WO2021174720A1 - 一种海藻涤纶长纤维及其制备方法 - Google Patents

一种海藻涤纶长纤维及其制备方法 Download PDF

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Publication number
WO2021174720A1
WO2021174720A1 PCT/CN2020/097921 CN2020097921W WO2021174720A1 WO 2021174720 A1 WO2021174720 A1 WO 2021174720A1 CN 2020097921 W CN2020097921 W CN 2020097921W WO 2021174720 A1 WO2021174720 A1 WO 2021174720A1
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preparation
seaweed
polyester
long fiber
polyester long
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PCT/CN2020/097921
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English (en)
French (fr)
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黄效华
刘彦明
黄效谦
刘宇
刘洁
甄丽
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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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Publication of WO2021174720A1 publication Critical patent/WO2021174720A1/zh

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—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
    • 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
    • C08B37/0003—General processes for their isolation or fractionation, e.g. purification or extraction from biomass
    • 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
    • C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
    • C08B37/0063—Glycosaminoglycans or mucopolysaccharides, e.g. keratan sulfate; Derivatives thereof, e.g. fucoidan
    • 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

Definitions

  • the invention belongs to the technical field of spinning, and specifically relates to a seaweed polyester long fiber 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
  • Seaweed is a pure natural marine biological product, which contains alginic acid, crude protein, multiple vitamins, enzymes and trace elements. Seaweed fiber has typical excellent properties such as good biocompatibility, high hygroscopicity, biodegradation and high oxygen permeability. In addition, it also has excellent antibacterial and antibacterial properties.
  • the preparation of fibers containing seaweed extract is useful The fields of civilian clothing, daily chemicals and sanitary products have huge market application prospects. However, during the preparation process, it was found that the extraction efficiency of seaweed extracts was low, and at the same time, carbonization deterioration was prone to occur during the preparation process, which affected the quality of the products.
  • the present invention provides a seaweed polyester long fiber and a preparation method thereof, so as to achieve the following invention objectives:
  • the present invention adopts the following technical solutions:
  • a preparation method of seaweed polyester long fiber characterized in that the content of seaweed extract in the polyester long fiber is 0.1-3%;
  • the preparation method includes the steps of preparation of seaweed extract, preparation of functional modifier containing seaweed extract, preparation of polyester functional particles, mixing and spinning forming steps;
  • the preparation of the seaweed extract includes extraction and fermentation steps; the extraction, the extraction liquid is a phosphate buffer with a pH of 7.8-8.2 prepared by dissolving dipotassium hydrogen phosphate and potassium dihydrogen phosphate in ethanol liquid;
  • the fermentation includes inoculating a double-nucleated biological enzyme into the concentrate, the fermentation temperature is 30-35°C, the humidity is 50 ⁇ 5%, and the fermentation time is 8-10h;
  • composition of the composite biological enzyme includes cellulase, protease and pectinase, and the mass ratio of cellulase, protease and pectinase is 3.3-5:1-1.2:0.4-0.7;
  • the preparation of the functional modifier containing the seaweed extract includes pretreatment, ultrasonic immersion and flocculation precipitation; the pretreatment, the mass ratio of tetrabutylammonium bromide to sulfuric acid is 1:20-23; sulfur The dosage of dilauryl dipropionate is 2.5-4wt% of the total solution;
  • the ultrasonic dipping, the ultrasonic power is 280-300HZ;
  • liquid caustic soda is added to adjust the pH of the solution to 8.5-10.5, and the addition amount of polyacrylamide is 1.2-3g/L;
  • the polyester functional particles are prepared in parts by weight, and the raw material composition includes: 40-50 parts of PET chips, 25-35 parts of functional modifier containing seaweed extract, and 3-10 parts of carboxymethyl cellulose Sodium, 6-15 parts of zinc stearate and 6-15 parts of dodecyl alcohol;
  • the rotation speed is 1000-1200rad/min
  • the temperature is 300-310°C
  • the water content of the mixed melt is 0.02-0.05wt%
  • the side blowing wind speed is 0.5-0.6 m/s
  • the winding spinning speed is 3650-3850 m/min
  • the three-time draft ratio is accordingly 1:0.8; 1:1.0; 1:1.2.
  • the polyester filament produced has a certain antibacterial effect, can reduce the adhesion of bacteria, and inhibits Staphylococcus aureus, Escherichia coli, Candida albicans and other bacteria that are easy to infect the human body.
  • the bacterial rate reaches 95.0-97.5%;
  • the processed antibacterial polyester textile can still reach 90-92%, and after 60 standard washings, it is antibacterial The rate is still 84-86%, with good antibacterial durability;
  • the seaweed polyester filament prepared by the present invention has uniform color and high transparency, and no obvious carbon black and particle agglomeration are visible to the naked eye;
  • the polyester filament obtained has good hydrophilicity and hygroscopicity, and the dripping water diffusion time is 0.22-0.35s;
  • the monofilament fineness of the polyester long fiber is 0.3-0.5dpf
  • the dry breaking strength of the fiber reaches 6.5cN/dtex-6.8cN/dtex
  • the wet breaking strength is 5.2-5.3cN /dtex
  • the elongation at break is 32-36%.
  • Example 1 A kind of seaweed polyester long fiber and its preparation method
  • Extraction Wash the seaweed, dry it, and then grind it into a fine powder with a particle size of 2-3mm. Use a Soxhlet extractor to add the extract for extraction at a temperature of 75°C and an extraction time of 24h;
  • the extract is a phosphate buffer solution with a pH of 7.8-8.0 prepared by dissolving dipotassium hydrogen phosphate and potassium dihydrogen phosphate in ethanol;
  • Fermentation inoculate compound biological enzymes into the concentrated liquid for fermentation, the fermentation temperature is 30°C, the humidity is 50%, and the fermentation time is 8h;
  • composition of the composite biological enzyme includes cellulase, protease and pectinase, and the mass ratio of cellulase, protease and pectinase is 3.3:1:0.4;
  • Post-processing the slurry obtained after fermentation is suction filtered and spray-dried to obtain seaweed extract powder.
  • the mass ratio of tetrabutylammonium bromide and sulfuric acid is 1:20;
  • the dosage of dilauryl thiodipropionate is 2.5wt% of the total solution
  • the concentration of the polyacrylamide is 1.2 g/L.
  • the functional modifier containing the seaweed extract and other raw materials into the mixing mixer for mixing and granulation, the mixing speed is 500r/min, stirring for 3 hours, to obtain polyester functional particles;
  • the composition of raw materials includes: 40 parts of PET chips, 25 parts of function modifier containing seaweed extract, 5 parts of sodium carboxymethyl cellulose, 15 parts of zinc stearate and 15 parts of dodecyl alcohol;
  • twin-screw equipment At the feeding port in the middle of the twin-screw equipment, add ordinary polyester chips, polyester functional particles, and add antistatic agents, and use a twin-screw extruder for melting and high-speed mixing.
  • the temperature is 300°C, and the water content of the mixed melt is 0.02wt%. ;
  • the melting high-speed blending is 1000 rad/min, and the mixing time is 60 min;
  • the functional particles accounted for 2.5 wt% of the total weight.
  • the spinning solution is introduced into the spinning box, the fibers are ejected from the holes of the spinneret, and the polyester filament containing the seaweed extract of the present invention is prepared by the melt spinning method;
  • the extrusion temperature of the melt spinning is 250°C
  • the side blowing cooling air temperature is 25°C
  • the side blowing wind speed is 0.5m/s
  • the winding spinning speed is 3650m/min
  • the three draft ratio is 1 accordingly. :0.8; 1:1.0; 1:1.2.
  • Example 1 Using the technical scheme of Example 1 to prepare seaweed polyester filament, the extraction rate of active ingredients in the seaweed reaches 74.5%, and the utilization rate is greatly improved; the obtained seaweed polyester filament is easy to infect the human body with Staphylococcus aureus, Escherichia coli, and white.
  • Candida and other bacteria have a bacteriostatic rate of 95.0%.
  • the antibacterial polyester textile fabric of knitted yarn prepared with a polyester/cotton ratio of 30/70 can still reach 90.5%, and after 60 standard washings, the bacteriostatic rate It is still 84.6% and has good antibacterial durability; at the same time, the fiber also has good hydrophilicity and hygroscopicity, and the dripping diffusion time is 0.27s; the single filament fineness of the polyester filament is 0.33dpf, and the dry breaking strength of the fiber reaches 6.51 cN/dtex, wet breaking strength is 5.20cN/dtex, breaking elongation is 33.6%, comprehensive performance is very excellent.
  • Example 2 A kind of seaweed polyester long fiber and its preparation method
  • Extraction Wash the seaweed, dry it, and then grind it into a fine powder with a particle size of 2-3mm. Use a Soxhlet extractor to add the extract for extraction, at a temperature of 78°C, and an extraction time of 28h;
  • the extract is a phosphate buffer with a pH of 8.0-8.2 prepared by dissolving dipotassium hydrogen phosphate and potassium dihydrogen phosphate in ethanol;
  • Fermentation inoculate compound biological enzymes into the concentrated liquid for fermentation, the fermentation temperature is 35°C, the humidity is 55%, and the fermentation time is 8h;
  • composition of the composite biological enzyme includes cellulase, protease and pectinase, and the mass ratio of cellulase, protease and pectinase is 4:1:0.5;
  • Post-processing the slurry obtained after fermentation is suction filtered and spray-dried to obtain seaweed extract powder.
  • the mass ratio of tetrabutylammonium bromide and sulfuric acid is 1:20;
  • the amount of dilauryl thiodipropionate is 3.0wt% of the total solution
  • the concentration of the polyacrylamide is 2.0 g/L.
  • the functional modifier containing the seaweed extract and other raw materials into the mixing mixer for mixing and granulation, the mixing speed is 600r/min, stirring for 4h, to obtain polyester functional granules;
  • the raw material composition includes: 50 parts of PET chips, 35 parts of functional modifier containing seaweed extract, 3 parts of sodium carboxymethyl cellulose, 6 parts of zinc stearate and 6 parts of dodecyl alcohol;
  • twin-screw equipment At the feeding port in the middle of the twin-screw equipment, add ordinary polyester chips, polyester functional particles, and add antistatic agents, and use a twin-screw extruder for melting and high-speed mixing.
  • the temperature is 310°C, and the water content of the mixed melt is 0.04wt%. ;
  • the functional particles account for 3.5wt% of the total weight
  • the spinning solution is introduced into the spinning box, the fibers are ejected from the holes of the spinneret, and the polyester filament containing the seaweed extract of the present invention is prepared by the melt spinning method;
  • the extrusion temperature of the melt spinning is 265°C
  • the side blowing cooling air temperature is 30°C
  • the side blowing wind speed is 0.6m/s
  • the winding spinning speed is 3700m/min
  • the three draft ratio is 1 accordingly. :0.8; 1:1.0; 1:1.2.
  • Example 2 Using the technical scheme of Example 2 to prepare seaweed polyester filament, the extraction rate of active ingredients in the seaweed reached 77.7%, and the utilization rate was greatly improved; the prepared seaweed polyester filament was easily infected with Staphylococcus aureus, Escherichia coli, and white. The antibacterial rate of Candida and other bacteria reached 97.5%.
  • the antibacterial polyester textile produced by knitting yarn prepared with a polyester/cotton ratio of 30/70 can still reach 91.3%, and after 60 standard washings, the antibacterial rate It is still 85.2%, and the antibacterial durability is good; at the same time, the fiber also has good hydrophilicity and hygroscopicity, and the dripping diffusion time is 0.22s; the monofilament fineness of the polyester filament is 0.40dpf, and the dry breaking strength of the fiber reaches 6.66 cN/dtex, wet breaking strength of 5.21cN/dtex, breaking elongation of 32.2%, and excellent overall performance.
  • Example 3 A kind of seaweed polyester long fiber and its preparation method
  • Extraction Wash the seaweed, dry it, and then grind it into a fine powder with a particle size of 3-4mm. Use a Soxhlet extractor to add the extract for extraction at a temperature of 78°C and an extraction time of 30h;
  • the extract is a phosphate buffer with a pH of 8.0-8.2 prepared by dissolving dipotassium hydrogen phosphate and potassium dihydrogen phosphate in ethanol;
  • Fermentation inoculate compound biological enzymes into the concentrated liquid for fermentation, the fermentation temperature is 35°C, the humidity is 52%, and the fermentation time is 10h;
  • composition of the composite biological enzyme includes cellulase, protease and pectinase, and the mass ratio of cellulase, protease and pectinase is 5:1.2:0.7;
  • Post-processing the slurry obtained after fermentation is suction filtered and spray-dried to obtain seaweed extract powder.
  • the montmorillonite is added to tetrabutylammonium bromide and sulfuric acid solution for activation treatment, sealed, heated and stirred, then filtered, and the filter cake is retained;
  • the seaweed extract powder is added to 8 times deionized water, and the accelerator sulfur is added Substitute dilauryl dipropionate, after stirring evenly, ultrasonic 15min at 20HZ frequency to obtain seaweed extract solution;
  • the mass ratio of tetrabutylammonium bromide and sulfuric acid is 1:23;
  • the dosage of dilauryl thiodipropionate is 4wt% of the total solution
  • the concentration of the polyacrylamide is 3 g/L.
  • the functional modifier containing the seaweed extract and other raw materials into the mixing mixer for mixing and granulation, the mixing speed is 600r/min, stirring for 4h, to obtain polyester functional granules;
  • the raw material composition includes: 50 parts of PET chips, 30 parts of functional modifier containing seaweed extract, 5 parts of sodium carboxymethyl cellulose, 7 parts of zinc stearate and 8 parts of dodecyl alcohol;
  • twin-screw extruder is used for melting and high-speed mixing, the temperature is 310°C, and the water content of the mixed melt is 0.05wt% ;
  • the functional particles account for 5wt% of the total weight
  • the spinning solution is introduced into the spinning box, the fibers are ejected from the holes of the spinneret, and the polyester filament containing the seaweed extract of the present invention is prepared by the melt spinning method;
  • the extrusion temperature of the melt spinning is 265°C
  • the side blowing cooling air temperature is 30°C
  • the side blowing wind speed is 0.6m/s
  • the winding spinning speed is 3850m/min
  • the three draft ratio is 1 accordingly. :0.8; 1:1.0; 1:1.2.
  • Example 3 Using the technical scheme of Example 3 to prepare seaweed polyester filament, the extraction rate of active ingredients in the seaweed reached 78.6%, and the utilization rate was greatly improved; the obtained seaweed polyester filament was easy to infect the human body with Staphylococcus aureus, Escherichia coli, and white. The antibacterial rate of Candida and other bacteria reached 96.6%, according to the ratio of polyester/cotton
  • the processed antibacterial polyester textile can still reach 91.8%, and after 60 standard washing, the antibacterial rate is still 85.7%, and the antibacterial durability is good; at the same time, the fiber also has good properties. Hydrophilicity and hygroscopicity, the dripping diffusion time is 0.35s; the filament size of the polyester long fiber is 0.51dpf, the dry breaking strength of the fiber reaches 6.78cN/dtex, the wet breaking strength is 5.27cN/dtex, and the elongation at break 35.5%, the overall performance is very excellent.

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Abstract

本发明提供一种海藻涤纶长纤维制备方法，其中，涤纶长纤维中海藻提取物含量为0.1-3％，该涤纶长纤维的制备方法包括海藻提取物的制备、含海藻提取物的功能改性剂的制备、聚酯功能性颗粒的制备、混炼和纺丝成型步骤，采用该方法制备的海藻涤纶长纤维，海藻中有效成分褐藻多糖硫酸酯类物质提取率大大提高，同时该涤纶长纤维具有良好的亲水性和吸湿性，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95.0-97.5％，该种涤纶长纤维单丝纤度0.3-0.5dpf，纤维的干断裂强度达到6.5cN/dtex-6.8cN/dtex，湿断裂强度为5.2-5.3cN/dtex，断裂伸长率32-36％，综合性能优异。

Description

一种海藻涤纶长纤维及其制备方法 技术领域
本发明属于纺丝技术领域，具体涉及一种海藻涤纶长纤维及其制备方法。
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。
海藻是一种纯天然的海洋生物产品，内含有藻胶酸，粗蛋白，多种维生素，酶和微量元素等。海藻纤维具有良好的生物相容性、自身高吸湿性、生物降解及高透氧性等典型的优异性能，除此之外，还具有优异的抑菌抗菌性，制备含海藻提取物的纤维在民用服装、日化及卫生用品领域有着巨大的市场应用前景，但是在制备过程中，发现海藻提取物提取效率低，同时在制备过程中易发生碳化变质，影响制品品质。
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，本发明提供一种海藻涤纶长纤维及其制备方法，以实现以下发明目的：
1、提高海藻提取物提取效率
2、提升抗菌功效
3、延长抗菌时间
为解决以上技术问题，本发明采用以下技术方案：
一种海藻涤纶长纤维制备方法，其特征在于，所述涤纶长纤维，海藻提取物含量为0.1-3％；
所述制备方法，包括海藻提取物的制备、含海藻提取物的功能改性剂的制备、聚酯功能性颗粒的制备、混炼和纺丝成型步骤；
所述海藻提取物的制备，包括抽提和发酵步骤；所述抽提，抽提液是将磷酸氢二钾与磷酸二氢钾溶解于乙醇中制得的pH为7.8-8.2的磷酸盐缓冲液；
所述发酵，包括向浓缩液中接种复核生物酶，发酵温度30-35℃，湿度50±5％，发酵时间8-10h；
所述复合生物酶，其组成包括纤维素酶、蛋白酶和果胶酶，纤维素酶、蛋白酶和果胶酶的质量比为3.3-5：1-1.2：0.4-0.7；
所述含海藻提取物的功能改性剂的制备，包括前处理、超声浸渍和絮凝沉淀；所述前处理，氯化四丁基溴化铵与硫酸的质量比为1：20-23；硫代二丙酸二月桂酯的用量是溶液总量的2.5-4wt％；
所述超声浸渍，超声功率280-300HZ；
所述絮凝沉淀，加入液碱调节溶液pH至8.5-10.5，聚丙烯酰胺加入量为1.2-3g/L；
所述聚酯功能性颗粒的制备，按重量份数计，原材料组成包括：40-50份PET切片、25-35份含海藻提取物的功能改性剂、3-10份羧甲基纤维素钠、6-15份硬脂酸锌和6-15份十二碳醇；
所述混炼，转速为1000-1200rad/min，温度为300-310℃，混合熔体含水量0.02-0.05wt％；
所述纺丝成型，侧吹风风速为0.5-0.6m/s，卷绕纺丝速度3650-3850m/min，三次牵伸比依此为1:0.8；1:1.0；1:1.2。
采用上述技术方案，本发明的有益效果为：
1、采用本发明海藻涤纶长纤维的制备方法，结合生物酶解技术，有效降低提取温度，提高提取率，海藻中有效成分褐藻多糖硫酸酯类物质提取率达到 74-79％；
2、采用本发明海藻涤纶长纤维的制备方法，制得涤纶长丝具有一定的抗菌效果，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95.0-97.5％；
3、采用本发明制备海藻涤纶长纤维，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；
4、采用本发明制备的海藻涤纶长纤维，色泽均匀，透明度高，肉眼看不到明显碳黑以及粒子团聚现象；
5、采用本发明海藻涤纶长纤维的制备方法，制得涤纶长纤维具有良好的亲水性和吸湿性，滴水扩散时间为0.22-0.35s；
6、采用本发明海藻涤纶长纤维的制备方法，制得涤纶长纤维单丝纤度0.3-0.5dpf，纤维的干断裂强度达到6.5cN/dtex-6.8cN/dtex，湿断裂强度为5.2-5.3cN/dtex，断裂伸长率32-36％。
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1一种海藻涤纶长纤维及其制备方法
1、海藻提取物的制备
1)抽提：将海藻洗净、晒干，后在研磨成粒径2-3mm的细粉，采用索氏提取器加入抽提液进行抽提，温度75℃，抽提时间24h；，
所述抽提液，是将磷酸氢二钾与磷酸二氢钾溶解于乙醇中制得的pH为7.8-8.0的磷酸盐缓冲液；
2)浓缩：将滤液进行旋转蒸发，转速80rpm，浓缩至溶剂剩余量10％；
3)发酵：向浓缩液中接种复合生物酶进行发酵，发酵温度30℃，湿度50％， 发酵时间8h；
所述复合生物酶，其组成包括纤维素酶、蛋白酶和果胶酶，纤维素酶、蛋白酶和果胶酶的质量比为3.3：1：0.4；
4)后处理：发酵后得到的浆料进行抽滤，喷雾干燥，即可制得海藻提取物粉料。
2、含海藻提取物的功能改性剂的制备
1)前处理
将蒙脱土加入到氯化四丁基溴化铵、硫酸溶液中进行活化处理，密封加热搅拌，后过滤，保留滤饼；将海藻提取物粉末加入到5倍去离子水中，加入促进剂硫代二丙酸二月桂酯，搅拌均匀后，在20HZ频率下超声8min，得到海藻提取物溶液；
所述氯化四丁基溴化铵与硫酸的质量比为1：20；
硫代二丙酸二月桂酯的用量是溶液总量的2.5wt％
2)超声浸渍
将活化处理的蒙脱土浸渍到海藻提取物溶液中，在超声功率为280HZ的条件下浸渍超声处理1.2h；
3)絮凝沉淀
超声结束，加入液碱调节溶液pH至8.5，加入聚丙烯酰胺，精制、分层、过滤，干燥，得到含海藻提取物的功能改性剂固体；
所述聚丙烯酰胺的浓度为1.2g/L。
3、聚酯功能性颗粒的制备
将PET切片与含海藻提取物的功能改性剂及其它原材料投入混合搅拌机中进行混合制粒，混合转速为500r/min，搅拌3-h，得到聚酯功能性颗粒；
按重量份数计，原材料组成包括：40份PET切片、25份含海藻提取物的功 能改性剂、5份羧甲基纤维素钠、15份硬脂酸锌和15份十二碳醇；
4、混炼
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，并加入防静电剂，采用双螺杆挤出机进行熔融高速混炼，温度为300℃，混合熔体含水量0.02wt％；
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2.5wt％。
5、纺丝成型
将纺丝液导入纺丝箱，纤维从喷丝板的孔中喷出，经熔融纺丝方法制得本发明的含有海藻提取物的涤纶长纤维；
所述熔融纺丝，熔融纺丝的挤出温度250℃，侧吹风冷却风温25℃，侧吹风风速为0.5m/s，卷绕纺丝速度3650m/min，三次牵伸比依此为1:0.8；1:1.0；1:1.2。
采用实施例1的技术方案制备海藻涤纶长纤维，海藻中有效成分提取率达到74.5％，利用率大大提高；制得的海藻涤纶长纤维，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％，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90.5％，且经过60次标准洗涤后，抑菌率仍在84.6％，抑菌持久性好；同时该纤维还具有良好的亲水性和吸湿性，滴水扩散时间为0.27s；该涤纶长纤维的单丝纤度0.33dpf，纤维的干断裂强度达到6.51cN/dtex，湿断裂强度为5.20cN/dtex，断裂伸长率33.6％，综合性能十分优异。
实施例2一种海藻涤纶长纤维及其制备方法
2、海藻提取物的制备
1)抽提：将海藻洗净、晒干，后在研磨成粒径2-3mm的细粉，采用索氏提 取器加入抽提液进行抽提，温度78℃，抽提时间28h；，
所述抽提液，是将磷酸氢二钾与磷酸二氢钾溶解于乙醇中制得的pH为8.0-8.2的磷酸盐缓冲液；
2)浓缩：将滤液进行旋转蒸发，转速100rpm，浓缩至溶剂剩余量10％；
3)发酵：向浓缩液中接种复合生物酶进行发酵，发酵温度35℃，湿度55％，发酵时间8h；
所述复合生物酶，其组成包括纤维素酶、蛋白酶和果胶酶，纤维素酶、蛋白酶和果胶酶的质量比为4：1：0.5；
4)后处理：发酵后得到的浆料进行抽滤，喷雾干燥，即可制得海藻提取物粉料。
2、含海藻提取物的功能改性剂的制备
1)前处理
将蒙脱土加入到氯化四丁基溴化铵、硫酸溶液中进行活化处理，密封加热搅拌，后过滤，保留滤饼；将海藻提取物粉末加入到5倍去离子水中，加入促进剂硫代二丙酸二月桂酯，搅拌均匀后，在20HZ频率下超声10min，得到海藻提取物溶液；
所述氯化四丁基溴化铵与硫酸的质量比为1：20；
硫代二丙酸二月桂酯的用量是溶液总量3.0wt％
2)超声浸渍
将活化处理的蒙脱土浸渍到海藻提取物溶液中，在超声功率为300HZ的条件下浸渍超声处理1.2h；
3)絮凝沉淀
超声结束，加入液碱调节溶液pH至9.8，加入聚丙烯酰胺，精制、分层、过滤，干燥，得到含海藻提取物的功能改性剂固体；
所述聚丙烯酰胺的浓度为2.0g/L。
3、聚酯功能性颗粒的制备
将PET切片与含海藻提取物的功能改性剂及其它原材料投入混合搅拌机中进行混合制粒，混合转速为600r/min，搅拌4h，得到聚酯功能性颗粒；
按重量份数计，原材料组成包括：50份PET切片、35份含海藻提取物的功能改性剂、3份羧甲基纤维素钠、6份硬脂酸锌和6份十二碳醇；
4、混炼
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，并加入防静电剂，采用双螺杆挤出机进行熔融高速混炼，温度为310℃，混合熔体含水量0.04wt％；
所述熔融高速共混，转速为1200rad/min，混合时间90min；
所述功能性颗粒占总重量的3.5wt％；
5、纺丝成型
将纺丝液导入纺丝箱，纤维从喷丝板的孔中喷出，经熔融纺丝方法制得本发明的含有海藻提取物的涤纶长纤维；
所述熔融纺丝，熔融纺丝的挤出温度265℃，侧吹风冷却风温30℃，侧吹风风速为0.6m/s，卷绕纺丝速度3700m/min，三次牵伸比依此为1:0.8；1:1.0；1:1.2。
采用实施例2的技术方案制备海藻涤纶长纤维，海藻中有效成分提取率达到77.7％，利用率大大提高；制得的海藻涤纶长纤维，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97.5％，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91.3％，且经过60次标准洗涤后，抑菌率仍在85.2％，抑菌持久性好；同时该纤维还具有良好的亲水性和吸湿性，滴水扩散时间为0.22s；该涤纶长纤维的单丝纤度0.40dpf， 纤维的干断裂强度达到6.66cN/dtex，湿断裂强度为5.21cN/dtex，断裂伸长率32.2％，综合性能十分优异。
实施例3一种海藻涤纶长纤维及其制备方法
3、海藻提取物的制备
1)抽提：将海藻洗净、晒干，后在研磨成粒径3-4mm的细粉，采用索氏提取器加入抽提液进行抽提，温度78℃，抽提时间30h；，
所述抽提液，是将磷酸氢二钾与磷酸二氢钾溶解于乙醇中制得的pH为8.0-8.2的磷酸盐缓冲液；
2)浓缩：将滤液进行旋转蒸发，转速100rpm，浓缩至溶剂剩余量20％；
3)发酵：向浓缩液中接种复合生物酶进行发酵，发酵温度35℃，湿度52％，发酵时间10h；
所述复合生物酶，其组成包括纤维素酶、蛋白酶和果胶酶，纤维素酶、蛋白酶和果胶酶的质量比为5：1.2：0.7；
4)后处理：发酵后得到的浆料进行抽滤，喷雾干燥，即可制得海藻提取物粉料。
2、含海藻提取物的功能改性剂的制备
1)前处理
将蒙脱土加入到氯化四丁基溴化铵、硫酸溶液中进行活化处理，密封加热搅拌，后过滤，保留滤饼；将海藻提取物粉末加入到8倍去离子水中，加入促进剂硫代二丙酸二月桂酯，搅拌均匀后，在20HZ频率下超声15min，得到海藻提取物溶液；
所述氯化四丁基溴化铵与硫酸的质量比为1：23；
硫代二丙酸二月桂酯的用量是溶液总量的4wt％
2)超声浸渍
将活化处理的蒙脱土浸渍到海藻提取物溶液中，在超声功率为300HZ的条件下浸渍超声处理1.5h；
3)絮凝沉淀
超声结束，加入液碱调节溶液pH至10.5，加入聚丙烯酰胺，精制、分层、过滤，干燥，得到含海藻提取物的功能改性剂固体；
所述聚丙烯酰胺的浓度为3g/L。
3、聚酯功能性颗粒的制备
将PET切片与含海藻提取物的功能改性剂及其它原材料投入混合搅拌机中进行混合制粒，混合转速为600r/min，搅拌4h，得到聚酯功能性颗粒；
按重量份数计，原材料组成包括：50份PET切片、30份含海藻提取物的功能改性剂、5份羧甲基纤维素钠、7份硬脂酸锌和8份十二碳醇；
4、混炼
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，并加入防静电剂，采用双螺杆挤出机进行熔融高速混炼，温度为310℃，混合熔体含水量0.05wt％；
所述熔融高速共混，转速为1200rad/min，混合时间90min；
所述功能性颗粒占总重量的5wt％；
5、纺丝成型
将纺丝液导入纺丝箱，纤维从喷丝板的孔中喷出，经熔融纺丝方法制得本发明的含有海藻提取物的涤纶长纤维；
所述熔融纺丝，熔融纺丝的挤出温度265℃，侧吹风冷却风温30℃，侧吹风风速为0.6m/s，卷绕纺丝速度3850m/min，三次牵伸比依此为1:0.8；1:1.0；1:1.2。
采用实施例3的技术方案制备海藻涤纶长纤维，海藻中有效成分提取率达 到78.6％，利用率大大提高；制得的海藻涤纶长纤维，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96.6％，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91.8％，且经过60次标准洗涤后，抑菌率仍在85.7％，抑菌持久性好；同时该纤维还具有良好的亲水性和吸湿性，滴水扩散时间为0.35s；该涤纶长纤维的单丝纤度0.51dpf，纤维的干断裂强度达到6.78cN/dtex，湿断裂强度为5.27cN/dtex，断裂伸长率35.5％，综合性能十分优异。
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. 一种海藻涤纶长纤维制备方法，其特征在于，所述涤纶长纤维，海藻提取物含量为0.1-3％。
  2. 根据权利要求1所述的涤纶长纤维制备方法，其特征在于，所述制备方法，包括海藻提取物的制备、含海藻提取物的功能改性剂的制备、聚酯功能性颗粒的制备、混炼和纺丝成型步骤。
  3. 根据权利要求2所述的涤纶长纤维制备方法，其特征在于，所述混炼，功能性颗粒占总重量的2.5-5wt％。
  4. 根据权利要求3所述的涤纶长纤维制备方法，其特征在于，所述混炼，转速为1000-1200rad/min，温度为300-310℃，混合熔体含水量0.02-0.05wt％。
  5. 根据权利要求2所述的涤纶长纤维制备方法，其特征在于，所述聚酯功能性颗粒的制备，按重量份数计，原材料组成包括：40-50份PET切片、25-35份含海藻提取物的功能改性剂、3-10份羧甲基纤维素钠、6-15份硬脂酸锌和6-15份十二碳醇。
  6. 根据权利要求2所述的涤纶长纤维制备方法，其特征在于，所述海藻提取物的制备，包括抽提和发酵步骤；所述抽提，抽提液是将磷酸氢二钾与磷酸二氢钾溶解于乙醇中制得的pH为7.8-8.2的磷酸盐缓冲液。
  7. 根据权利要求6所述的涤纶长纤维制备方法，其特征在于，所述发酵，包括向浓缩液中接种复核生物酶，发酵温度30-35℃，湿度50±5％，发酵时间8-10h；所述复合生物酶，其组成包括纤维素酶、蛋白酶和果胶酶，纤维素酶、蛋白酶和果胶酶的质量比为3.3-5：1-1.2：0.4-0.7。
  8. 根据权利要求2所述的涤纶长纤维制备方法，其特征在于，所述含海藻提取物的功能改性剂的制备，包括前处理、超声浸渍和絮凝沉淀；所述前处理，氯化四丁基溴化铵与硫酸的质量比为1：20-23；硫代二丙酸二月桂酯的用量是溶液总量的2.5-4wt％。
  9. 根据权利要求7所述的涤纶长纤维制备方法，其特征在于，所述超声浸渍，超声功率280-300HZ；所述絮凝沉淀，加入液碱调节溶液pH至8.5-10.5，聚丙烯酰胺加入量为1.2-3g/L。
  10. 根据权利要求2所述的涤纶长纤维制备方法，其特征在于，所述纺丝成型，侧吹风风速为0.5-0.6m/s，卷绕纺丝速度3650-3850m/min，三次牵伸比依此为1:0.8；1:1.0；1:1.2。
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CN110863252A (zh) * 2019-11-06 2020-03-06 百事基材料（青岛）股份有限公司 一种植物功能性涤纶长丝及其制备方法
CN111118652B (zh) * 2020-03-03 2021-09-07 百事基材料（青岛）股份有限公司 一种海藻涤纶长纤维及其制备方法
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