WO2024251042A1 - 热塑弹性体发泡纤维及其制备方法和应用 - Google Patents

热塑弹性体发泡纤维及其制备方法和应用 Download PDF

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WO2024251042A1
WO2024251042A1 PCT/CN2024/096672 CN2024096672W WO2024251042A1 WO 2024251042 A1 WO2024251042 A1 WO 2024251042A1 CN 2024096672 W CN2024096672 W CN 2024096672W WO 2024251042 A1 WO2024251042 A1 WO 2024251042A1
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thermoplastic elastomer
parts
fluid
supercritical
fiber
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French (fr)
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翟文涛
王泽林
赵丹
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Big Bear Guangzhou New Materials Technology Co Ltd
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Big Bear Guangzhou New Materials Technology Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C69/00—Combinations of shaping techniques not provided for in a single one of main groups B29C39/00 - B29C67/00, e.g. associations of moulding and joining techniques; Apparatus therefore
    • 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
    • D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
    • D01D5/247—Discontinuous hollow structure or microporous structure
    • 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
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
    • D01F11/06—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
    • D01F11/08—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • 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
    • D01F6/94—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 other polycondensation products
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the invention belongs to the technical field of polymer foamed fibers and processing thereof, and in particular relates to a thermoplastic elastomer foamed fiber and a preparation method and application thereof.
  • Polymer foam fiber combines the advantages of fiber and pore structure, and has unparalleled advantages of fiber materials, such as low density, high elasticity, large specific surface area, fast mass transfer rate, etc. It has important application prospects in many emerging fields such as functional clothing, wearables, consumer electronics, filtration separation, catalysis, etc.
  • Existing methods for preparing polymer foam fiber include coagulation bath phase separation and high inward emulsion template method, which involve the use of a large amount of organic solvents and complex processing processes. The processing process is not environmentally friendly, the applicable polymer system is limited, and the processing efficiency is low, which limits its application.
  • Supercritical fluids include supercritical CO 2 fluids and supercritical N 2 fluids. They are widely available, have no residue, and are environmentally friendly. They have become the most important and most promising polymer physical foaming agents.
  • the academic paper Polymer Engineering Sciences, 2013, 53: 2360. reported the research on continuous extrusion foaming thermoplastic polyurethane fibers (TPU).
  • the research used supercritical CO 2 fluid as a physical foaming agent, injected the supercritical fluid into the extruder system, and used high-pressure TPU/CO 2 melt to rapidly release pressure and foam at the extruder die to prepare TPU foamed fibers with a diameter of 0.3 to 1.2 mm and a wide size dispersion.
  • the pressure in the extruder system is as high as 30-50MPa.
  • the molten polymer/fluid melt is sprayed out in an extremely small die head for foaming, there is a huge shear stress inside the foamed fiber and the supercritical fluid escapes quickly in the TPU melt, resulting in the prepared TPU foamed fiber having uneven diameter, density higher than 0.9g/ cm3 , and uneven pore size, which is difficult to meet actual application requirements.
  • the present invention aims to provide a thermoplastic elastomer foam fiber and a preparation method and application thereof.
  • the diameter of the thermoplastic elastomer foam fiber prepared by the present invention is between 0.3 and 1.0 mm and can be uniformly controlled, the density is low, and the pore size is uniform.
  • there is no high extrusion system pressure in the preparation method of the present invention the polymer foaming occurs in the micro-extrusion foaming process, and the nucleation and growth degree of the pores are controlled by controlling the residence time of the polymer/foaming agent in the micro-extrusion foaming process.
  • the processing process is gentle and can be achieved. Large-scale continuous production.
  • thermoplastic elastomer foam fiber comprising the following components in parts by weight: 80 to 100 parts of thermoplastic elastomer, 0 to 10 parts of nucleating agent, 0 to 1 part of chain extender, and 0 to 0.5 part of antioxidant;
  • thermoplastic elastomer has a melting point of 180-230°C and a hardness of 45-82D;
  • the thermoplastic elastomer foam fiber has an open-cell structure on the surface and a closed-cell structure inside.
  • the thermoplastic elastomer foam fiber has a diameter of 0.3-1.0 mm, an average deviation of ⁇ 0.05 mm, a density of 0.60-0.90 g/cm 3 , and an average cell size of the closed-cell structure inside of 1-100 ⁇ m.
  • thermoplastic elastomer includes one or more of TPU, polyester elastomer (TPEE), nylon elastomer (PEBA), ethylene vinyl acetate (EVA), and polyolefin elastomer.
  • TPEE polyester elastomer
  • PEBA nylon elastomer
  • EVA ethylene vinyl acetate
  • polyolefin elastomer includes one or more of TPU, polyester elastomer (TPEE), nylon elastomer (PEBA), ethylene vinyl acetate (EVA), and polyolefin elastomer.
  • the nucleating agent includes at least one of calcium carbonate, talc, mica, montmorillonite, nano-silica, carbon black and carbon nanotubes.
  • the chain extender comprises at least one of a difunctional acid derivative, an isocyanate, an anhydride and an epoxide.
  • the antioxidant includes at least one of an amine antioxidant and a phosphorus antioxidant.
  • the wire feeding unit described in the present invention is responsible for stably feeding the polymer wire treated with supercritical fluid into the micro-extrusion foaming system.
  • the wire feeding unit uses rotating gears as power.
  • the gears of the wire feeding unit need to have a good extrusion force on the polymer.
  • the gears are not easy to wear during long-term use.
  • the gears of the wire feeding unit are made of hard aluminum, stainless steel, alloy steel, etc.
  • the heat insulation unit can prevent the heat of the heating unit from being transferred to the wire feeding unit, so that the wire material becomes significantly softer and affects the stability of wire feeding.
  • the temperature after cooling by the heat insulation unit is not greater than the softening temperature of the polymer wire material or the impregnated polymer wire material.
  • the wire feeding unit is provided with an aluminum part with a groove structure and an active cooling device with a fan.
  • the micro-extrusion heating unit can quickly heat the polymer filaments, so that the polymer system transitions from a glassy state to a highly elastic state and a viscous flow state, and cell nucleation and rapid cell growth occur.
  • the present invention also claims a method for preparing the thermoplastic elastomer foamed fiber, comprising the following steps:
  • thermoplastic elastomer wire impregnating the thermoplastic elastomer wire with a supercritical fluid, and after the impregnation is completed, taking out the polymer wire and subjecting it to low-temperature air-locking treatment to obtain an impregnated thermoplastic elastomer wire;
  • thermoplastic elastomer filament is heated and foamed, shaped in a channel, and stretched at a constant speed to obtain thermoplastic elastomer foamed fibers.
  • the melt extrusion adopts a twin-screw extruder, and the temperature of the melt extrusion is 100-250° C.
  • the temperature from the feed port to the extruder head of the extruder is set to 100/190/200/215/220/190-200° C.
  • step S1 all the components are dried by hot air after being premixed, and the moisture content of the materials after drying is less than 0.05%.
  • the diameter of the thermoplastic elastomer filament is 1.65-1.80 mm.
  • the supercritical fluid is supercritical CO2 fluid, supercritical N2 fluid or a mixed fluid of supercritical CO2 fluid and supercritical N2 fluid.
  • the solubility of the supercritical fluid in the thermoplastic elastomer filament is 0.5-7.0 wt. %. More preferably, the solubility of the supercritical fluid in the thermoplastic elastomer filament is 1.0-6.0 wt. %.
  • the temperature of the low-temperature gas lock is -18 to 0°C, and during the low-temperature gas lock treatment, the weight loss rate of the supercritical fluid is not higher than 20%.
  • the hardness of the impregnated thermoplastic elastomer filament is not less than Shore 40D.
  • the wire feeding speed of heating and foaming the impregnated thermoplastic elastomer wire is 50 to 100 mm/s, more preferably 70 to 100 mm/s.
  • the temperature of the heating and foaming is 170-260°C, and the residence time is 0.3-3.0s. More preferably, the temperature of the heating and foaming is 180-250°C, and the residence time is 0.5-2.0s.
  • the tunnel shaping in the present invention is used to keep the melt-foamed fibers warm to a certain extent, so that the foamed fibers are in a high elastic range, and through stretching, the foamed fibers have the ability of plastic deformation, thereby increasing the elasticity of the foamed fibers.
  • the temperature of the tunnel shaping is 80-140° C.
  • the residence time in the tunnel is 0.5-5 s.
  • the temperature of the tunnel shaping is 90-130° C.
  • the residence time in the tunnel is 1-4 s.
  • step S3 the speed of the constant speed stretching is 3-5 m/min.
  • the present invention also seeks to protect an application of the thermoplastic elastomer foamed fiber in the fields of catalysis, functional clothing, electronic wearable devices, and filtration separation.
  • the present invention has the following beneficial effects:
  • thermoplastic elastomer supercritical fluid micro-extruded foamed fiber of the present invention can be prepared continuously for a long time, and the surface opening and the inner
  • the foam has the advantages of uniform thickness, excellent elastic tensile properties, low density, wear resistance, weavability, dense pore distribution, simple and easy preparation process, low cost, and green environmental protection.
  • thermoplastic elastomer micro-extrusion foaming system of the present invention there is no high extrusion system pressure.
  • Polymer foaming occurs in the micro-extrusion foaming process, and the nucleation and growth degree of the pores are controlled by controlling the residence time of the polymer in the micro-extrusion foaming process, so that the pore structure of the foamed fiber is uniform, the thickness of the foamed fiber is uniform, and the diameter of the foamed fiber is uniform and controllable, thereby improving the production stability of the micro-extruded foamed fiber.
  • the processing process of the present invention is mild and can achieve large-scale continuous production.
  • FIG. 1 is a schematic diagram of a processing device for thermoplastic elastomer foamed fibers according to the present invention.
  • FIG. 2 is a product schematic diagram of the thermoplastic elastomer foamed fiber of the present invention.
  • FIG. 3 is a SEM photograph of the thermoplastic elastomer foamed fiber prepared in Example 3 of the present invention.
  • FIG. 4 is a SEM photograph of the thermoplastic elastomer foamed fiber prepared in Comparative Example 2 of the present invention.
  • Thermoplastic elastomer A (TPU):
  • A1 45D, melting point 210°C, brand 58134, Lubrizol, USA.
  • A2 60D, melting point 210°C, brand 58863, Lubrizol, USA.
  • A3 80D, melting point 210°C, brand 59600, Lubrizol, USA.
  • A4 60D, melting point 230°C, brand 260, Bayer, Germany.
  • A5 40D, melting point 190°C, brand B90A11U, BASF, Germany.
  • A6 60D, melting point 240°C, brand S60D, BASF, Germany.
  • thermoplastic Elastomer B (TPEE):
  • Thermoplastic Elastomer C (PEBA):
  • Calcium carbonate with an average particle size of 1 ⁇ m, is commercially available.
  • Talc powder with an average particle size of 1 ⁇ m, is commercially available.
  • Nano-silicon dioxide with an average particle size of 200 nm, is commercially available.
  • Carbon black with an average particle size of 3 ⁇ m, is commercially available.
  • Epoxy chain extender commercially available.
  • Hindered phenolic antioxidant commercially available.
  • thermoplastic elastomer foamed fibers of Examples 1 to 14 and Comparative Examples 1 to 2 are shown in Table 1.
  • thermoplastic elastomer foamed fiber of Examples 1 to 14 and Comparative Examples 1 to 2 comprises the following steps:
  • thermoplastic elastomer filament All components are premixed, added into a twin-screw extruder, melt-extruded, dried, and rolled to obtain a thermoplastic elastomer filament; wherein all components are dried by hot air after premixing, and the moisture content after drying is less than 0.05%, and the temperature from the feed port to the extruder head is set to 100/190/200/215/220/195°C, and the diameter of the rolled filament is 1.65-1.80mm;
  • thermoplastic elastomer filament Place the thermoplastic elastomer filament in a high-pressure device and immerse it in a supercritical fluid (supercritical CO2 fluid). After the immersion is completed, take out the polymer filament and perform low-temperature gas-locking treatment to obtain an impregnated thermoplastic elastomer filament; wherein the solubility of the supercritical fluid in the thermoplastic elastomer filament is 0.5 to 7.0 wt.%, the temperature of the low-temperature gas-locking is -18 to 0°C, and during the low-temperature gas-locking treatment, the weight loss rate of the supercritical fluid is not higher than 20%.
  • supercritical fluid supercritical CO2 fluid
  • the impregnated thermoplastic elastomer filament is loaded onto the unwinding wheel of a micro-extrusion foaming device, and is rapidly heated and foamed by the micro-extrusion device, shaped in a tunnel, and stretched at a constant speed to obtain a thermoplastic elastomer foamed fiber; wherein the hardness of the impregnated thermoplastic elastomer filament is not less than Shaw 40D, the temperature for heating and foaming is 170-260°C, the temperature for tunnel shaping is 80-140°C, the residence time in the tunnel is 0.5-5s, and the speed of constant stretching is 5m/min.
  • Example 3 Compared with Example 3, the only difference of this comparative example is that the temperature of the tunnel heating is 150°C.
  • thermoplastic elastomer foamed fiber finally obtained in this comparative example has a diameter of 0.4 mm and a density of 1.15 g/cm 3 .
  • the cells disappear, and the fiber has poor elasticity and is easily broken when rolled up.
  • thermoplastic elastomer filament obtained in step S1 does not go through step S2, but is directly extruded to obtain unfoamed thermoplastic elastomer fibers, and then the fibers are immersed in a supercritical fluid under the same conditions, and then the fibers are heated and foamed using an oil bath commonly used in the industry.
  • the diameter of the thermoplastic elastomer foamed fiber prepared in this comparative example is 0.4 mm, and the density is 1.20 g/cm 3 . Since the fiber is very thin, the supercritical fluid escapes from the fiber quickly, and there are no bubbles.
  • the diameter of the thermoplastic elastomer foamed fiber prepared in the embodiment of the present invention is between 0.3 and 1.0 mm and can be evenly controlled, the density is low and can be maintained in the range of 0.60 to 0.90 g/ cm3 , the pore size is uniform, the pore distribution is dense, and long-term continuous preparation can be achieved.

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  • Chemical & Material Sciences (AREA)
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Abstract

一种热塑弹性体发泡纤维及其制备方法和应用。所述热塑弹性体发泡纤维，包括以下重量份计的组分：热塑性弹性体80~100份、成核剂0~10份、扩链剂0~1份、抗氧剂0~0.5份；所述热塑性弹性体的熔点为180~230°C，硬度为45-82D；所述热塑性弹性体发泡纤维的表面存在开孔结构、内部为闭孔结构，所述热塑性弹性体发泡纤维的直径为0.3~1.0mm，平均偏差为±0.05mm，密度为0.60~0.90g/cm 3，内部闭孔结构的平均泡孔尺寸为1~100μm。制得的热塑弹性体发泡纤维的直径均匀、密度低、泡孔尺寸均匀。

Description

热塑弹性体发泡纤维及其制备方法和应用 技术领域
本发明属于聚合物发泡纤维及其加工技术领域，具体涉及一种热塑弹性体发泡纤维及其制备方法和应用。
背景技术
聚合物发泡纤维结合了纤维和泡孔结构的优点，具有纤维材料无与伦比的优势，例如，低密度、高弹性、比表面积大、传质速率快等特性，在功能服装、可穿戴、消费电子、过滤分离、催化等众多新兴领域具有重要的应用前景。现有制备聚合物发泡纤维的方法包括凝固浴相分离和高内向乳液模板法等，涉及使用大量有机溶剂和复杂的处理过程，加工过程不环保、适用聚合物体系有限、加工效率低，限制了其应用。
超临界流体包括超临界CO2流体、超临界N2流体，它来源广泛、无残留、环境友好，已经成为一类最重要的、最有发展前景的聚合物物理发泡剂。学术论文Polymer Engineering Sciences,2013,53:2360.报道了连续挤出发泡热塑性聚氨酯纤维(TPU)的研究，该研究以超临界CO2流体为物理发泡剂，通过超临界流体注入到挤出机系统中，采用高压TPU/CO2熔体在挤出机口模处快速泄压发泡，制备了直径为0.3～1.2mm的、宽尺寸分散度的TPU发泡纤维。不过，超临界流体挤出发泡过程中挤出机系统中的压力高达30-50MPa，处于熔融状态的聚合物/流体熔体在极细小的模头中喷出发泡时，发泡纤维内部存在极大的剪切应力且超临界流体在TPU熔体中快速逃逸，导致所制备的TPU发泡纤维存在直径不均匀、密度高于0.9g/cm3、泡孔尺寸不均匀的问题，难以满足实际的应用需求。
发明内容
本发明旨在提供一种热塑弹性体发泡纤维及其制备方法和应用。本发明制得的热塑弹性体发泡纤维的直径在0.3～1.0mm之间且可以均匀控制、密度低、泡孔尺寸均匀。同时本发明的制备方法中不存在高的挤出系统压力，聚合物发泡发生在微挤出发泡过程中，并通过控制微挤出发泡过程中聚合物/发泡剂的停留时间来控制泡孔的成核和增长程度，加工过程温和，可实现 大规模连续生产。
为了达到上述目的，本发明采用以下技术方案：一种热塑弹性体发泡纤维，包括以下重量份计的组分：热塑性弹性体80～100份、成核剂0～10份、扩链剂0～1份、抗氧剂0～0.5份；
所述热塑性弹性体的熔点为180～230℃，硬度为45-82D；
所述热塑性弹性体发泡纤维的表面存在开孔结构、内部为闭孔结构，所述热塑性弹性体发泡纤维的直径为0.3～1.0mm，平均偏差为±0.05mm，密度为0.60～0.90g/cm3，内部闭孔结构的平均泡孔尺寸为1～100μm。
优选地，所述热塑弹性体发泡纤维，包括以下重量份计的组分：热塑性弹性体90～95份、成核剂1～3份、扩链剂0.2～0.5份、抗氧剂0.2～0.3份。
优选地，所述热塑性弹性体包括TPU、聚酯弹性体(TPEE)、尼龙弹性体(PEBA)、乙烯醋酸乙烯酯(EVA)、聚烯烃弹性体中的一种或者多种。
优选地，所述成核剂包括碳酸钙、滑石粉、云母、蒙脱土、纳米二氧化硅、炭黑、碳纳米管中的至少一种。
优选地，所述扩链剂包括双官能团酸衍生物、异氰酸酯、酸酐和环氧化物中的至少一种。
优选地，所述抗氧剂包括胺类抗氧剂、磷类抗氧剂中的至少一种。
优选地，所述成核剂的粒径为0.05～5μm。
本发明还请求保护一种所述热塑弹性体发泡纤维的加工设备，依次包括送丝单元、绝热单元、微挤出加热单元、微挤出口模、加热甬道和牵伸单元。
本发明中所述送丝单元负责把经过超临界流体处理后的聚合物丝材稳定地送入微挤出发泡体系，送丝单元采用转动的齿轮为动力。送丝单元的齿轮需对聚合物有很好的挤压力。齿轮在长期使用过程中不易磨损，优选地，送丝单元的齿轮为硬质铝材质、不锈钢材质、合金钢材质等。
所述绝热单元可防止加热单元的热量传导到送丝单元，使丝材显著变软影响送丝的稳定性。经绝热单元冷却后的温度不大于聚合物丝材或者浸渍聚合物丝材的软化温度。优选地，送丝单元处带有沟槽结构的铝制件和带有风扇的主动冷却装置。
所述微挤出加热单元可以快速加热聚合物丝材，使其聚合物体系从玻璃态过渡到高弹态以及粘流态，发生泡孔成核和快速的泡孔增长。
本发明还请求保护一种所述热塑弹性体发泡纤维的制备方法，包括以下步骤：
S1、将所有组分经预混，熔融挤出、干燥、收卷，得到热塑弹性体丝材；
S2、将热塑弹性丝材浸渍超临界流体，浸渍完成后，取出聚合物丝材、低温锁气处理，得到浸渍的热塑弹性体丝材；
S3、微挤出发泡：将浸渍的热塑弹性体丝材进行加热升温发泡、甬道定型、定速牵伸，得到热塑弹性体发泡纤维。
优选地，步骤S1中，所述熔融挤出采用双螺杆挤出机，所述熔融挤出的温度为100～250℃。从加料口到挤出机挤出头的温度设置为100/190/200/215/220/190～200℃。
优选地，步骤S1中，所述所有组分经预混后需经热空气干燥，干燥后所用物料的水分含量低于0.05％。
优选地，步骤S1中，所述热塑弹性体丝材的直径为1.65～1.80mm。
优选地，步骤S2中，所述超临界流体为超临界CO2流体、超临界N2流体或超临界CO2流体与超临界N2流体的混合流体。
优选地，步骤S2中，所述超临界流体在热塑弹性体丝材中的溶解度为0.5～7.0wt.％。更优选地，所述超临界流体在热塑弹性体丝材中的溶解度为1.0～6.0wt.％。
优选地，步骤S2中，所述低温锁气的温度为-18～0℃，在低温锁气处理过程中，超临界流体的重量失重率不高于20％。
优选地，步骤S3中，所述浸渍的热塑弹性体丝材的硬度不低于邵氏40D。
优选地，步骤S3中，所述将浸渍的热塑弹性体丝材进行加热升温发泡的送丝速度为50～100mm/s。更优选为70～100mm/s。
优选地，步骤S3中，所述加热升温发泡的温度为170～260℃，停留时间为0.3～3.0s。更优选地，所述加热升温发泡的温度为180～250℃，停留时间为0.5～2.0s。
本发明中所述甬道定型用于对熔体发泡的纤维进行一定程度的保温，使发泡纤维处于高弹性的范围内，并通过牵伸使发泡纤维具有可塑变形的能力，增加发泡纤维的弹性。
优选地，步骤S3中，所述甬道定型的温度为80～140℃，在甬道中的停留时间为0.5～5s。
更优选地，所述甬道定型的温度为90～130℃，在甬道中的停留时间为1～4s。
优选地，步骤S3中，所述定速牵伸的速度为3～5m/min。
本发明还请求保护一种所述热塑弹性体发泡纤维在催化、功能性服装、电子可穿戴设备、过滤分离领域中的应用。
与现有技术相比，本发明具有以下有益效果：
(1)本发明的热塑弹性体超临界流体微挤出发泡纤维可持续长时间制备，表面开孔、内 部闭孔，其具有粗细均匀、弹性拉伸性能优异、密度低、耐磨损、可编织、泡孔分布密集、制备过程简单易行、成本低、绿色环保等优点。
(2)本发明的热塑弹性体微挤出发泡系统中不存在高的挤出系统压力，聚合物发泡发生在微挤出发泡过程中，并通过控制微挤出发泡过程中聚合物的停留时间来控制泡孔的成核和增长程度，使发泡纤维的泡孔结构均匀、发泡纤维的粗细均匀、发泡纤维的直径均匀可控，进而提高微挤出发泡纤维的生产稳定性，本发明的加工过程温和，可实现大规模连续生产。
附图说明
图1为本发明热塑弹性体发泡纤维的加工设备示意图。
图2为本发明热塑弹性体发泡纤维的产品示意图。
图3为本发明实施例3制得的热塑弹性体发泡纤维的SEM照片。
图4为本发明对比例2制得的热塑弹性体发泡纤维的SEM照片。
具体实施方式
下面将结合本发明实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例、对比例中，所使用的实验方法如无特殊说明，均为常规方法，所用的材料、试剂等，如无特殊说明，均可从商业途径得到。
实施例和对比例中使用的材料如下(涉及硬度的部分均指邵氏硬度)：
热塑弹性体A(TPU)：
A1：45D，熔点为210℃，牌号58134，美国路博润。
A2：60D，熔点为210℃，牌号58863，美国路博润。
A3：80D，熔点为210℃，牌号59600，美国路博润。
A4：60D，熔点为230℃，牌号260，德国拜耳。
A5：40D，熔点为190℃，牌号B90A11U，德国巴斯夫。
A6：60D，熔点为240℃，牌号S60D，德国巴斯夫。
热塑弹性体B(TPEE)：
60D，熔点210℃，牌号7246，美国杜邦。
热塑弹性体C(PEBA)：
60D，熔点200℃，牌号7033，法国阿科玛。
热塑弹性体D(EVA)：
45D，熔点190℃，型号750，日本东曹。
成核剂：
碳酸钙，平均粒径为1μm，市售。
滑石粉，平均粒径为1μm，市售。
纳米二氧化硅，平均粒径为200nm，市售。
炭黑，平均粒径为3μm，市售。
扩链剂：
环氧类扩链剂，市售。
抗氧剂：
受阻酚类抗氧剂，市售。
实施例1～14和对比例1～4
实施例1～14和对比例1～2的热塑弹性体发泡纤维，组分及重量份如表1所示。
实施例1～14和对比例1～2的热塑弹性体发泡纤维的制备方法，包括以下步骤：
S1、将所有组分经预混，加入双螺杆挤出机，熔融挤出、干燥、收卷，得到热塑弹性体丝材；其中所有组分经预混后需经热空气干燥，干燥后的水分含量低于0.05％，从加料口到挤出机挤出头的温度设置为100/190/200/215/220/195℃，收卷丝材的直径为1.65～1.80mm；
S2、将热塑弹性丝材置入高压装置中浸渍超临界流体(超临界CO2流体)，浸渍完成后，取出聚合物丝材、低温锁气处理，得到浸渍的热塑弹性体丝材；其中，超临界流体在热塑弹性体丝材中的溶解度为0.5～7.0wt.％，低温锁气的温度为-18～0℃，在低温锁气处理过程中，超临界流体的重量失重率不高于20％。
S3、将浸渍的热塑弹性体丝材装到微挤出发泡设备的放卷轮上，经微挤出设备快速加热升温发泡、甬道定型、定速牵伸，得到热塑弹性体发泡纤维；其中，浸渍后的热塑弹性体丝材的硬度不低于邵氏40D，加热升温发泡的温度为170～260℃，甬道定型的温度为80～140℃，在甬道中的停留时间为0.5～5s，定速牵伸的速度为5m/min。
表1实施例中组分用量(重量份)



对比例3
与实施例3相比，本对比例的区别仅在于，甬道加热的温度为150℃。
配方组分以及其他条件参数以及制备方法同实施例3。
本对比例最终制得的热塑弹性体发泡纤维的直径为0.4mm，密度为1.15g/cm3，泡孔消失，且纤维弹性差，收卷时易断。
对比例4
与实施例3相比，本对比例的区别在于，步骤S1制得的热塑性弹性体丝材不经过步骤S2，而是直接进行挤出得到未发泡的热塑弹性体纤维，然后将纤维在同条件下浸渍超临界流体，再将纤维采用行业内常用的油浴升温发泡。
配方组分同实施例3。
本对比例制备的热塑弹性体发泡纤维的直径为0.4mm，密度为1.20g/cm3，由于纤维很细，超临界流体很快从纤维中逃逸，无泡孔。
从表1中的数据可以得知，本发明实施例制得的热塑弹性体发泡纤维的直径在0.3～1.0mm之间且可以均匀控制、密度低，可以保持在0.60～0.90g/cm3的范围内、泡孔尺寸均匀、泡孔分布密集、且可实现长时间连续制备。
上述实施例仅例示性说明本发明的原理及其功效，而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下，对上述实施例进行修饰或改变。因此，举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变，仍应由本发明的权利要求所涵盖。

Claims (9)

  1. 一种热塑弹性体发泡纤维，其特征在于，包括以下重量份计的组分：热塑性弹性体80～100份、成核剂0～10份、扩链剂0～1份、抗氧剂0～0.5份；
    所述热塑性弹性体的熔点为180～230℃，硬度为45-82D；
    所述热塑性弹性体发泡纤维的表面存在开孔结构、内部为闭孔结构，所述热塑性弹性体发泡纤维的直径为0.3～1.0mm，平均偏差为±0.05mm，密度为0.60～0.90g/cm3，内部闭孔结构的平均泡孔尺寸为1～100μm。
  2. 如权利要求1所述热塑弹性体发泡纤维，其特征在于，包括以下重量份计的组分：热塑性弹性体90～95份、成核剂1～3份、扩链剂0.2～0.5份、抗氧剂0.2～0.3份。
  3. 如权利要求1所述热塑弹性体发泡纤维，其特征在于，至少包括以下(1)～(5)中的一项：
    (1)所述热塑性弹性体包括TPU、聚酯弹性体、尼龙弹性体、乙烯醋酸乙烯酯、聚烯烃弹性体中的一种或者多种；
    (2)所述成核剂包括碳酸钙、滑石粉、云母、蒙脱土、纳米二氧化硅、炭黑、碳纳米管中的至少一种；
    (3)所述扩链剂包括双官能团酸衍生物、异氰酸酯、酸酐和环氧化物中的至少一种；
    (4)所述抗氧剂包括胺类抗氧剂、磷类抗氧剂中的至少一种；
    (5)所述成核剂的粒径为0.05～5μm。
  4. 一种如权利要求1～3任一所述热塑弹性体发泡纤维的加工设备，其特征在于，依次包括送丝单元、绝热单元、微挤出加热单元、微挤出口模、加热甬道和牵伸单元。
  5. 一种如权利要求1～3任一所述热塑弹性体发泡纤维的制备方法，其特征在于，包括以下步骤：
    S1、将所有组分经预混，熔融挤出、干燥、收卷，得到热塑弹性体丝材；
    S2、将热塑弹性丝材浸渍超临界流体，浸渍完成后，取出聚合物丝材、低温锁气处理，得到浸渍的热塑弹性体丝材；
    S3、将浸渍的热塑弹性体丝材进行加热升温发泡、甬道定型、定速牵伸，得到热塑弹性体发泡纤维。
  6. 如权利要求5所述热塑弹性体发泡纤维的制备方法，其特征在于，至少包括以下(1)～(3)中的一项：
    (1)步骤S1中，所述熔融挤出采用双螺杆挤出机，所述熔融挤出的温度为100～250℃；
    (2)步骤S1中，所述所有组分经预混后需经热空气干燥，干燥后的水分含量低于0.05％；
    (3)步骤S1中，所述热塑弹性体丝材的直径为1.65～1.80mm。
  7. 如权利要求5所述热塑弹性体发泡纤维的制备方法，其特征在于，至少包括以下(1)～(3)中的一项：
    (1)步骤S2中，所述超临界流体为超临界CO2流体、超临界N2流体或超临界CO2流体与超临界N2流体的混合流体；
    (2)步骤S2中，所述超临界流体在热塑弹性体丝材中的溶解度为0.5～7.0wt.％；
    (3)步骤S2中，所述低温锁气的温度为-18～0℃，在低温锁气处理过程中，超临界流体的重量失重率不高于20％。
  8. 如权利要求5所述热塑弹性体发泡纤维的制备方法，其特征在于，至少包括以下(1)～(5)中的一项：
    (1)步骤S3中，所述浸渍的热塑弹性体丝材的硬度不低于邵氏40D；
    (2)步骤S3中，所述将浸渍的热塑弹性体丝材进行加热升温发泡的送丝速度为50～100mm/s；
    (3)步骤S3中，所述加热升温发泡的温度为170～260℃，加热升温发泡的停留时间为0.3～3.0s；
    (4)步骤S3中，所述甬道定型的温度为80～140℃，在甬道中的停留时间为0.5～5s；
    (5)步骤S3中，所述定速牵伸的速度为3～5m/min。
  9. 一种如权利要求1～3任一所述热塑弹性体发泡纤维在催化、功能性服装、电子可穿戴设备、过滤分离领域中的应用。
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