WO2021174719A1 - 一种含甲壳素的涤纶长丝及其制备方法 - Google Patents

一种含甲壳素的涤纶长丝及其制备方法 Download PDF

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Publication number
WO2021174719A1
WO2021174719A1 PCT/CN2020/097915 CN2020097915W WO2021174719A1 WO 2021174719 A1 WO2021174719 A1 WO 2021174719A1 CN 2020097915 W CN2020097915 W CN 2020097915W WO 2021174719 A1 WO2021174719 A1 WO 2021174719A1
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Prior art keywords
preparation
chitin
polyester
polyester filaments
parts
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PCT/CN2020/097915
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English (en)
French (fr)
Inventor
黄效华
刘彦明
黄效谦
刘宇
刘洁
甄丽
Original Assignee
百事基材料（青岛）股份有限公司
中科纺织研究院（青岛）有限公司
百草边大生物科技(青岛)有限公司
青岛百草新材料股份有限公司
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Priority to JP2022500815A priority Critical patent/JP2022539850A/ja
Publication of WO2021174719A1 publication Critical patent/WO2021174719A1/zh
Priority to US17/668,547 priority patent/US20220162774A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
    • C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
    • C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D01F1/103—Agents inhibiting growth of microorganisms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/02—Preparation of spinning solutions
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/02—Heat treatment
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—Wet spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/12—Stretch-spinning methods
    • D01D5/16—Stretch-spinning methods using rollers, or like mechanical devices, e.g. snubbing pins
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—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

Definitions

  • the invention belongs to the technical field of spinning, and specifically relates to a chitin-containing polyester filament and a preparation method thereof.
  • polyester polyethylene terephthalate fiber, or polyester fiber for short.
  • Polyester is the commercial name of this fiber in my country. It is a fiber-forming polymer made of purified terephthalic acid (PTA) and ethylene glycol (EG) through esterification and polycondensation reactions—polyethylene terephthalate (PET). Fibers made by spinning and post-processing have a wide range of applications in the field of apparel fabrics.
  • PTA purified terephthalic acid
  • EG ethylene glycol
  • PET polyethylene terephthalate
  • Chitin also known as chitin, chitin, etc.
  • Chitin is a rich natural resource. It is naturally synthesized by nearly 1 billion every year. It is the most abundant natural organic matter on the earth after cellulose fiber. Chitin is a natural polysaccharide. It has both the biological functions of collagen in higher animal tissues and cellulose in higher fabric tissues. It has good adaptability to animals and plants, and it is also biodegradable and biodegradable. It is non-toxic, so it has become a new material with a wide range of uses in recent years.
  • antibacterial polyester fibers can be prepared, and then a series of antibacterial textiles can be prepared.
  • the antibacterial agent is often sprayed uniformly on the surface of the fabric.
  • This method is simple and easy to implement, but the directly sprayed chitin antibacterial substance is easy to lose during use, which weakens the antibacterial effect and does not last for the antibacterial. It is added to spinning fiber products, but high-temperature carbonization is prone to occur during high-temperature spinning, which affects fiber elasticity and may affect its appearance for high-end products.
  • the present invention provides a chitin-containing polyester filament and a preparation method thereof, so as to achieve the following objectives of the invention:
  • the present invention adopts the following technical solutions:
  • a preparation method of chitin-containing polyester filament characterized in that the chitin content of the polyester filament is 0.1-3%;
  • the preparation method includes: preparation of modified chitin, preparation of chitin-containing functional modifier, preparation of polyester functional particles, preparation of mixed spinning solution and spinning forming;
  • the preparation of the modified chitin includes the steps of deacetylation, amination modification and separation and purification; the amination modification, the addition amount of hydroxypropyltrimethylammonium nitride is 0.50-0.58 of the weight of chitin Times;
  • the added catalyst is zinc phosphomolybdate, and its concentration is 0.11-0.32wt%;
  • the lye used is 40-45wt% sodium hydroxide and potassium hydroxide mixed lye in equal proportions, and the chitin accounts for 1/20-1/25 of the weight of the mixed lye; the prepared product contains amino groups
  • the chitosan suspension, the degree of deacetylation is 80-92%;
  • the volume ratio of the dropwise addition of acetone to the solution is 1:3-4;
  • the solvent used is triethyl citrate, and the mass ratio of modified chitin crystals to diatomaceous earth is 3.2-5.0:1;
  • the preparation of the chitin-containing functional modifier includes adding a porogen and a precipitant;
  • the porogen is CaCl2, MgCl2 or NaCl, and the added amount of the porogen accounts for 1.2-2.8 wt% of the total;
  • the precipitating agent is EVA, the vinyl acetate content is 25.0-28.5%, the melt index is 22-24g/10min (190°C, 2.15kg), and the added amount of the precipitating agent accounts for 8.0-12.5wt% of the total;
  • the rotating speed in the mixer is 1000-1200r/min, and the mixing time is 60-90min;
  • the polyester functional particles in parts by weight, the raw material composition includes: 50-60 parts of PET Granules, 20-25 parts of chitin-containing functional modifier, 3-6 parts of titanium dioxide, 6-12 parts of sodium carboxymethyl cellulose, 6-12 parts of diisopropyl trisulfide;
  • an accelerator is added.
  • the mixing ratio of the accelerator, amino silicone oil and n-butyl titanate is 0.25-0.40:1; the added amount of the accelerator accounts for 3% of the total spinning solution. -6wt%;
  • the first hot rolling temperature is 168-175°C
  • the drafting rate is 1200-1250m/min
  • the second hot rolling temperature is 85-90°C
  • the drafting rate is 3680-3700m/min
  • the winding speed is 1560 -1860/min.
  • the obtained polyester filament has excellent antibacterial effect, can reduce the adhesion of bacteria, and is easy to infect the human body such as Staphylococcus aureus, Escherichia coli, Candida albicans and other bacteria
  • the bacteriostasis rate reaches 95.0-98.5%
  • the processed antibacterial polyester textile can still reach 90-92%, and after 60 standard washings , The antibacterial rate is still 84-86%, and the antibacterial durability is good;
  • the chitin-containing polyester filament prepared by the present invention has a uniform color and a light transmittance of 71-75%, and no obvious carbon black and particle agglomeration are visible to the naked eye;
  • the monofilament fineness of the polyester filament is 2.0-3.5 dtex
  • the breaking strength is 5.2-5.8 cN/dtex
  • the elongation at break is 38.5-40.0%
  • the elongation at break is 38.5-40.0%.
  • the long CV value reaches 8.5-9.0%;
  • the chitin-containing polyester filament prepared by the present invention has a dry heat shrinkage rate of 2.5-3.2%.
  • Example 1 A polyester filament of chitin and its preparation method
  • the chitin accounts for 1/25 of the weight of the mixed lye
  • the chitosan has a degree of deacetylation of 80%;
  • the added amount of hydroxypropyltrimethylammonium nitride is 0.50 times the weight of chitin;
  • the catalyst is zinc phosphomolybdate, and its added concentration is 0.11wt%;
  • the volume ratio of the dropwise addition of acetone to the solution is 1:3.0.
  • the mass ratio of the modified chitin crystals to the diatomaceous earth is 3.2:1;
  • the porogen is CaCl2, and the added amount of the porogen accounts for 1.2wt% of the total;
  • the precipitating agent is EVA, the vinyl acetate content is 25.0%, the melt index is 22.1 g/10 min (190° C., 2.15 kg), and the added amount of the precipitating agent accounts for 8.0 wt% of the total.
  • the PET pellets, chitin-containing functional modifier, titanium dioxide, sodium carboxymethyl cellulose, and diisopropyl trisulfide were added to the mixer for stirring and granulation, and mixing was carried out at 1000r/min for 60min, The diameter of the produced particles is 1-2mm;
  • the polyester functional particles are calculated in parts by weight, and the raw material composition includes: 50 parts of PET pellets, 25 parts of chitin-containing functional modifier, 3 parts of titanium dioxide, 12 parts of sodium carboxymethyl cellulose, 10 parts Parts of diisopropyl trisulfide.
  • twin-screw equipment At the feeding port in the middle of the twin-screw equipment, add ordinary polyester chips, polyester functional particles, and accelerators, and use a twin-screw extruder for melting and high-speed mixing at a temperature of 320°C to obtain a mixed spinning solution;
  • the melting high-speed blending is 1000 rad/min, and the mixing time is 60 min;
  • the functional particles account for 2.0wt% of the total weight
  • the mixing ratio of the accelerator, amino silicone oil and n-butyl titanate is 0.25:1; the added amount of the accelerator accounts for 3 wt% of the total spinning solution.
  • the main spinning process parameters of polyester filament include:
  • the extrusion temperature of melt spinning is 250°C, the initial pressure is 8MPa, the side blowing cooling air temperature is 25°C, the first hot rolling temperature is 168°C, and the drawing rate is 1200m/min; the second hot rolling temperature is 85°C, and the drawing rate is 3680m/min; heat setting at 120°C and winding speed of 1560/min to obtain chitin-containing polyester filament.
  • the chitin-containing polyester filament prepared by using the technical scheme of Example 1 has an inhibitory rate of 95.2% against Staphylococcus aureus, Escherichia coli, Candida albicans and other bacteria that are easy to infect humans. According to the polyester/cotton ratio of 30/ 70.
  • the antibacterial polyester textile produced by the knitting yarn can still reach 91.5%, and after 60 times of standard washing, the antibacterial rate is still 84.6%, and the antibacterial durability is good; the monofilament size of the polyester filament is 2.0 dtex, breaking strength of 5.5cN/dtex, breaking elongation of 40.0%, breaking elongation of CV value of 8.5%, uniform color, light transmittance of 71.0%, no obvious carbon black and particle agglomeration phenomenon can be seen with naked eyes, dry heat The shrinkage rate is 2.8%, which is suitable for making high-end textile products.
  • Example 2 A polyester filament of chitin and its preparation method
  • the chitin accounts for 1/23 of the weight of the mixed lye
  • the chitosan has a degree of deacetylation of 85%;
  • the added amount of the hydroxypropyltrimethylammonium nitride is 0.55 times the weight of chitin;
  • the catalyst is zinc phosphomolybdate, and its added concentration is 0.22wt%;
  • the volume ratio of the dropwise addition of acetone to the solution is 1:3.4.
  • the mass ratio of the modified chitin crystals and diatomaceous earth is 3.9:1;
  • the porogen is MgCl2, and the added amount of the porogen accounts for 2.0 wt% of the total;
  • the precipitating agent is EVA with a vinyl acetate content of 26.8%, a melt index of 22.9 g/10 min (190° C., 2.15 kg), and the added amount of the precipitating agent accounts for 10.5% by weight of the total.
  • the PET pellets, chitin-containing functional modifier, titanium dioxide, sodium carboxymethyl cellulose, and diisopropyl trisulfide were added to the mixer for stirring and granulation, and mixing was carried out at 1200r/min for 90min, The diameter of the produced particles is 1-2mm;
  • the polyester functional particles are calculated in parts by weight, and the raw material composition includes: 50 parts of PET pellets, 20 parts of chitin-containing functional modifier, 6 parts of titanium dioxide, 12 parts of sodium carboxymethyl cellulose, 12 parts Parts of diisopropyl trisulfide.
  • twin-screw equipment At the feeding port in the middle of the twin-screw equipment, add ordinary polyester chips, polyester functional particles, and add accelerators, and use a twin-screw extruder for melting and high-speed mixing at a temperature of 330°C to obtain a mixed spinning solution;
  • the melting high-speed blending is 1000 rad/min, and the mixing time is 60 min;
  • the functional particles accounted for 3.1wt% of the total weight
  • the mixing ratio of the accelerator, amino silicone oil and n-butyl titanate is 0.30:1; the added amount of the accelerator accounts for 3.5 wt% of the total spinning solution.
  • the main spinning process parameters of polyester filament include:
  • the extrusion temperature of melt spinning is 265°C, the initial pressure is 8MPa, the side blowing cooling air temperature is 25°C, the first hot roll temperature is 175°C, and the drawing rate is 1250m/min; the second hot roll temperature is 90°C, and the drawing rate is 3700m/min; heat setting at 130°C and winding speed of 1860/min to obtain chitin-containing polyester filament.
  • the chitin-containing polyester filament prepared by the technical scheme of Example 2 has an inhibitory rate of 97.8% against Staphylococcus aureus, Escherichia coli, Candida albicans and other bacteria that are easy to infect humans. According to the polyester/cotton ratio 30/
  • the knitting yarn prepared by 70, the processed antibacterial polyester textile can still reach 90.2%, and after 60 times of standard washing, the antibacterial rate is still 85.5%, and the antibacterial durability is good;
  • the single filament fineness of polyester filament is 2.8 dtex, breaking strength of 5.8cN/dtex, breaking elongation of 39.2%, breaking elongation of CV value of 9.0%, uniform color, light transmittance of 74.5%, no obvious carbon black and particle agglomeration phenomenon can be seen with naked eyes, dry heat
  • the shrinkage rate is 2.5%, which is suitable for making high-end textile products.
  • Example 3 A polyester filament of chitin and its preparation method
  • the chitin accounts for 1/20 of the weight of the mixed lye
  • the chitosan has a degree of deacetylation of 92%
  • the added amount of the hydroxypropyltrimethylammonium nitride is 0.58 times the weight of chitin;
  • the catalyst is zinc phosphomolybdate, and its added concentration is 0.32wt%;
  • the volume ratio of the dropwise addition of acetone to the solution is 1:4.
  • the mass ratio of the modified chitin crystals and diatomaceous earth is 5.0:1;
  • the porogen is NaCl, and the added amount of the porogen accounts for 2.8 wt% of the total;
  • the precipitating agent is EVA, the vinyl acetate content is 28.5%, the melt index is 24.1g/10min (190°C, 2.15kg), and the added amount of the precipitating agent accounts for 12.5% by weight of the total;
  • the PET pellets, chitin-containing functional modifier, titanium dioxide, sodium carboxymethyl cellulose, and diisopropyl trisulfide were added to the mixer for stirring and granulation, and mixing was carried out at 1200r/min for 90min, The diameter of the produced particles is 1-2mm;
  • the polyester functional particles are calculated in parts by weight, and the raw material composition includes: 60 parts of PET pellets, 20 parts of chitin-containing functional modifier, 3 parts of titanium dioxide, 9 parts of sodium carboxymethyl cellulose, 8 parts Parts of diisopropyl trisulfide;
  • twin-screw equipment At the feeding port in the middle of the twin-screw equipment, add ordinary polyester chips, polyester functional particles, and add accelerators, and use a twin-screw extruder for melting and high-speed mixing at a temperature of 330°C to obtain a mixed spinning solution;
  • the functional particles account for 4.0wt% of the total weight
  • the mixing ratio of the accelerator, amino silicone oil and n-butyl titanate is 0.40:1; the added amount of the accelerator accounts for 6wt% of the total spinning solution;
  • the main spinning process parameters of polyester filament include:
  • the extrusion temperature of melt spinning is 265°C, the initial pressure is 8MPa, the side blowing cooling air temperature is 30°C, the first hot rolling temperature is 170°C, and the drawing rate is 1250m/min; the second hot rolling temperature is 90°C, and the drawing rate is 3700m/min; heat setting at 125°C and winding speed of 1860/min to obtain chitin-containing polyester filament.
  • the chitin-containing polyester filament prepared by the technical scheme of Example 3 has an inhibitory rate of 98.5% against Staphylococcus aureus, Escherichia coli, Candida albicans and other bacteria that are easy to infect humans.
  • the polyester/cotton ratio 30/ 70% of the antibacterial polyester textile produced by knitting yarn can still reach 92%, and after 60 times of standard washing, the antibacterial rate is still 85.7%, and the antibacterial durability is good;
  • the monofilament size of the polyester filament is 3.5 dtex, breaking strength of 5.2cN/dtex, breaking elongation of 38.5%, breaking elongation of CV value of 8.7%, uniform color, light transmittance of 75.2%, no obvious carbon black and particle agglomeration can be seen with naked eyes, dry heat
  • the shrinkage rate is 3.2%, which is suitable for making high-end textile products.

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Abstract

一种含甲壳素的涤纶长丝制备方法，其中甲壳素含量为0.1-3%，该涤纶长丝的制备方法包括：改性甲壳素的制备、含甲壳素的功能改性剂的制备、聚酯功能性颗粒的制备、混合纺丝液的制备和纺丝成型；通过该制备工艺，制得的涤纶长丝单丝纤度为2.0-3.5dtex，断裂强度为5.2-5.8cN/dtex，断裂伸长率38.5-40.0%，断裂伸长CV值达到8.5-9.0%；该涤纶长丝具有天然抑菌特性，对人体容易感染的金黄色葡萄球菌、大肠杆菌、白色念珠菌等细菌的抑菌率达到95.0-98.5%，色泽均匀，透光率达到71-75%，肉眼看不到明显碳黑以及粒子团聚现象，适宜制作高档纺织制品。

Description

一种含甲壳素的涤纶长丝及其制备方法 技术领域
本发明属于纺丝技术领域，具体涉及一种含甲壳素的涤纶长丝及其制备方法。
背景技术
涤纶的学名叫聚对苯二甲酸乙二酯纤维，简称聚酯纤维，涤纶是这种纤维在我国的商品名称。它是以精对苯二甲酸(PTA)和乙二醇(EG)为原料经酯化和缩聚反应而制得的成纤高聚物—聚对苯二甲酸乙二醇酯(PET)，经纺丝和后处理制成的纤维，在服装面料领域，具有广泛的应用。
甲壳素又名几丁质、甲壳质等，是一种丰富的天然资源，每年自然合成近10亿之多，是继纤维素纤维后地球上最丰富的天然有机物。甲壳素是一种天然多糖，兼具有高等动物组织中的胶原质和高等织物组织中的纤维素两者的生物功能，对动植物都具有良好的适应性，同时还具有生物可降解性和无毒性，因此近年来他已经成为一种用途广泛的新型材料。将从天然甲壳类改性物质加入涤纶中，可以制得抗菌涤纶纤维，进而制备一系列抗菌纺织品。
现有技术中往往是将抗菌剂均匀喷洒在织物表面，该方法简单易行，但直接喷洒的甲壳素抗菌物质在使用中易流失，使抗菌效果减弱，抗菌不持久，本发明技术人员将其添加到纺丝纤维制品中，但在高温纺丝过程容易发生高温碳化，影响纤维弹性，对于高端制品可能影响其美观。
发明内容
为解决现有技术存在的问题，对现有工艺进行进一步优化，本发明提供一种含甲壳素的涤纶长丝及其制备方法，以实现以下发明目的：
提高海藻提取物提取效率
1、减少抗菌物质流失
2、避免天然抗菌剂的高温碳化
3、提高纤维制品弹性
为解决以上技术问题，本发明采用以下技术方案：
一种含甲壳素的涤纶长丝制备方法，其特征在于，所述涤纶长丝，甲壳素含量为0.1-3％；
所述制备方法，包括：改性甲壳素的制备、含甲壳素的功能改性剂的制备、聚酯功能性颗粒的制备、混合纺丝液的制备和纺丝成型；
所述改性甲壳素的制备，包括脱乙酰化、胺化改性和分离提纯步骤；所述胺化改性，羟丙基三甲基氮化铵的加入量为甲壳素重量的0.50-0.58倍；所加入催化剂为磷钼酸锌，其加入浓度为0.11-0.32wt％；
所述脱乙酰化，所用碱液为40-45wt％的氢氧化钠与氢氧化钾等比例混合碱液，所述甲壳素占混合碱液重量的1/20-1/25；制得含有氨基的壳聚糖悬浊液，脱乙酰度为80-92％；
所述分离提纯，滴加丙酮与溶液的体积比为1:3-4；
所述含甲壳素的功能改性剂的制备，所用溶剂为柠檬酸三乙酯，改性甲壳素晶体与硅藻土的质量比为3.2-5.0:1；
所述含甲壳素的功能改性剂的制备，包括加入致孔剂和沉淀剂；所述致孔剂为CaCl2、MgCl2或NaCl，致孔剂的加入量占总量的1.2-2.8wt％；
所述沉淀剂为EVA，其醋酸乙烯含量为25.0-28.5％，熔融指数为22-24g/10min(190℃、2.15kg)，沉淀剂的加入量占总量的8.0-12.5wt％；
所述聚酯功能性颗粒的制备，混合机中转速在1000-1200r/min，混合时间60-90min；所述聚酯功能性颗粒，按重量份数计，原材料组成包括：50-60份PET粒料、20-25份含甲壳素的功能改性剂、3-6份钛白粉、6-12份羧甲基纤维 素钠、6-12份二异丙基三硫醚；
所述混合纺丝液的制备，功能性颗粒占总重量的2-4wt％；
所述混合纺丝液的制备，还加入促进剂，所述促进剂，氨基硅油和钛酸正丁酯的混合比为0.25-0.40:1；促进剂的加入量占纺丝液总量的3-6wt％；
所述纺丝成型，第一热滚温度168-175℃，牵伸速率为1200-1250m/min；第二热滚温度85-90℃，牵伸速率为3680-3700m/min；卷绕速度1560-1860/min。
采用上述技术方案，本发明的有益效果为：
1、采用本发明含甲壳素涤纶长丝的制备方法，制得涤纶长丝具有优异的抗菌效果，可减少细菌的附着，对人体容易感染的金黄色葡萄球菌、大肠杆菌、白色念珠菌等细菌的抑菌率达到95.0-98.5％；
2、采用本发明制备的含甲壳素涤纶长丝，按照涤纶/棉比例30/70制备的的针织纱，加工出的抗菌涤纶纺织物仍可达到90-92％，且经过60次标准洗涤后，抑菌率仍在84-86％，抑菌持久性好；
3、采用本发明制备的含甲壳素涤纶长丝，色泽均匀，透光率达到71-75％，肉眼看不到明显碳黑以及粒子团聚现象；
4、采用本发明含甲壳素涤纶长丝的制备方法，制得涤纶长丝单丝纤度为2.0-3.5dtex，断裂强度为5.2-5.8cN/dtex，断裂伸长率38.5-40.0％，断裂伸长CV值达到8.5-9.0％；
5、采用本发明制备的含甲壳素涤纶长丝，干热收缩率2.5-3.2％。
具体实施方式：
下面结合具体的实施例，进一步阐述本发明。
实施例1一种甲壳素的涤纶长丝及其制备方法
1、改性甲壳素的制备
1)脱乙酰化
称取甲壳素加入到40wt％的氢氧化钠与氢氧化钾等比例混合碱液中，升高温度至65℃，提高搅拌转速至260转/分钟，保温搅拌10h，通过脱乙酰化反应，生成含有氨基的壳聚糖悬浊液；
所述甲壳素占混合碱液重量的1/25；
所述壳聚糖，脱乙酰度为80％；
2)胺化改性
向上述壳聚糖悬浊液中加入羟丙基三甲基氮化铵，后加入催化剂，升高温度至70℃，在此温度下反应10h，悬浊液逐渐变成清澈黄色季胺盐溶液；
所述羟丙基三甲基氮化铵的加入量为甲壳素重量的0.50倍；
所述催化剂为磷钼酸锌，其加入浓度为0.11wt％；
3)分离提纯
向溶液中缓慢滴加丙酮，后置于零下20℃冰箱中过夜，静置沉淀，抽滤，并采用冰乙醇洗涤滤饼至滤液无色，置于45℃真空干燥箱内进行干燥，得到改性甲壳素晶体；
所述分离提纯，滴加丙酮与溶液的体积比为1:3.0。
2、含甲壳素的功能改性剂的制备
取上述改性甲壳素晶体加入到10倍柠檬酸三乙酯溶液中，搅拌溶解，后将硅藻土加入其中，加入致孔剂和沉淀剂，升高温度至80℃，转速1800-2000r/min，快速搅拌混合30min，EVA包裹颗粒逐渐沉淀析出，静置随室温冷却，得到含甲壳素的功能改性剂；
所述改性甲壳素晶体与硅藻土的质量比为3.2:1；
所述致孔剂为CaCl2，致孔剂的加入量占总量的1.2wt％；
所述沉淀剂为EVA，其醋酸乙烯含量为25.0％，熔融指数为22.1g/10min(190℃、2.15kg)，沉淀剂的加入量占总量的8.0wt％。
3、聚酯功能性颗粒的制备
后将PET粒料、含甲壳素的功能改性剂、钛白粉、羧甲基纤维素钠、二异丙基三硫醚加入到混合机中进行搅拌制粒，在1000r/min下混合60min，制得颗粒直径1-2mm；
所述聚酯功能性颗粒，按重量份数计，原材料组成包括：50份PET粒料、25份含甲壳素的功能改性剂、3份钛白粉、12份羧甲基纤维素钠、10份二异丙基三硫醚。
4、混合纺丝液的制备
在双螺杆设备中部加料口，加入普通涤纶切片、聚酯功能性颗粒，并加入促进剂，采用双螺杆挤出机进行熔融高速混炼，温度为320℃，得到混合纺丝液；
所述熔融高速共混，转速为1000rad/min，混合时间60min；
所述功能性颗粒占总重量的2.0wt％；
所述促进剂，氨基硅油和钛酸正丁酯的混合比为0.25:1；促进剂的加入量占纺丝液总量的3wt％。
5、纺丝成型
涤纶长丝的主要纺丝工艺参数包括：
熔融纺丝的挤出温度250℃，初始压力8MPa，侧吹风冷却风温25℃，第一热滚温度168℃，牵伸速率为1200m/min；第二热滚温度85℃，牵伸速率为3680m/min；热定型120℃，卷绕速度1560/min，得到含甲壳素的涤纶长丝。
采用实施例1的技术方案制备的含甲壳素的涤纶长丝，对人体容易感染的金黄色葡萄球菌、大肠杆菌、白色念珠菌等细菌的抑菌率达到95.2％，按照涤纶/棉比例30/70制备的的针织纱，加工出的抗菌涤纶纺织物仍可达到91.5％，且经过60次标准洗涤后，抑菌率仍在84.6％，抑菌持久性好；涤纶长丝单丝纤度为2.0dtex，断裂强度为5.5cN/dtex，断裂伸长率40.0％，断裂伸长CV值达到 8.5％，色泽均匀，透光率达到71.0％，肉眼看不到明显碳黑以及粒子团聚现象，干热收缩率为2.8％，适宜制作高档纺织制品。
实施例2一种甲壳素的涤纶长丝及其制备方法
1、改性甲壳素的制备
1)脱乙酰化
称取甲壳素加入到45wt％的氢氧化钠与氢氧化钾等比例混合碱液中，升高温度至0℃，提高搅拌转速至300转/分钟，保温搅拌10h，通过脱乙酰化反应，生成含有氨基的壳聚糖悬浊液；
所述甲壳素占混合碱液重量的1/23；
所述壳聚糖，脱乙酰度为85％；
2)胺化改性
向上述壳聚糖悬浊液中加入羟丙基三甲基氮化铵，后加入催化剂，升高温度至80℃，在此温度下反应12h，悬浊液逐渐变成清澈黄色季胺盐溶液；
所述羟丙基三甲基氮化铵的加入量为甲壳素重量的0.55倍；
所述催化剂为磷钼酸锌，其加入浓度为0.22wt％；
3)分离提纯
向溶液中缓慢滴加丙酮，后置于零下20℃冰箱中过夜，静置沉淀，抽滤，并采用冰乙醇洗涤滤饼至滤液无色，置于45℃真空干燥箱内进行干燥，得到改性甲壳素晶体；
所述分离提纯，滴加丙酮与溶液的体积比为1:3.4。
2、含甲壳素的功能改性剂的制备
取上述改性甲壳素晶体加入到10倍柠檬酸三乙酯溶液中，搅拌溶解，后将硅藻土加入其中，加入致孔剂和沉淀剂，升高温度至85℃，转速2000r/min，快速搅拌混合50min，EVA包裹颗粒逐渐沉淀析出，静置随室温冷却，得到含甲 壳素的功能改性剂；
所述改性甲壳素晶体与硅藻土的质量比为3.9:1；
所述致孔剂为MgCl2，致孔剂的加入量占总量的2.0wt％；
所述沉淀剂为EVA，其醋酸乙烯含量为26.8％，熔融指数为22.9g/10min(190℃、2.15kg)，沉淀剂的加入量占总量的10.5wt％。
3、聚酯功能性颗粒的制备
后将PET粒料、含甲壳素的功能改性剂、钛白粉、羧甲基纤维素钠、二异丙基三硫醚加入到混合机中进行搅拌制粒，在1200r/min下混合90min，制得颗粒直径1-2mm；
所述聚酯功能性颗粒，按重量份数计，原材料组成包括：50份PET粒料、20份含甲壳素的功能改性剂、6份钛白粉、12份羧甲基纤维素钠、12份二异丙基三硫醚。
4、混合纺丝液的制备
在双螺杆设备中部加料口，加入普通涤纶切片、聚酯功能性颗粒，并加入促进剂，采用双螺杆挤出机进行熔融高速混炼，温度为330℃，得到混合纺丝液；
所述熔融高速共混，转速为1000rad/min，混合时间60min；
所述功能性颗粒占总重量的3.1wt％；
所述促进剂，氨基硅油和钛酸正丁酯的混合比为0.30:1；促进剂的加入量占纺丝液总量的3.5wt％。
5、纺丝成型
涤纶长丝的主要纺丝工艺参数包括：
熔融纺丝的挤出温度265℃，初始压力8MPa，侧吹风冷却风温25℃，第一热滚温度175℃，牵伸速率为1250m/min；第二热滚温度90℃，牵伸速率为3700m/min；热定型130℃，卷绕速度1860/min，得到含甲壳素的涤纶长丝。
采用实施例2的技术方案制备的含甲壳素的涤纶长丝，对人体容易感染的金黄色葡萄球菌、大肠杆菌、白色念珠菌等细菌的抑菌率达到97.8％，按照涤纶/棉比例30/70制备的的针织纱，加工出的抗菌涤纶纺织物仍可达到90.2％，且经过60次标准洗涤后，抑菌率仍在85.5％，抑菌持久性好；涤纶长丝单丝纤度为2.8dtex，断裂强度为5.8cN/dtex，断裂伸长率39.2％，断裂伸长CV值达到9.0％，色泽均匀，透光率达到74.5％，肉眼看不到明显碳黑以及粒子团聚现象，干热收缩率为2.5％，适宜制作高档纺织制品。
实施例3一种甲壳素的涤纶长丝及其制备方法
1、改性甲壳素的制备
1)脱乙酰化
称取甲壳素加入到45wt％的氢氧化钠与氢氧化钾等比例混合碱液中，升高温度至70℃，提高搅拌转速至300转/分钟，保温搅拌12h，通过脱乙酰化反应，生成含有氨基的壳聚糖悬浊液；
所述甲壳素占混合碱液重量的1/20；
所述壳聚糖，脱乙酰度为92％；
2)胺化改性
向上述壳聚糖悬浊液中加入羟丙基三甲基氮化铵，后加入催化剂，升高温度至80℃，在此温度下反应12h，悬浊液逐渐变成清澈黄色季胺盐溶液；
所述羟丙基三甲基氮化铵的加入量为甲壳素重量的0.58倍；
所述催化剂为磷钼酸锌，其加入浓度为0.32wt％；
3)分离提纯
向溶液中缓慢滴加丙酮，后置于零下30℃冰箱中过夜，静置沉淀，抽滤，并采用冰乙醇洗涤滤饼至滤液无色，置于45℃真空干燥箱内进行干燥，得到改性甲壳素晶体；
所述分离提纯，滴加丙酮与溶液的体积比为1:4。
2、含甲壳素的功能改性剂的制备
取上述改性甲壳素晶体加入到12倍柠檬酸三乙酯溶液中，搅拌溶解，后将硅藻土加入其中，加入致孔剂和沉淀剂，升高温度至85℃，转速2000r/min，快速搅拌混合50min，EVA包裹颗粒逐渐沉淀析出，静置随室温冷却，得到含甲壳素的功能改性剂；
所述改性甲壳素晶体与硅藻土的质量比为5.0:1；
所述致孔剂为NaCl，致孔剂的加入量占总量的2.8wt％；
所述沉淀剂为EVA，其醋酸乙烯含量为28.5％，熔融指数为24.1g/10min(190℃、2.15kg)，沉淀剂的加入量占总量的12.5wt％；
3、聚酯功能性颗粒的制备
后将PET粒料、含甲壳素的功能改性剂、钛白粉、羧甲基纤维素钠、二异丙基三硫醚加入到混合机中进行搅拌制粒，在1200r/min下混合90min，制得颗粒直径1-2mm；
所述聚酯功能性颗粒，按重量份数计，原材料组成包括：60份PET粒料、20份含甲壳素的功能改性剂、3份钛白粉、9份羧甲基纤维素钠、8份二异丙基三硫醚；
4、混合纺丝液的制备
在双螺杆设备中部加料口，加入普通涤纶切片、聚酯功能性颗粒，并加入促进剂，采用双螺杆挤出机进行熔融高速混炼，温度为330℃，得到混合纺丝液；
所述熔融高速共混，转速为1200rad/min，混合时间80min；
所述功能性颗粒占总重量的4.0wt％；
所述促进剂，氨基硅油和钛酸正丁酯的混合比为0.40:1；促进剂的加入量占纺丝液总量的6wt％；
5、纺丝成型
涤纶长丝的主要纺丝工艺参数包括：
熔融纺丝的挤出温度265℃，初始压力8MPa，侧吹风冷却风温30℃，第一热滚温度170℃，牵伸速率为1250m/min；第二热滚温度90℃，牵伸速率为3700m/min；热定型125℃，卷绕速度1860/min，得到含甲壳素的涤纶长丝。
采用实施例3的技术方案制备的含甲壳素的涤纶长丝，对人体容易感染的金黄色葡萄球菌、大肠杆菌、白色念珠菌等细菌的抑菌率达到98.5％，按照涤纶/棉比例30/70制备的的针织纱，加工出的抗菌涤纶纺织物仍可达到92％，且经过60次标准洗涤后，抑菌率仍在85.7％，抑菌持久性好；涤纶长丝单丝纤度为3.5dtex，断裂强度为5.2cN/dtex，断裂伸长率38.5％，断裂伸长CV值达到8.7％，色泽均匀，透光率达到75.2％，肉眼看不到明显碳黑以及粒子团聚现象，干热收缩率为3.2％，适宜制作高档纺织制品。
最后应说明的是：以上所述仅为本发明的优选实施例，并不用于限制本发明，尽管参照前述实施例对本发明进行了详细说明，对于本领域的技术人员来说，其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种含甲壳素的涤纶长丝制备方法，其特征在于，所述涤纶长丝，甲壳素含量为0.1-3％。
  2. 根据权利要求1所述的制备方法，其特征在于，所述制备方法，包括：改性甲壳素的制备、含甲壳素的功能改性剂的制备、聚酯功能性颗粒的制备、混合纺丝液的制备和纺丝成型；所述混合纺丝液的制备，功能性颗粒占总重量的2-4wt％。
  3. 根据权利要求2所述的制备方法，其特征在于，所述混合纺丝液的制备，还加入促进剂，所述促进剂，氨基硅油和钛酸正丁酯的混合比为0.25-0.40:1；促进剂的加入量占纺丝液总量的3-6wt％。
  4. 根据权利要求2所述的制备方法，其特征在于，所述含甲壳素的功能改性剂的制备，所用溶剂为柠檬酸三乙酯，改性甲壳素晶体与硅藻土的质量比为3.2-5.0:1。
  5. 根据权利要求4所述的制备方法，其特征在于，所述含甲壳素的功能改性剂的制备，包括加入致孔剂和沉淀剂；所述致孔剂为CaCl2、MgCl2或NaCl，致孔剂的加入量占总量的1.2-2.8wt％；所述沉淀剂为EVA，其醋酸乙烯含量为25.0-28.5％，190℃、2.15kg条件下的熔融指数为22-24g/10min，沉淀剂的加入量占总量的8.0-12.5wt％。
  6. 根据权利要求2所述的制备方法，其特征在于，所述改性甲壳素的制备，包括脱乙酰化、胺化改性和分离提纯步骤；所述胺化改性，羟丙基三甲基氮化铵的加入量为甲壳素重量的0.50-0.58倍；所加入催化剂为磷钼酸锌，其加入浓度为0.11-0.32wt％。
  7. 根据权利要求6所述的制备方法，其特征在于，所述脱乙酰化，所用碱液为40-45wt％的氢氧化钠与氢氧化钾等比例混合碱液，所述甲壳素占混合碱液重量的1/20-1/25；制得含有氨基的壳聚糖悬浊液，脱乙酰度为80-92％。
  8. 根据权利要求6所述的制备方法，其特征在于，所述分离提纯，滴加丙酮与溶液的体积比为1:3-4。
  9. 根据权利要求2所述的制备方法，其特征在于，所述聚酯功能性颗粒的制备，混合机中转速在1000-1200r/min，混合时间60-90min；所述聚酯功能性颗粒，按重量份数计，原材料组成包括：50-60份PET粒料、20-25份含甲壳素的功能改性剂、3-6份钛白粉、6-12份羧甲基纤维素钠、6-12份二异丙基三硫醚。
  10. 根据权利要求2所述的制备方法，其特征在于，所述纺丝成型，第一热滚温度168-175℃，牵伸速率为1200-1250m/min；第二热滚温度85-90℃，牵伸速率为3680-3700m/min；卷绕速度1560-1860/min。
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