher to obtain a nano biomass charcoal material with the average particle size of 2-6 nm;
(3) dissolving bis (dioctyloxypyrophosphate) ethylene titanate or a chelate of bis (dioctyloxypyrophosphate) ethylene titanate and triethanolamine in water according to the addition of 1-5 wt% to obtain a modifier solution;
(4) adding the nano biomass charcoal material into a modifier solution according to the addition of 5-25 wt%, and performing ultrasonic dispersion to obtain a nano biomass charcoal mixed solution; the main purpose of the step is to fully disperse the nano biomass charcoal material in a chelate solution of (dioctyloxy pyrophosphate) ethylene titanate or bis (dioctyloxy pyrophosphate) ethylene titanate and triethanolamine. When the addition proportion is less than 5%, the efficiency is low, and energy is wasted; because the nano biomass charcoal material has small particle size and large surface energy, agglomeration is easy to occur, and when the addition amount is more than 25 percent, the dispersion is not uniform, so that the particle size distribution of the biomass charcoal is influenced; the catalyst is not fully contacted with bis (dioctyloxy pyrophosphate) ethylene titanate or a chelate of bis (dioctyloxy pyrophosphate) ethylene titanate and triethanolamine, so that the subsequent activation effect is influenced;
(5) and (3) putting the nano biomass charcoal mixed solution into a closed container, heating to 150-250 ℃ at the speed of 5-10 ℃/min, preserving the heat for 1-2 hours, carrying out hydrothermal activation, and then drying the hydrothermal activation product to obtain the modified nano biomass charcoal material.
According to the preparation method of the nano biochar modified melt direct-spun superfine denier polyester fiber, in the step (1), the biomass raw material is phyllostachys pubescens, corncobs, Chinese torreya shells or coconut shells; the yield of the biomass charcoal material is 30-45%.
According to the preparation method of the nano biochar modified melt direct spinning superfine denier polyester fiber, in the step (4), the ultrasonic frequency is 50-100 kHz, and the ultrasonic time is 15-45 minutes;
the drying treatment in the step (5) is carried out at the temperature of 100-110 ℃ for 6 hours.
The method for preparing the nano biochar modified melt direct spinning superfine denier polyester fiber comprises the step of modifying and modifying the surface of the nano biomass carbon material to contain groups
Figure BDA0003664407930000041
Or are each
Figure BDA0003664407930000042
In the modified nano biomass charcoal material, the content of a chelate of bis (dioctyloxy pyrophosphate) ethylene titanate or bis (dioctyloxy pyrophosphate) ethylene titanate and triethanolamine is 4-20 wt%;
the specific surface area of the modified nano biomass charcoal material is 100-500 m 2 Per g, the average pore diameter is 1 to 2nm, and the total pore volume is 0.1 to 1.0cm 3 /g；
After the modified nano biomass charcoal material is stood in water for 15 days, the Zeta potential is-50 to-55 mV; zeta potential is used for representing the dispersion stability of the nano material, and the higher the absolute value of the Zeta potential is, the more stable the system is, namely the dissolution or dispersion can resist aggregation.
The preparation method of the nano biochar modified melt direct spinning superfine denier polyester fiber comprises the following specific preparation steps:
(1) mixing terephthalic acid and ethylene glycol according to a molar ratio of 1: 1.05-2.0 to prepare slurry, and adding the prepared slurry into an esterification reaction kettle to perform esterification reaction;
(2) after the esterification reaction is finished, adding the modified nano biomass charcoal material, and then carrying out polycondensation reaction;
(3) pressurizing the polyester melt after polycondensation reaction by a melt booster pump, conveying the polyester melt to a spinning manifold through a melt cooler, filtering by a spinning assembly, and extruding by a superfine denier spinneret plate to form nascent fiber;
(4) the nascent fiber is sequentially cooled, blown, solidified, bundled, oiled, drawn and wound to prepare the nano biomass charcoal modified melt direct spinning superfine denier polyester fiber.
The preparation method of the nano biochar modified melt direct spinning superfine denier polyester fiber comprises the steps of (1) dividing esterification into a first esterification reaction and a second esterification reaction;
the temperature of the first esterification reaction is 225-250 ℃, the pressure is 0-0.4 MPa, and the reaction time is 0.5-4 h;
the temperature of the second esterification reaction is 240-260 ℃, the pressure is normal pressure, and the reaction time is 0.5-lh.
The preparation method of the nano biochar modified melt direct spinning superfine denier polyester fiber comprises the following steps of (1) mixing the prepared slurry with a catalyst before adding the slurry into an esterification reaction kettle for carrying out a first esterification reaction;
the catalyst is titanium catalyst, antimony catalyst or their combination; the addition amount of the catalyst is 120-550 ppm based on the mass of the terephthalic acid.
According to the preparation method of the nano biochar modified melt direct spinning superfine denier polyester fiber, the titanium catalyst is tetrabutyl titanate, and the antimony catalyst is antimony trioxide, antimony acetate or ethylene glycol antimony.
The preparation method of the nano biochar modified melt direct spinning superfine denier polyester fiber comprises the steps of (1) mixing the prepared slurry with a heat stabilizer and an antioxidant before adding the slurry into an esterification reaction kettle for carrying out a first esterification reaction;
the heat stabilizer is more than one of trimethyl phosphate, alkyl phosphodiester and tri (nonylphenyl) phosphite, and the antioxidant is more than one of antioxidant 1010, antioxidant 168 and antioxidant 616;
the addition amount of the heat stabilizer is 0.001-0.02 wt% of the terephthalic acid, and the addition amount of the antioxidant is 0.001-0.03 wt% of the terephthalic acid.
According to the preparation method of the nano biochar modified melt direct spinning superfine denier polyester fiber, the addition amount of the modified and modified nano biomass carbon material in the step (2) is 0.5-3 wt% of the theoretical yield of polyester;
the polycondensation reaction comprises a pre-polycondensation reaction and a final polycondensation reaction;
the temperature of the pre-polycondensation reaction is 220-270 ℃, the pressure is 0.5-1.0 KPa, the time is 0.5-2.5 h, and the stirring speed is 5-15 rpm;
the temperature of the final polycondensation reaction is 220-270 ℃, the pressure is 0-200 Pa, the time is 1.0-3.0 h, and the stirring speed is 5-10 rpm.
The pre-polycondensation reaction temperature is controlled to be 220-270 ℃, can be changed within a proper range, but is not too high, because the pre-polycondensation reaction cannot be carried out due to too low reaction temperature, and the thermal degradation side reaction of the bis (dioctyloxy pyrophosphate) ethylene titanate or the chelate of the bis (dioctyloxy pyrophosphate) ethylene titanate and triethanolamine on the surface of the biomass charcoal and the polyester is increased due to too high reaction temperature, so that the melt quality is influenced. The reaction time can be properly prolonged at a lower temperature, the bis (dioctyloxy pyrophosphate) ethylene titanate or the chelate of the bis (dioctyloxy pyrophosphate) ethylene titanate and the triethanolamine on the surface of the biomass charcoal fully reacts with the polyester, so that the biomass charcoal is uniformly and stably dispersed in the melt, and the molecular chain segments of the bis (dioctyloxy pyrophosphate) ethylene titanate or the chelate of the bis (dioctyloxy pyrophosphate) ethylene titanate and the triethanolamine are uniformly embedded into the molecular chain of the polyester, so that the fluidity of the polyester melt is improved;
the pre-polycondensation reaction pressure is controlled to be 0.5-1.0 KPa, compared with the final polycondensation vacuum degree, the pre-polycondensation reaction pressure can be changed in a proper range, but the pre-polycondensation reaction pressure is not too high, a low-viscosity prepolymer and part of biomass carbon materials in the pre-polycondensation reaction can be extracted due to too low pressure (namely, a high vacuum effect) to block a pipeline, so that a polycondensation accident is caused, the removal of small molecules in the polycondensation reaction can not be realized due to too high pressure (namely, a poor vacuum effect), and the pre-polycondensation reaction can not be normally carried out;
the pre-polycondensation reaction time is 0.5-2.5 h, the pre-polycondensation reaction time can be changed in a proper range, but the pre-polycondensation reaction time is not too long, the pre-polycondensation reaction time is too short, the reaction is insufficient, the pre-polycondensation reaction time is too long, thermal degradation side reactions in the pre-polycondensation reaction process at high temperature are increased, and the effective increase of the molecular weight cannot be realized;
the stirring speed of the pre-polycondensation reaction is 5-15 rpm, the viscosity of the material in the pre-polycondensation reaction process is higher than that of an esterification reaction product and lower than that of a final polycondensation reaction product, the stirring speed of the pre-polycondensation reaction can be changed within a proper range, but the stirring speed is not too high, the pre-polycondensation product with lower viscosity can be brought out in a vacuum environment due to the too high stirring speed, the reaction is not favorable, and the effect of uniformly stirring the material cannot be achieved due to the too low stirring speed;
the final polycondensation reaction temperature is controlled to be 220-270 ℃, can be changed within a proper range, but is not too high, the final polycondensation reaction cannot be carried out due to too low reaction temperature, thermal degradation side reactions are increased in the final polycondensation reaction process due to too high reaction temperature, the uniformity of a melt is influenced, and the spinnability of superfine denier fibers is adversely affected;
the final polycondensation reaction pressure is controlled to be 0-200 Pa, can be changed within a proper range, but is not too high, too low pressure (namely, higher vacuum effect) has higher requirement on equipment, too high pressure (namely, poorer vacuum effect) can cause that small molecules in the polycondensation reaction cannot be removed, and the final polycondensation reaction cannot be normally carried out;
the final polycondensation reaction time is controlled to be 1.0-3.0 h, the final polycondensation reaction time can be changed in a proper range, but the final polycondensation reaction time is not too long, the formed product cannot reach the spinning grade due to too short final polycondensation reaction time, the thermal degradation side reaction of the polymer under the high-temperature condition is obviously increased due to too long final polycondensation reaction time, and the number average molecular weight of the product is rapidly reduced due to thermal degradation after reaching the maximum number average molecular weight;
the stirring speed of the final polycondensation reaction is 5-10 rpm, and after the modified nano biomass charcoal is used for modifying the polyester melt, the fluidity of the melt is improved, and the stirring speed can be properly reduced. Too fast stirring speed can not realize the effect of stirring to high viscosity polymer system, still can damage the motor because the electric current is too big simultaneously, and too low stirring speed can not play the even effect of material stirring.
According to the preparation method of the nano biochar modified melt direct spinning superfine denier polyester fiber, in the step (3), the spinning temperature is 275-290 ℃, and can be adjusted within a proper range. The polyester melt is easy to degrade when the temperature is too high; the temperature is too low, which affects the fluidity of the melt and produces stiff silk, broken ends and the like; the linear density of the nascent fiber is 54-576 dtex;
the melt obtained by the polymerization reaction is conveyed to spinning through a pipeline, and the biomass nano powder is added into the melt, so that the biomass nano powder is prevented from being deposited on the melt pipeline, the quality of the melt is influenced, and by utilizing the principle of 'non-stick pan', the inner wall of the melt conveying pipeline is treated by an organic coating, the roughness of the pipeline is reduced, the sliding speed and the conveying speed of the melt on the wall surface of the pipeline are improved, and the viscosity drop of the melt is reduced;
the filtering material adopted in the spinning assembly consists of 0.5-15 mu m acute angle type metal sand and a 1200-mesh superfine stainless steel filter screen (the metal sand is placed on the filter screen); the sharp-angle metal sand is adopted for matching with the superfine denier melt direct spinning, and the melt generates multiple high shearing on the sharp surface of the metal sand, so that the submicron impurity-containing block mass is efficiently stripped, and the uniformity of the melt is improved;
the specification of the superfine denier spinneret plate is 36-144 holes, the length-diameter ratio of spinneret holes is 4.0, orifice bulking is eliminated, and uniform and stable extrusion of a melt is achieved.
The preparation method of the nano biochar modified melt direct-spun superfine denier polyester fiber comprises the following steps of (4) spinning at a speed of 2600-2900 m/min, slow cooling pipe length of 50-60 cm, cooling air temperature of 20-22 ℃, cooling air speed of 0.3-0.5 m/s and cooling air humidity of 80%;
the bundling position is 600-900 mm away from the spinneret plate surface; beam splitting and oiling by using an oil nozzle, wherein the oil content in the oil agent is 0.5-0.7 wt%;
the drafting temperature is 80-135 ℃, and the drafting multiple is 3-4 times.
According to the preparation method of the nano biochar modified melt direct spinning superfine denier polyester fiber, the biochar content in the nano biochar modified melt direct spinning superfine denier polyester fiber is 0.5-3 wt%;
the filament number of the nano biochar modified melt direct spinning superfine denier polyester fiber is 0.3-1.0 dtex, the breaking strength is more than or equal to 2.5cN/dtex, the moisture regain is more than 0.6%, and the temperature rise is 5-35 ℃ after 30s of irradiation under a heat source of 100W.
Mechanism of the invention
The invention relates to a preparation method of a nano biomass charcoal modified melt direct spinning superfine denier polyester fiber, which comprises the steps of firstly designing a preparation method of high-uniformity and high-stability dispersed nano biomass charcoal, adopting a carbonization-activation dispersion one-step method in the process, firstly carrying out primary carbonization on a biomass raw material at a higher temperature to ensure that the biomass raw material has a higher pore structure and a higher specific surface area, retaining part of cellulose and lignin in the biomass raw material, then crushing the biomass raw material, and grinding the biomass raw material for multiple times to prepare a biomass charcoal material with the particle size of 2-6 nanometers; then mixing the nano biochar material with an aqueous solution containing bis (dioctyloxy pyrophosphate) ethylene titanate or a chelate of bis (dioctyloxy pyrophosphate) ethylene titanate and triethanolamine, and then carrying out low-temperature hydrothermal activation, wherein in the process, the nano biochar material is fully and uniformly mixed with the (dioctyloxy pyrophosphate) ethylene titanate or the chelate of bis (dioctyloxy pyrophosphate) ethylene titanate and triethanolamine, and under the action of water vapor, water molecules further etch the biochar material, so that micropores are generated and surface groups of the biochar material are enriched; bis (dioctyloxypyrophosphate) ethylene titanate or a chelate of bis (dioctyloxypyrophosphate) ethylene titanate and triethanolamine) is dissolved in water, and is attached to the biomass charcoal or in pores during the activation process of water vapor, so that the particle size of the biomass charcoal is not increased; and because the biomass charcoal material contains partial incompletely decomposed cellulose and lignin, the biomass charcoal material can be used for producing the biomass charcoal material under the action of heatReacting (dioctyloxy pyrophosphate) ethylene titanate or a chelate of bis (dioctyloxy pyrophosphate) ethylene titanate and triethanolamine with a group of cellulose and lignin to generate
Figure BDA0003664407930000071
Figure BDA0003664407930000072
The structure is anchored on the surface of the biomass charcoal, and plays a role in stable dispersion. And secondly, due to the access of the long carbon chain, the compatibility with a polyester system is improved, the change of the surface energy on the interface of the nano biomass charcoal material and the polyester is caused, the nano biomass charcoal material has the functions of flexibility and stress transfer, the self-lubricating effect is generated, and the flow property and the processing technology of the polyester can be improved.
In addition, after esterification of polyester and before polycondensation, modified biomass charcoal material, (dioctyloxy pyrophosphate) ethylene titanate or the unsaturated bond in the chelate of bis (dioctyloxy pyrophosphate) ethylene titanate and triethanolamine is added to produce polycondensation reaction with polyester in the polycondensation process to form
Figure BDA0003664407930000073
Figure BDA0003664407930000081
Structure, embedded in a PET molecular chain segment. On one hand, the embedding of the chain segments damages the regularity of a polyester molecular chain, and the segmented sequence length of the PET chain is limited, so that the crystal size and distribution of the polyester are changed, the crystal grain size is reduced, and the crystallization uniformity and stability are improved; secondly, as the PET chain segments are fully mixed, a local ordered micro-area structure cannot be formed, secondary crystallization is eliminated, and fiber drafting is facilitated, so that preparation of the superfine fiber is facilitated; on the other hand, because two unsaturated bonds on the chelate of the bis (dioctyloxypyrophosphate) ethylene titanate or the bis (dioctyloxypyrophosphate) ethylene titanate and the triethanolamine respectively react with the biomass charcoal and the polyester to play a role of bridging, the biomass charcoal is fixed on the polyIn the ester, the nano biomass charcoal material is prevented from agglomerating, and the dispersibility of the biomass charcoal is greatly improved. Therefore, the invention can obtain the melt direct spinning superfine denier polyester fiber modified by the nano biomass carbon.
Has the advantages that:
(1) the preparation method of the nano biochar modified melt direct spinning superfine denier polyester fiber solves the problem of dispersibility of nano biochar in polyester, is suitable for preparing the melt direct spinning superfine denier fiber, and improves the replacement period of a spinneret plate filter assembly;
(2) the nano biochar modified melt direct spinning superfine denier polyester fiber has small fiber filament number (0.3-1.0 dtex), excellent mechanical property, better far infrared heating function, high added value of products and high application and popularization values;
(3) the preparation method of the nano biochar modified melt direct spinning superfine denier polyester fiber has the advantages of simple and convenient process, reasonable preparation flow and extremely high market popularization value.
Drawings
FIG. 1 is a surface electron microscope image of a nano biomass charcoal modified polyester fiber in example 1;
FIG. 2 is an infrared image (30s) of the modified polyester fiber fabric of example 2.
Detailed Description
The present invention will be further described with reference to the following embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
A method for preparing a nano biochar modified melt direct spinning superfine denier polyester fiber comprises the following specific steps:
(1) heating a biomass raw material (phyllostachys pubescens) to 600 ℃ at a speed of 5 ℃/min in a nitrogen atmosphere, and preserving heat for 1 hour to obtain a biomass charcoal material, wherein the yield of the biomass charcoal material is 32.06%;
(2) crushing, grinding, filtering and secondarily grinding the biomass charcoal material in a crusher to obtain a nano biomass charcoal material with the average particle size of 2 nm;
(3) dissolving bis (dioctyloxy pyrophosphate) ethylene titanate in water according to the addition of 1 wt% to obtain a modifier solution;
(4) adding the nano biomass charcoal material obtained in the step (2) into a modifier solution according to the addition of 5 wt%, and performing ultrasonic dispersion (the ultrasonic frequency is 60kHz, and the ultrasonic time is 20 minutes) to obtain a nano biomass charcoal mixed solution;
(5) filling the nano biomass charcoal mixed solution into a closed container, heating to 250 ℃ at the speed of 5 ℃/min, preserving heat for 1 hour, performing hydrothermal activation, and drying a hydrothermal activation product at 100 ℃ for 6 hours to obtain a modified and modified nano biomass charcoal material;
the specific surface area of the prepared modified nano biomass charcoal material is 483m 2 (g) average particle diameter of 5.5nm, average pore diameter of 1.7nm, and total pore volume of 0.98cm 3 Per g, its surface contains the groups:
Figure BDA0003664407930000091
in the prepared modified nano biomass charcoal material, the content of bis (dioctyloxy pyrophosphate) ethylene titanate is 20 wt%;
standing the prepared modified nano biomass charcoal material in water for 15 days, wherein the Zeta potential is-55 mV;
(6) mixing terephthalic acid and ethylene glycol according to a molar ratio of 1:1.05 to prepare slurry, and then mixing the prepared slurry with a catalyst, a heat stabilizer and an antioxidant;
wherein the catalyst is tetrabutyl titanate; based on the mass of terephthalic acid, the addition amount of the catalyst is 200 ppm;
the heat stabilizer is trimethyl phosphate, and the addition amount of the heat stabilizer is 0.001 wt% of terephthalic acid;
the antioxidant is antioxidant 1010; the addition amount of the antioxidant is 0.03 wt% of the terephthalic acid;
(7) adding the slurry mixed with the catalyst, the heat stabilizer and the antioxidant into an esterification reaction kettle for esterification reaction;
wherein the esterification reaction is divided into a first esterification reaction and a second esterification reaction; the temperature of the first esterification reaction is 225 ℃, the pressure is 0.1MPa, and the reaction time is 4 h; the temperature of the second esterification reaction is 240 ℃, the pressure is normal pressure, and the reaction time is 1 h;
(8) after the esterification reaction is finished, adding the modified nano biomass charcoal material prepared in the step (5), and then carrying out polycondensation reaction;
wherein the addition amount of the modified nano biomass charcoal material is 3 wt% of the theoretical yield of the polyester;
the polycondensation reaction comprises a pre-polycondensation reaction and a final polycondensation reaction; the temperature of the pre-polycondensation reaction is 220 ℃, the pressure is 1KPa, the time is 2.5h, and the stirring speed is 5 rpm; the temperature of the final polycondensation reaction is 220 ℃, the pressure is 100Pa, the time is 3h, and the stirring speed is 3 rpm;
(9) pressurizing the polyester melt after polycondensation reaction by a melt booster pump, conveying the polyester melt to a spinning manifold through a melt cooler, filtering by a spinning assembly, and extruding by a superfine denier spinneret plate to form nascent fiber with the linear density of 54 dtex;
wherein the spinning temperature is 275 ℃; the filtering material adopted in the spinning assembly consists of 10-micron acute angle metal sand and a 1200-mesh superfine stainless steel filter screen; the specification of the superfine denier spinneret plate is 36 holes, and the length-diameter ratio of the spinneret hole is 4.0;
(10) sequentially cooling, blowing, solidifying, bundling, oiling, drafting and winding the nascent fiber to obtain the nano biomass charcoal modified melt direct spinning superfine denier polyester fiber;
wherein the spinning speed is 2900m/min, the length of the slow cooling pipe is 55cm, the cooling air temperature is 20 ℃, the cooling air speed is 0.5m/s, and the cooling air humidity is 80%; the bundling position is 750mm away from the spinneret plate surface; beam splitting and oiling by using an oil nozzle, wherein the oil content in the oil agent is 0.7 wt%; the drafting temperature is 100 ℃, and the drafting multiple is 3.3 times;
the content of the biochar in the finally prepared nano biochar modified melt direct spinning superfine denier polyester fiber is 0.5 wt%; the filament number of the prepared nano biochar modified melt direct spinning superfine denier polyester fiber is 0.45dtex, the breaking strength is 4.14cN/dtex, the moisture regain is 0.61%, the temperature rise of the fiber under the irradiation of a heat source of 100W for 30s is 5.6 ℃, and the surface electron microscope image thereof is shown in figure 1.
Example 2
A method for preparing nano biochar modified melt direct spinning superfine denier polyester fibers comprises the following specific steps:
(1) heating a biomass raw material (corncob) to 400 ℃ at a speed of 15 ℃/min in a nitrogen atmosphere, and preserving heat for 1.5 hours to obtain a biomass charcoal material, wherein the yield of the biomass charcoal material is 44.83%;
(2) crushing, grinding, filtering and secondarily grinding the biomass charcoal material in a crusher to obtain a nano biomass charcoal material with the average particle size of 6 nm;
(3) dissolving a chelate of bis (dioctyloxypyrophosphate) ethylene titanate and triethanolamine in water according to the addition of 1 wt% to obtain a modifier solution;
(4) adding the nano biomass charcoal material obtained in the step (2) into a modifier solution according to the addition of 25 wt%, and performing ultrasonic dispersion (the ultrasonic frequency is 60kHz, and the ultrasonic time is 30 minutes) to obtain a nano biomass charcoal mixed solution;
(5) putting the nano biomass charcoal mixed solution into a closed container, heating to 150 ℃ at the speed of 10 ℃/min, preserving heat for 2 hours, carrying out hydrothermal activation, and drying a hydrothermal activation product at 100 ℃ for 6 hours to obtain a modified and modified nano biomass charcoal material;
the specific surface area of the prepared modified nano biomass charcoal material is 154m 2 Per g, average particle diameter of 2.6nm, average pore diameter of 1.1nm, total pore volume of 0.13cm 3 Per g, its surface contains the groups:
Figure BDA0003664407930000101
in the prepared modified nano biomass charcoal material, the content of the chelate of bis (dioctyloxy pyrophosphate) ethylene titanate and triethanolamine is 4 wt%;
standing the prepared modified nano biomass charcoal material in water for 15 days, wherein the Zeta potential is-50 mV;
(6) mixing terephthalic acid and ethylene glycol according to a molar ratio of 1:2 to prepare slurry, and then mixing the prepared slurry with a catalyst, a heat stabilizer and an antioxidant;
wherein the catalyst is antimony trioxide; the addition amount of the catalyst is 300ppm based on the mass of the terephthalic acid;
the heat stabilizer is alkyl phosphate diester, and the addition amount of the heat stabilizer is 0.005 wt% of terephthalic acid;
the antioxidant is antioxidant 168; the addition amount of the antioxidant is 0.02 wt% of the terephthalic acid;
(7) adding the slurry mixed with the catalyst, the heat stabilizer and the antioxidant into an esterification reaction kettle for esterification reaction;
wherein the esterification reaction is divided into a first esterification reaction and a second esterification reaction; the temperature of the first esterification reaction is 250 ℃, the pressure is 0MPa, and the reaction time is 0.5 h; the temperature of the second esterification reaction is 245 ℃, the pressure is normal pressure, and the reaction time is 0.8 h;
(8) adding the modified and modified nano biomass charcoal material prepared in the step (5) after the esterification reaction is finished, and then carrying out polycondensation reaction;
wherein the addition amount of the modified nano biomass charcoal material is 0.5 wt% of the theoretical yield of the polyester;
the polycondensation reaction comprises a pre-polycondensation reaction and a final polycondensation reaction; the temperature of the pre-polycondensation reaction is 270 ℃, the pressure is 0.8KPa, the time is 0.8h, and the stirring speed is 10 rpm; the temperature of the final polycondensation reaction is 270 ℃, the pressure is 120Pa, the time is 1h, and the stirring speed is 10 rpm;
(9) pressurizing the polyester melt after polycondensation reaction by a melt booster pump, conveying the polyester melt to a spinning manifold through a melt cooler, filtering by a spinning assembly, and extruding by a superfine denier spinneret plate to form nascent fiber with the linear density of 576 dtex;
wherein the spinning temperature is 290 ℃; the filtering material adopted in the spinning component consists of 8-micron acute-angle metal sand and a 1200-mesh superfine stainless steel filter screen; the specification of the superfine denier spinneret plate is 144 holes, and the length-diameter ratio of spinneret holes is 4.0;
(10) sequentially cooling, blowing, solidifying, bundling, oiling, drafting and winding the nascent fiber to obtain the nano biomass charcoal modified melt direct spinning superfine denier polyester fiber;
wherein the spinning speed is 2600m/min, the length of the slow cooling pipe is 50cm, the cooling air temperature is 20 ℃, the cooling air speed is 0.3m/s, and the cooling air humidity is 80%; the bundling position is 600mm away from the spinneret plate surface; beam splitting and oiling by using an oil nozzle, wherein the oil content in the oil agent is 0.65 wt%; the drafting temperature is 80 ℃, and the drafting multiple is 4 times;
the biochar content in the finally prepared nano biochar modified melt direct spinning superfine denier polyester fiber is 3 wt%; the filament number of the prepared nano biochar modified melt direct spinning superfine denier polyester fiber is 1dtex, the breaking strength is 2.63cN/dtex, the moisture regain is 0.94%, the temperature rise is 34.7 ℃ after 30s of irradiation under a heat source of 100W, and an infrared imaging graph (30s) is shown in figure 2.
Example 3
A method for preparing nano biochar modified melt direct spinning superfine denier polyester fibers comprises the following specific steps:
(1) heating a biomass raw material (Chinese torreya shells) to 500 ℃ at a speed of 10 ℃/min in a nitrogen atmosphere, and preserving heat for 2 hours to obtain a biomass charcoal material, wherein the yield of the biomass charcoal material is 37.42%;
(2) crushing, grinding, filtering and secondarily grinding the biomass charcoal material in a crusher to obtain a nano biomass charcoal material with the average particle size of 3 nm;
(3) dissolving bis (dioctyloxypyrophosphate) ethylene titanate in water according to the addition of 2 wt% to obtain a modifier solution;
(4) adding the nano biomass charcoal material obtained in the step (2) into a modifier solution according to the addition of 16 wt%, and performing ultrasonic dispersion (the ultrasonic frequency is 80kHz, and the ultrasonic time is 35 minutes) to obtain a nano biomass charcoal mixed solution;
(5) filling the nano biomass charcoal mixed solution into a closed container, heating to 150 ℃ at the speed of 6 ℃/min, preserving heat for 1.5 hours, carrying out hydrothermal activation, and then drying a hydrothermal activation product at 100 ℃ for 6 hours to obtain a modified and modified nano biomass charcoal material;
the specific surface area of the prepared modified nano biomass charcoal material is 386m 2 G, average particle diameter of 3.7nm, average pore diameter of 1.5nm, and total pore volume of 0.42cm 3 Per g, the surface of which contains the groups:
Figure BDA0003664407930000121
in the prepared modified nano biomass charcoal material, the content of bis (dioctyloxy pyrophosphate) ethylene titanate is 12.5 wt%;
standing the modified nano biomass charcoal material in water for 15 days, wherein the Zeta potential is-51 mV;
(6) mixing terephthalic acid and ethylene glycol according to a molar ratio of 1:1.15 to prepare slurry, and then mixing the prepared slurry with a catalyst, a heat stabilizer and an antioxidant;
wherein the catalyst is antimony acetate; the addition amount of the catalyst is 120ppm based on the mass of the terephthalic acid;
the heat stabilizer is tris (nonylphenyl) phosphite ester, and the addition amount of the heat stabilizer is 0.01 wt% of the terephthalic acid;
the antioxidant is antioxidant 616; the addition amount of the antioxidant is 0.01 wt% of the terephthalic acid;
(7) adding the slurry mixed with the catalyst, the heat stabilizer and the antioxidant into an esterification reaction kettle for esterification reaction;
wherein the esterification reaction is divided into a first esterification reaction and a second esterification reaction; the temperature of the first esterification reaction is 230 ℃, the pressure is 0.2MPa, and the reaction time is 3.5 h; the temperature of the second esterification reaction is 250 ℃, the pressure is normal pressure, and the reaction time is 0.5 h;
(8) adding the modified and modified nano biomass charcoal material prepared in the step (5) after the esterification reaction is finished, and then carrying out polycondensation reaction;
wherein the addition amount of the modified nano biomass charcoal material is 2.5 wt% of the theoretical yield of the polyester;
the polycondensation reaction comprises a pre-polycondensation reaction and a final polycondensation reaction; the temperature of the pre-polycondensation reaction is 260 ℃, the pressure is 0.5KPa, the time is 1h, and the stirring speed is 12 rpm; the temperature of the final polycondensation reaction is 260 ℃, the pressure is 0Pa, the time is 1.5h, and the stirring speed is 5 rpm;
(9) pressurizing the polyester melt after polycondensation reaction by a melt booster pump, conveying the polyester melt to a spinning manifold through a melt cooler, filtering by a spinning assembly, and extruding by a superfine denier spinneret plate to form nascent fiber with the linear density of 288 dtex;
wherein the spinning temperature is 285 ℃; the filtering material adopted in the spinning component consists of 0.5 mu m acute angle type metal sand and a 1200-mesh superfine stainless steel filter screen; the specification of the superfine denier spinneret plate is 144 holes, and the length-diameter ratio of the spinneret hole is 4.0;
(10) cooling, blowing, solidifying, bundling, oiling, drafting and winding the nascent fiber in sequence to obtain a nano biomass charcoal modified melt direct-spun superfine denier polyester fiber;
wherein the spinning speed is 2750m/min, the length of the slow cooling pipe is 60cm, the cooling air temperature is 21 ℃, the cooling air speed is 0.4m/s, and the cooling air humidity is 80%; the bundling position is 800mm away from the spinneret plate surface; beam splitting and oiling by using an oil nozzle, wherein the oil content in the oil agent is 0.6 wt%; the drafting temperature is 110 ℃, and the drafting multiple is 3.8 times;
the content of the biochar in the finally prepared nano biochar modified melt direct spinning superfine denier polyester fiber is 2.5 wt%; the filament number of the prepared nano biochar modified melt direct spinning superfine denier polyester fiber is 0.53dtex, the breaking strength is 2.99cN/dtex, the moisture regain is 0.87%, and the temperature rise is 31.9 ℃ after 30s irradiation under a heat source of 100W.
Example 4
A method for preparing nano biochar modified melt direct spinning superfine denier polyester fibers comprises the following specific steps:
(1) heating a biomass raw material (coconut shell) to 450 ℃ at a speed of 10 ℃/min in a nitrogen atmosphere, and preserving heat for 2 hours to obtain a biomass charcoal material, wherein the yield of the biomass charcoal material is 40.22%;
(2) crushing, grinding, filtering and secondarily grinding the biomass charcoal material in a crusher to obtain a nano biomass charcoal material with the average particle size of 4 nm;
(3) dissolving a chelate of bis (dioctyloxypyrophosphate) ethylene titanate and triethanolamine in water according to the addition of 3 wt% to obtain a modifier solution;
(4) adding the nano biomass charcoal material obtained in the step (2) into a modifier solution according to the addition of 20 wt%, and performing ultrasonic dispersion (the ultrasonic frequency is 100kHz, and the ultrasonic time is 30 minutes) to obtain a nano biomass charcoal mixed solution;
(5) filling the nano biomass charcoal mixed solution into a closed container, heating to 180 ℃ at the speed of 7 ℃/min, preserving heat for 2 hours, carrying out hydrothermal activation, and then drying a hydrothermal activation product at 105 ℃ for 6 hours to obtain a modified and modified nano biomass charcoal material;
the specific surface area of the prepared modified nano biomass charcoal material is 209m 2 (g) average particle diameter of 3.5nm, average pore diameter of 1.3nm, and total pore volume of 0.33cm 3 Per g, the surface of which contains the groups:
Figure BDA0003664407930000131
in the prepared modified nano biomass charcoal material, the content of the chelate of bis (dioctyloxy pyrophosphate) ethylene titanate and triethanolamine is 15 wt%;
standing the modified nano biomass charcoal material in water for 15 days, wherein the Zeta potential is-52 mV;
(6) mixing terephthalic acid and ethylene glycol according to a molar ratio of 1:1.5 to prepare slurry, and then mixing the prepared slurry with a catalyst, a heat stabilizer and an antioxidant;
wherein the catalyst is ethylene glycol antimony; based on the mass of terephthalic acid, the addition amount of the catalyst is 400 ppm;
the heat stabilizer is trimethyl phosphate, and the addition amount of the heat stabilizer is 0.015 wt% of the terephthalic acid;
the antioxidant is antioxidant 1010; the addition amount of the antioxidant is 0.001 wt% of the terephthalic acid;
(7) adding the slurry mixed with the catalyst, the heat stabilizer and the antioxidant into an esterification reaction kettle for esterification reaction;
wherein the esterification reaction is divided into a first esterification reaction and a second esterification reaction; the temperature of the first esterification reaction is 235 ℃, the pressure is 0.4MPa, and the reaction time is 1 h; the temperature of the second esterification reaction is 255 ℃, the pressure is normal pressure, and the reaction time is 1 h;
(8) after the esterification reaction is finished, adding the modified nano biomass charcoal material prepared in the step (5), and then carrying out polycondensation reaction;
wherein the addition amount of the modified nano biomass charcoal material is 1 wt% of the theoretical yield of the polyester;
the polycondensation reaction comprises a pre-polycondensation reaction and a final polycondensation reaction; the temperature of the pre-polycondensation reaction is 230 ℃, the pressure is 1KPa, the time is 2.5h, and the stirring speed is 15 rpm; the temperature of the final polycondensation reaction is 230 ℃, the pressure is 200Pa, the time is 2.5h, and the stirring speed is 6 rpm;
(9) pressurizing the polyester melt after polycondensation reaction by a melt booster pump, conveying the polyester melt to a spinning manifold through a melt cooler, filtering by a spinning assembly, and extruding by a superfine denier spinneret plate to form nascent fiber with the linear density of 108 dtex;
wherein the spinning temperature is 280 ℃; the filtering material adopted in the spinning component consists of 12 mu m acute angle type metal sand and a 1200-mesh superfine stainless steel filter screen; the specification of the superfine denier spinneret plate is 48 holes, and the length-diameter ratio of the spinneret hole is 4.0;
(10) cooling, blowing, solidifying, bundling, oiling, drafting and winding the nascent fiber in sequence to obtain a nano biomass charcoal modified melt direct-spun superfine denier polyester fiber;
wherein the spinning speed is 2800m/min, the length of the slow cooling pipe is 55cm, the cooling air temperature is 21 ℃, the cooling air speed is 0.4m/s, and the cooling air humidity is 80%; the bundling position is 900mm away from the spinneret plate surface; beam splitting and oiling by using an oil nozzle, wherein the oil content in the oil agent is 0.5 wt%; the drafting temperature is 85 ℃, and the drafting multiple is 3.7 times;
the content of the biochar in the finally prepared nano biochar modified melt direct spinning superfine denier polyester fiber is 1 wt%; the filament number of the prepared nano biochar modified melt direct spinning superfine denier polyester fiber is 0.61dtex, the breaking strength is 3.82cN/dtex, the moisture regain is 0.66 percent, and the temperature rise is 16.4 ℃ when the nano biochar modified melt direct spinning superfine denier polyester fiber is irradiated for 30s under a heat source of 100W.
Example 5
A method for preparing a nano biochar modified melt direct spinning superfine denier polyester fiber comprises the following specific steps:
(1) heating a biomass raw material (corncob) to 550 ℃ at a speed of 15 ℃/min in a nitrogen atmosphere, and preserving heat for 1 hour to obtain a biomass charcoal material, wherein the yield of the biomass charcoal material is 31.67%;
(2) crushing, grinding, filtering and secondarily grinding the biomass charcoal material in a crusher to obtain a nano biomass charcoal material with the average particle size of 4 nm;
(3) dissolving bis (dioctyloxy pyrophosphate) ethylene titanate in water according to the addition of 3.5 wt% to obtain a modifier solution;
(4) adding the nano biomass charcoal material obtained in the step (2) into a modifier solution according to the addition of 25 wt%, and performing ultrasonic dispersion (the ultrasonic frequency is 100kHz, and the ultrasonic time is 40 minutes) to obtain a nano biomass charcoal mixed solution;
(5) putting the nano biomass charcoal mixed solution into a closed container, heating to 200 ℃ at the speed of 8 ℃/min, preserving heat for 1.5 hours, carrying out hydrothermal activation, and then drying a hydrothermal activation product at 105 ℃ for 6 hours to obtain a modified and modified nano biomass charcoal material;
the prepared modified nano biomass charcoal materialHas a specific surface area of 422m 2 Per g, average particle diameter of 5.3nm, average pore diameter of 1.7nm, total pore volume of 0.82cm 3 Per g, the surface of which contains the groups:
Figure BDA0003664407930000151
in the prepared modified nano biomass charcoal material, the content of bis (dioctyloxy pyrophosphate) ethylene titanate is 14 wt%;
standing the modified nano biomass charcoal material in water for 15 days, wherein the Zeta potential is-52 mV;
(6) mixing terephthalic acid and ethylene glycol according to a molar ratio of 1:1.65 to prepare slurry, and then mixing the prepared slurry with a catalyst, a heat stabilizer and an antioxidant;
wherein the catalyst is a mixture of tetrabutyl titanate and antimony trioxide in a mass ratio of 1: 1; the addition amount of the catalyst is 550ppm based on the mass of the terephthalic acid;
the heat stabilizer is alkyl phosphate diester, and the addition amount of the heat stabilizer is 0.02 wt% of the terephthalic acid;
the antioxidant is antioxidant 168; the addition amount of the antioxidant is 0.005 wt% of the terephthalic acid;
(7) adding the slurry mixed with the catalyst, the heat stabilizer and the antioxidant into an esterification reaction kettle for esterification reaction;
wherein the esterification reaction is divided into a first esterification reaction and a second esterification reaction; the temperature of the first esterification reaction is 235 ℃, the pressure is 0.3MPa, and the reaction time is 3 h; the temperature of the second esterification reaction is 260 ℃, the pressure is normal pressure, and the reaction time is 0.8 h;
(8) adding the modified and modified nano biomass charcoal material prepared in the step (5) after the esterification reaction is finished, and then carrying out polycondensation reaction;
wherein the addition amount of the modified nano biomass charcoal material is 2 wt% of the theoretical yield of the polyester;
the polycondensation reaction comprises a pre-polycondensation reaction and a final polycondensation reaction; the temperature of the pre-polycondensation reaction is 250 ℃, the pressure is 0.8KPa, the time is 2.2h, and the stirring speed is 15 rpm; the temperature of the final polycondensation reaction is 250 ℃, the pressure is 80Pa, the time is 2h, and the stirring speed is 8 rpm;
(9) pressurizing the polyester melt after polycondensation reaction by a melt booster pump, conveying the polyester melt to a spinning manifold through a melt cooler, filtering by a spinning assembly, and extruding by a superfine denier spinneret plate to form nascent fiber with the linear density of 192 dtex;
wherein the spinning temperature is 275 ℃; the filtering material adopted in the spinning assembly consists of 5-micron acute angle metal sand and a 1200-mesh superfine stainless steel filter screen; the specification of the superfine denier spinneret plate is 96 holes, and the length-diameter ratio of the spinneret hole is 4.0;
(10) cooling, blowing, solidifying, bundling, oiling, drafting and winding the nascent fiber in sequence to obtain a nano biomass charcoal modified melt direct-spun superfine denier polyester fiber;
wherein the spinning speed is 2650m/min, the length of the slow cooling pipe is 50cm, the cooling air temperature is 21 ℃, the cooling air speed is 0.5m/s, and the cooling air humidity is 80%; the bundling position is 700mm away from the spinneret plate surface; beam splitting and oiling by using an oil nozzle, wherein the oil content in the oil agent is 0.6 wt%; the drafting temperature is 90 ℃, and the drafting multiple is 3 times;
the biochar content in the finally prepared nano biochar modified melt direct spinning superfine denier polyester fiber is 2 wt%; the filament number of the prepared nano biochar modified melt direct spinning superfine denier polyester fiber is 0.67dtex, the breaking strength is 3.14cN/dtex, the moisture regain is 0.79 percent, and the temperature rise is 29.3 ℃ when the nano biochar modified melt direct spinning superfine denier polyester fiber is irradiated for 30s under a heat source of 100W.
Example 6
A method for preparing nano biochar modified melt direct spinning superfine denier polyester fibers comprises the following specific steps:
(1) heating a biomass raw material (coconut shell) to 500 ℃ at a speed of 10 ℃/min in a nitrogen atmosphere, and preserving heat for 1.5 hours to obtain a biomass charcoal material, wherein the yield of the biomass charcoal material is 39.19%;
(2) crushing, grinding, filtering and secondarily grinding the biomass charcoal material in a crusher to obtain a nano biomass charcoal material with the average particle size of 3 nm;
(3) dissolving a chelate of bis (dioctyloxypyrophosphate) ethylene titanate and triethanolamine in water according to the addition of 4 wt% to obtain a modifier solution;
(4) adding the nano biomass charcoal material obtained in the step (2) into a modifier solution according to the addition of 20 wt%, and performing ultrasonic dispersion (the ultrasonic frequency is 80kHz, and the ultrasonic time is 30 minutes) to obtain a nano biomass charcoal mixed solution;
(5) putting the nano biomass charcoal mixed solution into a closed container, heating to 220 ℃ at the speed of 9 ℃/min, preserving heat for 1 hour, carrying out hydrothermal activation, and drying a hydrothermal activation product at 105 ℃ for 6 hours to obtain a modified and modified nano biomass charcoal material;
the specific surface area of the prepared modified nano biomass charcoal material is 402m 2 (g) average particle diameter of 4.5nm, average pore diameter of 1.6nm, and total pore volume of 0.63cm 3 Per g, the surface of which contains the groups:
Figure BDA0003664407930000161
in the prepared modified nano biomass charcoal material, the content of the chelate of bis (dioctyloxy pyrophosphate) ethylene titanate and triethanolamine is 20 wt%;
standing the modified nano biomass charcoal material in water for 15 days, wherein the Zeta potential is-53 mV;
(6) mixing terephthalic acid and ethylene glycol according to a molar ratio of 1:1.75 to prepare slurry, and then mixing the prepared slurry with a catalyst, a heat stabilizer and an antioxidant;
wherein the catalyst is a mixture of tetrabutyl titanate and antimony acetate in a mass ratio of 1: 1; the addition of the catalyst was 500ppm based on the mass of terephthalic acid;
the heat stabilizer is tris (nonylphenyl) phosphite ester, and the addition amount of the heat stabilizer is 0.005 wt% of the terephthalic acid;
the antioxidant is antioxidant 616; the addition amount of the antioxidant is 0.015 wt% of the terephthalic acid;
(7) adding the slurry mixed with the catalyst, the heat stabilizer and the antioxidant into an esterification reaction kettle for esterification reaction;
wherein the esterification reaction is divided into a first esterification reaction and a second esterification reaction; the temperature of the first esterification reaction is 240 ℃, the pressure is 0.2MPa, and the reaction time is 1.5 h; the temperature of the second esterification reaction is 245 ℃, the pressure is normal pressure, and the reaction time is 0.5 h;
(8) adding the modified and modified nano biomass charcoal material prepared in the step (5) after the esterification reaction is finished, and then carrying out polycondensation reaction;
wherein the addition amount of the modified nano biomass charcoal material is 1.5 wt% of the theoretical yield of the polyester;
the polycondensation reaction comprises a pre-polycondensation reaction and a final polycondensation reaction; the temperature of the pre-polycondensation reaction is 240 ℃, the pressure is 0.5KPa, the time is 2h, and the stirring speed is 12 rpm; the temperature of the final polycondensation reaction is 240 ℃, the pressure is 50Pa, the time is 1.5h, and the stirring speed is 10 rpm;
(9) pressurizing the polyester melt after polycondensation reaction by a melt booster pump, conveying the polyester melt to a spinning manifold through a melt cooler, filtering by a spinning assembly, and extruding by a superfine denier spinneret plate to form nascent fiber with the linear density of 96 dtex;
wherein the spinning temperature is 290 ℃; the filtering material adopted in the spinning component consists of 15 mu m acute angle type metal sand and a 1200-mesh superfine stainless steel filter screen; the specification of the superfine denier spinneret plate is 96 holes, and the length-diameter ratio of the spinneret hole is 4.0;
(10) cooling, blowing, solidifying, bundling, oiling, drafting and winding the nascent fiber in sequence to obtain a nano biomass charcoal modified melt direct-spun superfine denier polyester fiber;
wherein the spinning speed is 2700m/min, the length of the slow cooling pipe is 60cm, the temperature of cooling air is 21 ℃, the cooling air speed is 0.3m/s, and the humidity of the cooling air is 80 percent; the bundling position is 650mm away from the spinneret plate surface; beam splitting and oiling by using an oil nozzle, wherein the oil content in the oil agent is 0.6 wt%; the drafting temperature is 95 ℃, and the drafting multiple is 3.2 times;
the content of the biochar in the finally prepared nano biochar modified melt direct spinning superfine denier polyester fiber is 1.5 wt%; the filament number of the prepared nano biochar modified melt direct spinning superfine denier polyester fiber is 0.31dtex, the breaking strength is 3.66cN/dtex, the moisture regain is 0.71%, and the temperature rise is 25.7 ℃ when the nano biochar modified melt direct spinning superfine denier polyester fiber is irradiated for 30s under a heat source of 100W.
Example 7
A method for preparing nano biochar modified melt direct spinning superfine denier polyester fibers comprises the following specific steps:
(1) heating a biomass raw material (phyllostachys pubescens) to 450 ℃ at a speed of 5 ℃/min in a nitrogen atmosphere, and preserving heat for 1.5 hours to obtain a biomass charcoal material, wherein the yield of the biomass charcoal material is 41.23%;
(2) crushing, grinding, filtering and secondarily grinding the biomass charcoal material in a crusher to obtain a nano biomass charcoal material with the average particle size of 5 nm;
(3) dissolving bis (dioctyloxy pyrophosphate) ethylene titanate in water according to the addition of 4.5 wt% to obtain a modifier solution;
(4) adding the nano biomass charcoal material obtained in the step (2) into a modifier solution according to the addition of 22.5 wt%, and performing ultrasonic dispersion (the ultrasonic frequency is 90kHz, and the ultrasonic time is 45 minutes) to obtain a nano biomass charcoal mixed solution;
(5) filling the nano biomass charcoal mixed solution into a closed container, heating to 240 ℃ at the speed of 7 ℃/min, preserving heat for 2 hours, carrying out hydrothermal activation, and then drying a hydrothermal activation product at 110 ℃ for 6 hours to obtain a modified and modified nano biomass charcoal material;
the specific surface area of the prepared modified nano biomass charcoal material is 274m 2 Per g, average particle diameter of 4.1nm, average pore diameter of 1.2nm, and total pore volume of 0.51cm 3 Per g, its surface contains the groups:
Figure BDA0003664407930000181
in the prepared modified nano biomass charcoal material, the content of bis (dioctyloxy pyrophosphate) ethylene titanate is 20 wt%;
standing the modified nano biomass charcoal material in water for 15 days, wherein the Zeta potential is-53 mV;
(6) mixing terephthalic acid and ethylene glycol according to a molar ratio of 1:1.3 to prepare slurry, and then mixing the prepared slurry with a catalyst, a heat stabilizer and an antioxidant;
wherein the catalyst is a mixture of tetrabutyl titanate and ethylene glycol antimony in a mass ratio of 1: 1; the addition amount of the catalyst is 350ppm based on the mass of the terephthalic acid;
the heat stabilizer is trimethyl phosphate, and the addition amount of the heat stabilizer is 0.01 wt% of terephthalic acid;
the antioxidant is antioxidant 1010; the addition amount of the antioxidant is 0.02 wt% of the terephthalic acid;
(7) adding the slurry mixed with the catalyst, the heat stabilizer and the antioxidant into an esterification reaction kettle for esterification reaction;
wherein the esterification reaction is divided into a first esterification reaction and a second esterification reaction; the temperature of the first esterification reaction is 245 ℃, the pressure is 0.1MPa, and the reaction time is 2.5 h; the temperature of the second esterification reaction is 250 ℃, the pressure is normal pressure, and the reaction time is 0.8 h;
(8) adding the modified and modified nano biomass charcoal material prepared in the step (5) after the esterification reaction is finished, and then carrying out polycondensation reaction;
wherein the addition amount of the modified nano biomass charcoal material is 2 wt% of the theoretical yield of the polyester;
the polycondensation reaction comprises a pre-polycondensation reaction and a final polycondensation reaction; the temperature of the pre-polycondensation reaction is 260 ℃, the pressure is 0.8KPa, the time is 1.5h, and the stirring speed is 10 rpm; the temperature of the final polycondensation reaction is 260 ℃, the pressure is 150Pa, the time is 1.5h, and the stirring speed is 8 rpm;
(9) pressurizing the polyester melt after polycondensation reaction by a melt booster pump, conveying the polyester melt to a spinning manifold through a melt cooler, filtering by a spinning assembly, and extruding by a superfine denier spinneret plate to form nascent fiber with the linear density of 144 dtex;
wherein the spinning temperature is 285 ℃; the filtering material adopted in the spinning assembly consists of 10-micron acute angle metal sand and a 1200-mesh superfine stainless steel filter screen; the specification of the superfine denier spinneret plate is 72 holes, and the length-diameter ratio of the spinneret hole is 4.0;
(10) cooling, blowing, solidifying, bundling, oiling, drafting and winding the nascent fiber in sequence to obtain a nano biomass charcoal modified melt direct-spun superfine denier polyester fiber;
wherein the spinning speed is 2850m/min, the length of the slow cooling pipe is 55cm, the cooling air temperature is 22 ℃, the cooling air speed is 0.4m/s, and the cooling air humidity is 80%; the bundling position is 850mm away from the spinneret plate surface; beam splitting and oiling by using an oil nozzle, wherein the oil content in the oil agent is 0.6 wt%; the drafting temperature is 120 ℃, and the drafting multiple is 4 times;
the content of the biochar in the finally prepared nano biochar modified melt direct spinning superfine denier polyester fiber is 1 wt%; the filament number of the prepared nano biochar modified melt direct spinning superfine denier polyester fiber is 0.5dtex, the breaking strength is 3.71cN/dtex, the moisture regain is 0.69%, and the temperature rise is 17.3 ℃ after 30s of irradiation under a heat source of 100W.
Example 8
A method for preparing a nano biochar modified melt direct spinning superfine denier polyester fiber comprises the following specific steps:
(1) heating a biomass raw material (Chinese torreya shells) to 600 ℃ at a speed of 10 ℃/min in a nitrogen atmosphere, and preserving heat for 2 hours to obtain a biomass charcoal material, wherein the yield of the biomass charcoal material is 30.47%;
(2) crushing, grinding, filtering and secondarily grinding the biomass charcoal material in a crusher to obtain a nano biomass charcoal material with the average particle size of 5 nm;
(3) dissolving a chelate of bis (dioctyloxypyrophosphate) ethylene titanate and triethanolamine in water according to the addition of 5 wt% to obtain a modifier solution;
(4) adding the nano biomass charcoal material obtained in the step (2) into a modifier solution according to the addition of 25 wt%, and performing ultrasonic dispersion (the ultrasonic frequency is 100kHz, and the ultrasonic time is 45 minutes) to obtain a nano biomass charcoal mixed solution;
(5) putting the nano biomass charcoal mixed solution into a closed container, heating to 160 ℃ at the speed of 8 ℃/min, preserving heat for 1.5 hours, carrying out hydrothermal activation, and drying a hydrothermal activation product at 110 ℃ for 6 hours to obtain a modified and modified nano biomass charcoal material;
the specific surface area of the prepared modified nano biomass charcoal material is 491m 2 (ii)/g, average particle diameter of 6nm, average pore diameter of 1.9nm, and total pore volume of 0.92cm 3 Per g, its surface contains the groups:
Figure BDA0003664407930000191
in the prepared modified nano biomass charcoal material, the content of the chelate of bis (dioctyloxy pyrophosphate) ethylene titanate and triethanolamine is 20 wt%;
standing the prepared modified nano biomass charcoal material in water for 15 days, wherein the Zeta potential is-54 mV;
(6) mixing terephthalic acid and ethylene glycol according to a molar ratio of 1:1.9 to prepare slurry, and then mixing the prepared slurry with a catalyst, a heat stabilizer and an antioxidant;
wherein the catalyst is tetrabutyl titanate; the addition of the catalyst was 450ppm based on the mass of terephthalic acid;
the heat stabilizer is a mixture of alkyl phosphate diester and tris (nonylphenyl) phosphite ester with the mass ratio of 1:1, and the addition amount of the heat stabilizer is 0.015 wt% of terephthalic acid;
the antioxidant is a mixture of the antioxidant 168 and the antioxidant 616 in a mass ratio of 1: 1; the addition amount of the antioxidant is 0.025 wt% of the terephthalic acid;
(7) adding the slurry mixed with the catalyst, the heat stabilizer and the antioxidant into an esterification reaction kettle for esterification reaction;
wherein the esterification reaction is divided into a first esterification reaction and a second esterification reaction; the temperature of the first esterification reaction is 245 ℃, the pressure is 0.3MPa, and the reaction time is 2 h; the temperature of the second esterification reaction is 255 ℃, the pressure is normal pressure, and the reaction time is 1 h;
(8) adding the modified and modified nano biomass charcoal material prepared in the step (5) after the esterification reaction is finished, and then carrying out polycondensation reaction;
wherein the addition amount of the modified nano biomass charcoal material is 2 wt% of the theoretical yield of the polyester;
the polycondensation reaction comprises a pre-polycondensation reaction and a final polycondensation reaction; the temperature of the pre-polycondensation reaction is 250 ℃, the pressure is 1KPa, the time is 2h, and the stirring speed is 5 rpm; the temperature of the final polycondensation reaction is 250 ℃, the pressure is 180Pa, the time is 1.9h, and the stirring speed is 6 rpm;
(9) pressurizing the polyester melt after polycondensation reaction by a melt booster pump, conveying the polyester melt to a spinning manifold through a melt cooler, filtering by a spinning assembly, and extruding by a superfine denier spinneret plate to form a nascent fiber with the linear density of 484 dtex;
wherein the spinning temperature is 280 ℃; the filtering material adopted in the spinning assembly consists of 3-micron acute angle metal sand and a 1200-mesh superfine stainless steel filter screen; the specification of the superfine denier spinneret plate is 144 holes, and the length-diameter ratio of the spinneret hole is 4.0;
(10) sequentially cooling, blowing, solidifying, bundling, oiling, drafting and winding the nascent fiber to obtain the nano biomass charcoal modified melt direct spinning superfine denier polyester fiber;
wherein the spinning speed is 2750m/min, the length of the slow cooling pipe is 55cm, the cooling air temperature is 22 ℃, the cooling air speed is 0.4m/s, and the cooling air humidity is 80%; the bundling position is 750mm away from the spinneret plate surface; beam splitting and oiling by using an oil nozzle, wherein the oil content in the oil agent is 0.55 wt%; the drafting temperature is 115 ℃, and the drafting multiple is 3.6 times;
the biochar content in the finally prepared nano biochar modified melt direct spinning superfine denier polyester fiber is 2.5 wt%; the filament number of the prepared nano biochar modified melt direct spinning superfine denier polyester fiber is 0.93dtex, the breaking strength is 3.01cN/dtex, the moisture regain is 0.86%, and the temperature rise is 32.8 ℃ after 30s of irradiation under a heat source of 100W.

Claims (14)

1. A method for preparing nano biochar modified melt direct spinning superfine denier polyester fibers is characterized by comprising the following steps: adding a modified nano biomass charcoal material after the polyester esterification reaction is finished, then carrying out polycondensation reaction, and spinning a polyester melt after the polycondensation reaction to obtain a nano biochar modified melt direct-spun superfine denier polyester fiber;
the average particle size of the modified nano biomass charcoal material is 2-6 nm;
the modified nano biomass charcoal material is prepared by mixing a nano biomass charcoal material with a modifier solution and then carrying out hydrothermal activation;
the modifier solution is an aqueous solution of bis (dioctyloxy pyrophosphate) ethylene titanate or an aqueous solution of a chelate of bis (dioctyloxy pyrophosphate) ethylene titanate and triethanolamine;
the temperature of the hydrothermal activation is 150-250 ℃.
2. The preparation method of the nano biochar modified melt direct spinning superfine denier polyester fiber according to claim 1, wherein the specific preparation steps of the modified and modified nano biomass carbon material are as follows:
(1) heating the biomass raw material to 400-600 ℃ at a speed of 5-15 ℃/min in a nitrogen atmosphere, and preserving heat for 1-2 hours to obtain a biomass charcoal material;
(2) crushing, grinding, filtering and secondarily grinding the biomass charcoal material in a crusher to obtain a nano biomass charcoal material with the average particle size of 2-6 nm;
(3) dissolving bis (dioctyloxypyrophosphate) ethylene titanate or a chelate of bis (dioctyloxypyrophosphate) ethylene titanate and triethanolamine in water according to the addition of 1-5 wt% to obtain a modifier solution;
(4) adding the nano biomass charcoal material into a modifier solution according to the addition of 5-25 wt%, and performing ultrasonic dispersion to obtain a nano biomass charcoal mixed solution;
(5) and (3) putting the nano biomass charcoal mixed solution into a closed container, heating to 150-250 ℃ at the speed of 5-10 ℃/min, preserving the heat for 1-2 hours, performing hydrothermal activation, and then drying a hydrothermal activation product to obtain the modified nano biomass charcoal material.
3. The method for preparing nano biochar modified melt direct-spun superfine denier polyester fibers according to claim 2, wherein the biomass raw material in the step (1) is phyllostachys pubescens, corncobs, torreya grandis shells or coconut shells; the yield of the biomass charcoal material is 30-45%.
4. The preparation method of the nano biochar modified melt direct-spun superfine denier polyester fiber according to claim 2 is characterized in that in the step (4), the ultrasonic frequency is 50-100 kHz, and the ultrasonic time is 15-45 minutes;
the drying treatment in the step (5) is carried out at the temperature of 100-110 ℃ for 6 hours.
5. The method for preparing the nano biochar modified melt direct spinning superfine denier polyester fiber according to claim 1 or 2, wherein the surface of the modified nano biomass carbon material contains groups
Figure FDA0003664407920000021
Or
Figure FDA0003664407920000022
Figure FDA0003664407920000023
In the modified nano biomass charcoal material, the content of bis (dioctyloxy pyrophosphate) ethylene titanate or a chelate of bis (dioctyloxy pyrophosphate) ethylene titanate and triethanolamine is 4-20 wt%;
the specific surface area of the modified nano biomass charcoal material is 100-500 m 2 (ii) a total pore volume of 0.1 to 1.0cm, an average pore diameter of 1 to 2nm 3 /g；
The Zeta potential of the modified nano biomass charcoal material is-50 to-55 mV after the material is stood in water for 15 days.
6. The method for preparing the nano biochar modified melt directly spun superfine denier polyester fiber according to any one of claims 1 to 5, wherein the specific preparation steps of the nano biochar modified melt directly spun superfine denier polyester fiber are as follows:
(1) mixing terephthalic acid and ethylene glycol according to a molar ratio of 1: 1.05-2.0 to prepare slurry, and adding the prepared slurry into an esterification reaction kettle to carry out esterification reaction;
(2) adding the modified nano biomass charcoal material after the esterification reaction is finished, and then carrying out polycondensation reaction;
(3) pressurizing the polyester melt after polycondensation reaction by a melt booster pump, conveying the polyester melt to a spinning manifold through a melt cooler, filtering by a spinning assembly, and extruding by a superfine denier spinneret plate to form nascent fiber;
(4) the nascent fiber is sequentially cooled, blown, solidified, bundled, oiled, drawn and wound to prepare the nano biomass charcoal modified melt direct spinning superfine denier polyester fiber.
7. The method for preparing nano biochar modified melt direct-spun superfine denier polyester fiber according to claim 6, wherein the esterification reaction in the step (1) is divided into a first esterification reaction and a second esterification reaction;
the temperature of the first esterification reaction is 225-250 ℃, the pressure is 0-0.4 MPa, and the reaction time is 0.5-4 h;
the temperature of the second esterification reaction is 240-260 ℃, the pressure is normal pressure, and the reaction time is 0.5-lh.
8. The method for preparing nano biochar modified melt direct-spun superfine denier polyester fiber according to claim 6, wherein the step (1) is to mix the prepared slurry with a catalyst before adding the slurry into an esterification reaction kettle for the first esterification reaction;
the catalyst is titanium catalyst, antimony catalyst or their combination; the addition amount of the catalyst is 120-550 ppm based on the mass of the terephthalic acid.
9. The method for preparing nano biochar modified melt direct-spun superfine denier polyester fibers according to claim 8, wherein the titanium catalyst is tetrabutyl titanate, and the antimony catalyst is antimony trioxide, antimony acetate or ethylene glycol antimony.
10. The method for preparing nano biochar modified melt direct-spun superfine denier polyester fiber according to claim 6, wherein in the step (1), the prepared slurry is mixed with a heat stabilizer and an antioxidant before being added into an esterification reaction kettle for a first esterification reaction;
the heat stabilizer is more than one of trimethyl phosphate, alkyl phosphodiester and tri (nonylphenyl) phosphite, and the antioxidant is more than one of antioxidant 1010, antioxidant 168 and antioxidant 616;
the addition amount of the heat stabilizer is 0.001-0.02 wt% of the terephthalic acid, and the addition amount of the antioxidant is 0.001-0.03 wt% of the terephthalic acid.
11. The preparation method of the nano biochar modified melt direct-spun superfine denier polyester fiber according to claim 6, wherein the addition amount of the modified nano biomass carbon material in the step (2) is 0.5-3 wt% of the theoretical yield of polyester;
the polycondensation reaction comprises a pre-polycondensation reaction and a final polycondensation reaction;
the temperature of the pre-polycondensation reaction is 220-270 ℃, the pressure is 0.5-1.0 KPa, the time is 0.5-2.5 h, and the stirring speed is 5-15 rpm;
the temperature of the final polycondensation reaction is 220-270 ℃, the pressure is 0-200 Pa, the time is 1.0-3.0 h, and the stirring speed is 5-10 rpm.
12. The preparation method of the nano biochar modified melt directly spun superfine denier polyester fiber according to claim 6, wherein the spinning temperature in the step (3) is 275-290 ℃; the linear density of the nascent fiber is 54-576 dtex;
the filtering material adopted in the spinning assembly consists of 0.5-15 mu m acute angle type metal sand and a 1200-mesh superfine stainless steel filter screen;
the specification of the superfine denier spinneret plate is 36-144 holes, and the length-diameter ratio of spinneret holes is 4.0.
13. The preparation method of the nano biochar modified melt directly spun superfine denier polyester fiber according to claim 6, wherein in the step (4), the spinning speed is 2600-2900 m/min, the length of a slow cooling pipe is 50-60 cm, the cooling air temperature is 20-22 ℃, the cooling air speed is 0.3-0.5 m/s, and the cooling air humidity is 80%;
the bundling position is 600-900 mm away from the spinneret plate surface; beam splitting and oiling by using an oil nozzle, wherein the oil content in the oil agent is 0.5-0.7 wt%;
the drafting temperature is 80-135 ℃, and the drafting multiple is 3-4 times.
14. The method for preparing the nano biochar modified melt direct-spun superfine denier polyester fiber according to claim 6, wherein the biochar content in the nano biochar modified melt direct-spun superfine denier polyester fiber is 0.5-3 wt%;
the filament number of the nano biochar modified melt direct spinning superfine denier polyester fiber is 0.3-1.0 dtex, the breaking strength is more than or equal to 2.5cN/dtex, the moisture regain is more than 0.6%, and the temperature rise is 5-35 ℃ after 30s of irradiation under a heat source of 100W.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115928246A (en) * 2022-11-17 2023-04-07 福建经纬新纤科技实业有限公司 Preparation method of polyester staple fibers

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103014906A (en) * 2012-11-16 2013-04-03 东华大学 Preparation method of inflaming retarding hydrophilic polyester fiber
CN104746172A (en) * 2015-04-09 2015-07-01 苏州金辉纤维新材料有限公司 Preparation method of coffee carbon polyester fiber with high-efficient adsorption and hygroscopic properties
CN105504700A (en) * 2015-10-27 2016-04-20 济南圣泉集团股份有限公司 Graphene-containing composite polyester material and preparation method and use thereof
CN105926060A (en) * 2016-06-12 2016-09-07 福建百宏聚纤科技实业有限公司 Melt direct spinning superfine denier polyester filament and making method thereof
CN112795999A (en) * 2020-12-31 2021-05-14 扬州富威尔复合材料有限公司 Fine-denier black polyester filament and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103014906A (en) * 2012-11-16 2013-04-03 东华大学 Preparation method of inflaming retarding hydrophilic polyester fiber
CN104746172A (en) * 2015-04-09 2015-07-01 苏州金辉纤维新材料有限公司 Preparation method of coffee carbon polyester fiber with high-efficient adsorption and hygroscopic properties
CN105504700A (en) * 2015-10-27 2016-04-20 济南圣泉集团股份有限公司 Graphene-containing composite polyester material and preparation method and use thereof
CN105926060A (en) * 2016-06-12 2016-09-07 福建百宏聚纤科技实业有限公司 Melt direct spinning superfine denier polyester filament and making method thereof
CN112795999A (en) * 2020-12-31 2021-05-14 扬州富威尔复合材料有限公司 Fine-denier black polyester filament and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115928246A (en) * 2022-11-17 2023-04-07 福建经纬新纤科技实业有限公司 Preparation method of polyester staple fibers

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