WO2014166420A1 - 一种聚合物/填料/金属复合纤维及其制备方法 - Google Patents

一种聚合物/填料/金属复合纤维及其制备方法 Download PDF

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Publication number
WO2014166420A1
WO2014166420A1 PCT/CN2014/075168 CN2014075168W WO2014166420A1 WO 2014166420 A1 WO2014166420 A1 WO 2014166420A1 CN 2014075168 W CN2014075168 W CN 2014075168W WO 2014166420 A1 WO2014166420 A1 WO 2014166420A1
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Prior art keywords
metal
polymer
filler
composite fiber
alloy
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PCT/CN2014/075168
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English (en)
French (fr)
Inventor
乔金樑
朱燚磊
张晓红
王良诗
蔡传伦
戚桂村
张红彬
宋志海
赖金梅
李秉海
王亚
王湘
高建明
陈刚
蒋海斌
Original Assignee
中国石油化工股份有限公司
中国石油化工股份有限公司北京化工研究院
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Priority claimed from CN201310128099.9A external-priority patent/CN104099682B/zh
Priority claimed from CN201310127994.9A external-priority patent/CN104099681B/zh
Priority claimed from CN201310128266.XA external-priority patent/CN104099684B/zh
Priority claimed from CN201310127922.4A external-priority patent/CN104099680B/zh
Priority claimed from CN201310128100.8A external-priority patent/CN104099683B/zh
Application filed by 中国石油化工股份有限公司, 中国石油化工股份有限公司北京化工研究院 filed Critical 中国石油化工股份有限公司
Priority to CA2909301A priority Critical patent/CA2909301C/en
Priority to EP14782688.7A priority patent/EP2985370B1/en
Priority to US14/783,813 priority patent/US10787754B2/en
Priority to JP2016506774A priority patent/JP6434492B2/ja
Priority to KR1020157031983A priority patent/KR101917257B1/ko
Publication of WO2014166420A1 publication Critical patent/WO2014166420A1/zh

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Classifications

    • 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
    • D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
    • 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
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • 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
    • D01F8/06—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin 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
    • D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide 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
    • D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2101/00—Inorganic fibres
    • D10B2101/20—Metallic fibres

Definitions

  • This invention relates to the field of synthetic fibers. Further, the present invention relates to a polymer/filler/metal composite fiber and a process for its preparation, and to a corresponding polymer/filler/metal blend. Background technique
  • synthetic fibers are characterized by low price, low density and low moisture absorption rate. They are widely used in textile and garment, woven bags and other fields for daily production and life.
  • synthetic fibers have good electrical insulation properties, high electrical resistivity, and are prone to static electricity during use, which can cause harm to industrial production and people's lives.
  • static electricity and electrostatic adsorption of dust are one of the direct causes of modern electronic equipment failure, short circuit, loss of signal, bit error, and low yield.
  • static electricity and electrostatic adsorption of dust are one of the direct causes of modern electronic equipment failure, short circuit, loss of signal, bit error, and low yield.
  • In the petroleum, chemical, precision machinery, coal, food, pharmaceutical and other industries there are special requirements for the protection of static electricity. Therefore, it has become an urgent issue to develop fibers having superior electrical properties to reduce the harm caused by static electricity.
  • the carbon nanotubes are nano-scale tubular structures like a coiled graphite composed of a carbon six-membered ring.
  • Carbon nanotubes are widely used in the field of polymer-based composites or composite fibers because of their excellent electrical and mechanical properties.
  • the carbon nanotubes due to the high surface energy of the nanoparticles themselves, the carbon nanotubes have a severe agglomeration effect, thereby increasing the loading amount and cost of the nanoparticles.
  • the production of a large amount of nanoparticle fillers has also made it difficult. How to reduce the amount of carbon nanotubes and reduce production difficulties is an urgent problem to be solved.
  • Patent CN102409421A discloses a preparation method for preparing polypropylene/nano-tin dioxide/carbon nanotube composite fiber. Although the technique reduces the electrical resistivity of the composite fiber, the third component added is also a nanoparticle, which increases the difficulty of processing the raw material, the surface of the fiber is rough, the hand feel is poor, the mechanical properties are degraded, and the yarn is easily broken during production.
  • Patent CN102021671A discloses a polymer/low melting point metal composite wire and a method of manufacturing the same
  • a patent CN102140707A discloses a sheath-core composite electromagnetic shielding fiber and a preparation method thereof.
  • the above two techniques utilize a sheath-core composite technique to prepare a polymer coated low melting point metal wire or fiber.
  • this technology requires a special composite spinning machine, and as the core of the fiber, the specific gravity of the metal is increased, although the lower resistivity of the fiber is ensured, a large amount of metal is required, which increases the production cost. Summary of the invention
  • Another object of the present invention is to provide a method for preparing the above polymer/filler/metal composite fiber, which comprises preparing a polymer/filler/metal composite fiber by in-situ method, that is, as a dispersed phase in the preparation of polymer fibers.
  • a method for preparing a melting point metal by stretching metal particles to form metal short fibers Due to the presence of the filler in the system, the viscosity of the system increases greatly during the blending process. Under the same shear rate, the system undergoes greater shearing action, thereby dispersing the low melting point metal in the matrix of the polymer material.
  • the smaller the diameter also reduces the probability of recombination of metal particles after collision, making the particle size of the metal particles smaller, the number of metal particles larger, and the distance between the metal particles smaller, so in the metal particles
  • the diameter of the short fibers is made smaller, and the distance between the short fibers is shorter; in addition, in the case of a conductive filler (for example, carbon nanotubes), the conductive filler dispersed between the metal fibers also functions as a connection;
  • the method of the present invention is implemented on existing conventional fiber production equipment, thereby making the preparation method have good applicability and low equipment cost.
  • a polymer/filler/metal composite fiber of the present invention comprising a polymer fiber comprising a filler and a metal short fiber, the microstructure of which is a metal short fiber distributed as a dispersed phase in a polymer fiber, and a metal as a dispersed phase is short
  • the fibers are distributed parallel along the axis of the polymer fibers; the filler is dispersed within the polymer fibers and distributed between the metal staple fibers.
  • the filler Due to the presence of the filler, the diameter of the short fibers is smaller, and the distance between the short fibers is shorter; in addition, in the case of a conductive filler (for example, carbon nanotubes), the presence of the conductive filler also serves to join the short fibers of the metal, and It is easy to form a conductive network; the antistatic property of the prepared composite fiber is improved, and the fiber is maintained in a good hand.
  • a conductive filler for example, carbon nanotubes
  • the "parallel distribution" means that the short metal fibers are oriented in parallel along the direction of the polymer fiber axis, but there may be less due to the preparation process of the composite fiber (for example, a stretching process).
  • the orientation of the partial metal short fibers is at an angle to the direction of the polymer fiber axis, and the "parallel distribution" described in the present invention also includes such a case.
  • the polymer of the polymer fiber is a thermoplastic resin, preferably a thermoplastic resin having a melting point of 90 to 450 ° C, more preferably a melting point of 100 to 290 ° C.
  • Thermoplastic resin Most preferably selected from the group consisting of polyethylene, polypropylene, polyamide or polyester.
  • the polyamides described therein include any of the types of spinnable polyamides of the prior art, preferably nylon 6, nylon 66, nylon 11 or nylon 12.
  • the polyester may be any spinnable polyester of the prior art, preferably polyethylene terephthalate (PET) or poly(trimethylene terephthalate) (PTT).
  • the filler described in a polymer/filler/metal composite fiber of the present invention is a filler which does not melt at the processing temperature of the polymer.
  • the shape of the filler is not limited, and may be any shape of filler, which may be spherical or spheroidal, ellipsoidal, linear, needle-shaped, fibrous, rod-shaped, sheet-like, etc.; Any limitation, as long as it can be dispersed in the polymer matrix and smaller than the diameter of the finally prepared fiber, preferably at least one dimension is smaller than its three-dimensional size
  • the 0-dimensional nano-sized fillers are spherical or spheroidal fillers whose diameter is preferably in the nanometer scale; the 1D nanomaterials are fillers in the shape of linear, needle-shaped, fibrous, etc. with radial dimensions in the nanometer scale;
  • nanoscale size generally refers to a size smaller than 100 nm, but some known nanoscale fillers in the prior art, such as carbon nanotubes, although their diameters range from tens of nanometers to hundreds of nanometers, are also customary. It is called nanoscale; for example, nanometer calcium sulfate whiskers generally have an average diameter of several hundred nanometers, but are also commonly referred to as nanoscale. Thus, the nanoscale sized fillers herein are referred to as nanoscale fillers conventionally recognized in the art. More preferably, the nanoscale filler has at least one dimension in its three dimensional dimension of less than 100 nm, and most preferably less than 50 nm.
  • the filler described in the polymer/filler/metal composite fiber of the present invention may be a conductive filler and/or a non-conductive filler.
  • the conductive filler and the non-conductive filler may be various conductive fillers and non-conductive fillers disclosed in the prior art.
  • the prior art uses an index of powder resistivity to distinguish between a non-conductive filler and a conductive filler, wherein a filler having a powder resistivity of less than 1 ⁇ 10 9 ⁇ « ⁇ is called a conductive filler, and the powder resistivity is greater than or equal to 1 ⁇ 10 9 ⁇ .
  • the « ⁇ packing is called a non-conductive packing.
  • the conductive filler in the polymer/filler/metal composite fiber of the present invention is preferably a one-component metal, a metal alloy, a metal oxide, a metal salt, a metal nitride, or a non- At least one of metal nitride, metal hydroxide, conductive polymer, conductive carbon material; more preferably gold, silver, copper, iron, gold alloy, silver alloy, copper alloy, iron alloy, titanium dioxide, ferric oxide At least one of triiron tetroxide, silver oxide, zinc oxide, carbon black, carbon nanotubes, graphene, and linear conductive polyaniline.
  • the filler in the polymer/filler/metal composite fiber of the present invention is a carbon nanotube.
  • the carbon nanotubes are various carbon nanotubes in the prior art, and are generally selected from at least one of single-walled carbon nanotubes, double-walled carbon nanotubes, and multi-walled carbon nanotubes, preferably from multi-walled carbon nanotubes.
  • the diameter of the carbon nanotubes is
  • the non-conductive filler in the polymer/filler/metal composite fiber of the present invention is preferably a non-conductive metal salt, a metal nitride, a non-metal nitride, a non-metal carbide, a metal hydroxide, a metal oxide, a non-metal At least one of an oxide and a natural ore; more preferably calcium carbonate, barium sulfate, calcium sulfate, silver chloride, aluminum hydroxide, magnesium hydroxide, aluminum oxide, magnesium oxide, silicon dioxide, asbestos, talc, kaolin At least one of mica, feldspar, wollastonite, and montmorillonite.
  • the filler in the polymer/filler/metal composite fiber of the present invention is montmorillonite.
  • the montmorillonite is various montmorillonites disclosed in the prior art, and generally includes non-modified pure montmorillonite and/or organically modified montmorillonite in the prior art, preferably organic modified montmorillonite. earth.
  • the non-modified pure montmorillonite can be divided into non-acidic montmorillonite and acidic montmorillonite according to the pH value of the suspension of montmorillonite dispersed in water.
  • the non-modified pure montmorillonite according to the invention is preferably sodium-based unmodified pure montmorillonite, calcium-based unmodified pure montmorillonite, magnesium-based unmodified pure montmorillonite, acid calcium-based non-modified pure Montmorillonite, aluminum-based non-modified pure montmorillonite, sodium-calcium-based non-modified pure montmorillonite, calcium-sodium-based non-modified pure montmorillonite, sodium-magnesium-based unmodified pure montmorillonite, magnesium-sodium base Non-modified pure montmorillonite, sodium-aluminum-based non-modified pure montmorillonite, aluminum-sodium-based non-modified pure montmorillonite, magnesium-calcium-based non-
  • the organically modified montmorillonite is selected from the group consisting of organically modified montmorillonite obtained by ion exchange reaction using a cationic surfactant and an exchangeable cation between clay sheets, and/or using a modifier and clay surface activity
  • Organic modified montmorillonite obtained by grafting reaction of hydroxyl group preferably organic quaternary ammonium salt modified montmorillonite, quaternary salt modified montmorillonite, silicone modified montmorillonite, siloxane modified montmorillonite At least one of earth, amine modified montmorillonite.
  • the weight ratio of the filler to the polymer fiber in the polymer/filler/metal composite fiber of the present invention is from 0.1:100 to 30:100, preferably from 0.5:100 to 10:100, more preferably from 1:100 to 2:100.
  • the metal of the metal short fibers in the polymer/filler/metal composite fiber of the present invention is a low-melting metal, i.e., has a melting point of 20 to 480 ° C, preferably 100 to 250 ° C, more preferably 120 to 230. At least one of the one-component metal and the metal alloy of C, and the melting point thereof is simultaneously lower than the processing temperature of the polymer.
  • the one-component metal as the metal is an elemental metal of gallium, germanium, antimony, indium, tin, antimony, cadmium, or lead;
  • the metal alloy as the metal is gallium, germanium, antimony, indium, tin
  • the volume ratio of the metal short fibers to the polymer fibers in the polymer/filler/metal composite fiber of the present invention is from 0.01:100 to 20:100, preferably from 0.1:100 to 4:100, more preferably. It is 0 ⁇ 5:100 ⁇ 2:100.
  • the diameter of the metal short fibers dispersed in the polymer fiber is preferably less than or equal to 12 ⁇ m, more preferably less than or equal to 8 ⁇ m, and most preferably less than or equal to 3 ⁇ m. .
  • the method for preparing the polymer/filler/metal composite fiber of the present invention comprises the following steps:
  • Step 1 Melt blending the polymer, the filler, and the component in the metal by a given amount to obtain a polymer/filler/metal blend.
  • melt blending is carried out using a processing condition in which a thermoplastic resin is usually melt-blended.
  • the microscopic morphology of the resulting polymer/filler/metal blend is:
  • the metal is distributed as a dispersed phase in a polymer matrix (thermoplastic resin) as a continuous phase.
  • the filler is dispersed between the metal particles. Due to the presence of the filler in the system, the viscosity of the blend is greatly increased. Under the same shear rate, the system is subjected to greater shearing, so that the low melting point metal is polymerized.
  • the particle size of the dispersion in the substrate becomes smaller, on the other hand, the probability of recombination of the metal particles after collision is also reduced, the particle size of the metal particles is made smaller, the number of metal particles is larger, and the distance between the metal particles is smaller. .
  • Step 2 The polymer/filler/metal blend obtained in the first step is spun on a spinning device to obtain a polymer/filler/metal composite strand.
  • the spinning apparatus is a spinning apparatus which is generally used in the prior art, and is spun at a usual spinning and winding speed under the usual spinning conditions of the thermoplastic resin spinning.
  • Step 3 The polymer/filler/metal composite strand obtained in the second step is heated and stretched at a temperature lower than the melting point of the polymer used and a temperature higher than or equal to the melting point of the low melting point metal to obtain a polymer. / filler / metal composite fiber.
  • the stretching ratio of the heating stretching may be a normal stretching ratio, preferably greater than Or equal to 2 times, more preferably 5 times or more, and most preferably 10 times or more.
  • the draw ratio increases, the diameter of the metal short fibers becomes smaller, the electrical properties of the composite fibers increase, and at the same time, the dispersed phase metal particles of the polymer/filler/metal blend obtained in the first step due to the presence of the filler in the system
  • the particle size becomes smaller, the number of metal particles is larger, and the distance between the metal particles is smaller, so the diameter of the metal short fibers in the composite fiber prepared after the second step and the third step is smaller, and the distance between the metal short fibers is further Short, making the electrical properties of the composite fiber better.
  • the method used in the first step of the preparation method of the polymer/filler/metal composite fiber of the present invention for melt blending the polymer, the filler and the metal is a usual melt blending method in the rubber and plastic processing, and the blending temperature. That is, the usual processing temperature of the thermoplastic resin, that is, it should be selected within a range that ensures that the thermoplastic resin and the metal to be used are completely melted without decomposing the thermoplastic resin to be used. In addition, according to the processing needs, a suitable amount of a conventional additive for processing a thermoplastic resin can be added to the blended material.
  • the components such as the thermoplastic resin, the filler and the metal may be simultaneously melt-blended by being added to the melt blending device by means of metering or the like; or the respective mixing devices may be used in advance.
  • the components are mixed and then melt blended through a rubber-plastic blending device.
  • the rubber-plastic blending apparatus used in the first step of the production method may be an open mill, an internal mixer, a single-screw extruder, a twin-screw extruder or a torque rheometer.
  • the material mixing device is selected from the group consisting of high speed mixers, kneaders and the like mechanical mixing devices of the prior art.
  • the raw materials used in the first step of the preparation process may also contain auxiliaries which are commonly used in the field of plastics processing. Such as antioxidants, plasticizers and other processing aids. These commonly used adjuvants are used in conventional amounts or adjusted as appropriate to the actual situation.
  • the heating and stretching of the third step in the method for preparing the composite fiber of the present invention is a necessary condition for ensuring the polymer/filler/metal composite fiber of the present invention.
  • the viscosity of the blend system is greatly improved due to the presence of the filler in the system.
  • the microscopic morphology of the polymer/filler/metal composite fiber thus prepared is as follows: metal short fibers are distributed as dispersed phase in the polymer fiber, and metal short fibers as a dispersed phase are distributed in parallel along the polymer fiber axis; Between the short metal fibers, the short fiber diameter is shorter due to the presence of the filler, and the distance between the short fibers is shorter; in addition, in the case of a conductive filler such as carbon nanotubes, the conductive filler additionally serves as a connection, which is easier.
  • the metal is stretched at a suitable temperature, the length of the metal becomes longer as the stretching progresses, and in the plane perpendicular to the axial direction of the fiber, as the stretching ratio increases, the distance of the metal fiber is
  • the conductive filler also has a connection function, and it is easier to form a conductive network.
  • This special structure leads to an improvement in the internal conductive network of the conjugate fiber of the present invention as the draw ratio is increased, so that the electrical properties of the conjugate fiber of the present invention are continuously improved.
  • the composite fiber of the present invention increases in fiber draw ratio At the same time as the breaking strength is increased, the electrical properties are not affected, but are also increased, thereby achieving the objective of simultaneously improving the mechanical properties and electrical properties of the conjugate fiber of the present invention.
  • the invention proposes to prepare an antistatic polymer/filler/metal composite fiber by using a universal spinning device, which greatly reduces the cost and has wide applicability.
  • the low melting point metal selected for the polymer/filler/metal composite fiber of the present invention can improve the processability of the granulation process and the spinning performance of the fiber during the spinning process, improve the production efficiency, and save the production cost;
  • a thermoplastic resin having a large difference in melting point is selected in combination with a metal to broaden the production conditions and is easy to produce.
  • Figure 1 is a nano-X-ray tomography (Nano-CT) photograph of a polymer/carbon nanotube/metal composite fiber prepared in Example 5.
  • the black elongated material is metal fiber
  • the grayish white cylindrical material is polymer fiber.
  • the metal fibers are arranged in parallel along the direction in which the composite fibers are stretched. detailed description
  • the test method of the diameter and length of the short metal fibers is to remove the polymer matrix from the composite fiber by using a chemical solvent, and then observe and measure by using an environmental scanning electron microscope (XL-30 field emission environment scanning electron microscope, manufactured by FEI, USA).
  • the polymer of this embodiment is polypropylene (Sinopean Ningbo Zhenhai Refining & Chemical Co., Ltd.
  • the volume ratio of tin-bismuth alloy to polypropylene is 0.5:100, the weight ratio of carbon nanotubes to polypropylene is 2:100, and an appropriate amount of antioxidant 1010 (produced by Ciba Giga, Switzerland) and antioxidant 168 (Switzerland) are added. Cibajiaji production) and zinc stearate (commercially available); wherein 100 parts by weight of polypropylene, 0.5 parts of antioxidant 1010, 0.5 parts of antioxidant 168, 1 part of zinc stearate .
  • the raw materials and the ratio of the polymer, the carbon nanotubes and the metal alloy are uniformly mixed in a high-speed mixer. After that, it was extruded and pelletized by a German company PolymLab twin-screw extruder.
  • the temperatures of the extruder were: 190 °C, 200 °C, 210 °C, 210 °C, 210 °C, 200 °C (head) temperature).
  • the pellets were fed into a capillary rheometer (English Malvern RH70 capillary rheometer) to obtain a composite yarn at 200 ° C, a plunger speed of 5 mm/min, and a winding speed of 60 m/min.
  • the composite raw yarn was stretched at 150 ° C (3216 universal material testing machine of INSTRON, USA) to obtain polymer/carbon nanotube/metal composite fiber 5 times after the original length, and various tests were carried out. Listed in Table 1.
  • the diameter of the metal short fibers in the composite fiber was 1.87 ⁇ m ⁇ or less as observed by scanning electron microscopy.
  • the length is greater than or equal to 6 ⁇ m. There is little breakage in the spinning process.
  • the resulting fiber surface is smooth.
  • the polymer/carbon nanotube/metal composite fiber obtained was tested in the same manner as in Example 1 except that the volume ratio of the metal alloy to the polymer was 1:100, and the test results are shown in Table 1. It was observed by scanning electron microscopy that the diameter of the metal short fibers in the composite fiber was 2.15 ⁇ m or less. The length is greater than or equal to 7.6 ⁇ . Broken filaments rarely occur during the spinning process, and the resulting fiber surface is smooth.
  • the obtained polymer/carbon nanotube/metal composite fiber was subjected to various tests, and the test results are shown in Tables 1 and 2.
  • the diameter of the metal short fibers in the composite fiber was 3.46 ⁇ m ⁇ or less as observed by scanning electron microscopy. The length is greater than or equal to 9 ⁇ . Broken filaments are rarely observed during the spinning process, and the resulting fiber surface is smooth.
  • Example 2 Except that the metal alloy was not added, the same procedure as in Example 1 was carried out, and the obtained polypropylene/carbon nanotube fibers were subjected to various tests, and the test results are shown in Tables 1 and 2. A large number of broken filaments occur during the spinning process, and the resulting fiber surface is rough.
  • Example 3 Except that the composite raw yarn was stretched at 150 ° C to 10 times of the original length, the same as in Example 3, the obtained polymer/carbon nanotube/metal composite fiber was subjected to various tests, and the test results are listed in the table. 1 and Table 2.
  • the diameter of the metal short fibers in the composite fiber was 1.45 ⁇ m or less as observed by scanning electron microscopy. The length is greater than or equal to 9 ⁇ . There is little breakage in the spinning process, and the resulting fiber surface is smooth.
  • Example 5 Except that the metal alloy was not added, the same procedure as in Example 4 was carried out, and the obtained polypropylene/carbon nanotube fibers were subjected to various tests, and the test results are shown in Tables 1 and 2. A large number of broken filaments occur during the spinning process, and the resulting fiber surface is rough.
  • Example 5 Except that the metal alloy was not added, the same procedure as in Example 4 was carried out, and the obtained polypropylene/carbon nanotube fibers were subjected to various tests, and the test results are shown in Tables 1 and 2. A large number of broken filaments occur during the spinning process, and the resulting fiber surface is rough. Example 5
  • Example 3 Except that the composite raw yarn was stretched at 150 ° C to 15 times of the original length, the same procedure as in Example 3 was carried out, and the obtained polypropylene/carbon nanotube/metal composite fiber was subjected to various tests, and the test results are listed in the table. 1 and Table 2.
  • the diameter of the metal short fibers in the composite fiber was 0.8 ⁇ m or less as observed by scanning electron microscopy. The length is greater than or equal to 6 ⁇ . There is little breakage in the spinning process and the resulting fiber surface is smooth.
  • the polypropylene/carbon nanotube fibers obtained were subjected to various tests except that the metal alloy was not added, and the test results are shown in Tables 1 and 2. A large number of broken filaments occur during the spinning process, and the resulting fiber surface is rough.
  • the diameter of the short metal fibers in the composite fiber was 2.46 ⁇ m ⁇ or less as observed by scanning electron microscopy.
  • the length is greater than or equal to 5 ⁇ . There is little breakage in the spinning process, and the resulting fiber surface is smooth.
  • the diameter of the metal short fibers in the composite fiber was 1.46 ⁇ m ⁇ or less as observed by scanning electron microscopy.
  • the length is greater than or equal to 7 ⁇ . There is little breakage in the spinning process, and the resulting fiber surface is smooth.
  • the polypropylene/carbon nanotube fibers obtained were subjected to various tests except that the metal alloy was not added, and the test results are shown in Table 1. Spinning process A large number of broken filaments occur and the resulting fiber surface is rough.
  • the polymer of this embodiment is polypropylene (Sinbo, Ningbo Zhenhai Refining & Chemical Co., Ltd., grade Z30S, melting point is 167 ° C), the metal alloy is tin-bismuth alloy (melting point 138 ° C), nano titanium dioxide (Japan Ishihara titanium dioxide FT-3000, average The diameter is 270nm, the average length is 5.15 ⁇ ), the volume ratio of tin-bismuth alloy to polypropylene is 2:100, the weight ratio of titanium dioxide to polypropylene is 10:100, and the appropriate amount of antioxidant 1010 is added (produced by Ciba Jiaji, Switzerland) , antioxidant 168 (produced by Ciba Jiaji, Switzerland) and zinc stearate (commercially available); wherein, in terms of 100 parts by weight of polypropylene, 0.5 parts of antioxidant 1010 and 0.5 parts of antioxidant 168 Zinc stearate is 1 part.
  • the raw materials and the ratio of the above-mentioned polymer, titanium oxide and metal alloy are uniformly mixed in a high-speed mixer. After that, it was extruded and pelletized by a German company PolymLab twin-screw extruder.
  • the temperatures of the extruder were: 190 °C, 200 °C, 210 °C, 210 °C, 210 °C, 200 °C (head) temperature).
  • the pellets were fed into a capillary rheometer and spun at 200 ° C to obtain a composite strand having a plunger speed of 5 mm/min and a winding speed of 60 m/min.
  • the composite raw yarn was stretched at 150 °C to 15 times the original length to obtain a polymer/titania/metal composite fiber, and various tests were conducted.
  • the test results are shown in Table 1.
  • the diameter of the metal short fibers in the composite fiber was 2.46 ⁇ m ⁇ or less as observed by scanning electron microscopy.
  • the length is greater than or equal to 5.9 ⁇ . There is little breakage in the spinning process, and the resulting fiber surface is smooth.
  • the polypropylene/titania fibers obtained were subjected to various tests except that the metal alloy was not added, and the test results are shown in Table 1. A large number of broken filaments occur during the spinning process, and the resulting fiber surface is rough.
  • Example 8 Except that the weight ratio of titanium dioxide to polypropylene was 30:100, the same as in Example 8, the obtained polymer/titanium dioxide/metal composite fiber was subjected to various tests. The test results are listed in Table 1. It was observed by scanning electron microscopy that the diameter of the metal short fibers in the composite fiber was 4.66 ⁇ m or less. The length is greater than or equal to 5.3 ⁇ . There is little breakage in the spinning process, and the resulting fiber surface is smooth.
  • the polypropylene/titania fibers obtained were subjected to various tests except that the metal alloy was not added, and the test results are shown in Table 1. A large number of broken filaments occur during the spinning process, and the resulting fiber surface is rough.
  • the polymer of this embodiment is polypropylene (Sinbo, Ningbo Zhenhai Refining & Chemical Co., Ltd., grade Z30S, melting point is 167 ° C), the metal alloy is tin-bismuth alloy (melting point 138 ° C), nano titanium dioxide (Japan Ishihara titanium dioxide FT-3000, average The diameter is 270nm, the average length is 5.15 ⁇ ), the volume ratio of tin-bismuth alloy to polypropylene is 1:100, the weight ratio of titanium dioxide to polypropylene is 10:100, and the appropriate amount of antioxidant 1010 is added (produced by Ciba Jiaji, Switzerland) , antioxidant 168 (produced by Ciba Jiaji, Switzerland) and zinc stearate (commercially available); wherein, in terms of 100 parts by weight of polypropylene, 0.5 parts of antioxidant 1010 and 0.5 parts of antioxidant 168 Zinc stearate is 1 part.
  • the raw materials and the ratio of the above-mentioned polymer, titanium oxide and metal alloy are uniformly mixed in a high-speed mixer. After that, it was extruded and pelletized by a German company PolymLab twin-screw extruder.
  • the temperatures of the extruder were: 190 °C, 200 °C, 210 °C, 210 °C, 210 °C, 200 °C (head) temperature).
  • the pellets were fed into a capillary rheometer and spun at 200 ° C to obtain a composite strand having a plunger speed of 5 mm/min and a winding speed of 60 m/min.
  • the composite raw yarn was stretched at 150 ° C to 5 times the original length to obtain a polymer / titania / metal composite fiber, and various tests were carried out.
  • the test results are shown in Table 1.
  • the diameter of the metal short fibers in the composite fiber was 4.46 ⁇ m ⁇ or less as observed by scanning electron microscopy.
  • the length is greater than or equal to 5 ⁇ . There is little breakage in the spinning process, and the resulting fiber surface is smooth.
  • Comparative example 7 The polypropylene/titania fibers obtained were subjected to various tests except that the metal alloy was not added, and the test results are shown in Table 1. A large number of broken filaments occur during the spinning process, and the resulting fiber surface is rough.
  • the polymer/titania/metal composite fiber obtained was subjected to various tests except that the weight ratio of titanium oxide to polypropylene was 30:100, and the test results are shown in Table 1.
  • the diameter of the metal short fibers in the composite fiber was 4.66 ⁇ m ⁇ or less as observed by scanning electron microscopy.
  • the length is greater than or equal to 5 ⁇ . There is little breakage in the spinning process and the resulting fiber surface is smooth.
  • the polypropylene/titania fibers obtained were subjected to various tests except that the metal alloy was not added, and the test results are shown in Table 1. A large number of broken filaments occur during the spinning process, and the resulting fiber surface is rough.
  • the polymer of this embodiment is polypropylene (Ningbo Ningbo Zhenhai Refining & Chemical Co., Ltd., grade Z30S, melting point is 167 ° C), the metal alloy is tin-bismuth alloy (melting point 138 ° C), silver powder (Ningbo Jingxin Electronic Material Co., Ltd., high Density spherical silver powder, average particle size 500nm, melting point 960 ° C), tin-bismuth alloy to polypropylene volume ratio of 2:100, silver powder to polypropylene weight ratio of 10:100, adding appropriate amount of antioxidant 1010 (Switzerland Ciba Jiaji production), antioxidant 168 (produced by Ciba Jiaji, Switzerland) and zinc stearate (commercially available); 0.5 parts by weight of polypropylene, 100 parts of antioxidant 1010, anti-oxidation The agent 168 was 0.5 part, and the zinc stearate was 1 part.
  • the raw materials and the ratio of the above-mentioned polymer, silver powder and metal alloy are uniformly mixed in a high-speed mixer. After that, it was extruded and granulated by a German HAAKE company PolymLab twin-screw extruder. The temperature of each section of the extruder was: 190 ° C, 200 ° C, 210 ° C, 210 ° C, 210 ° C, 200 ° C (head) The pellets were added to a capillary rheometer and spun at 200 ° C to obtain a composite strand with a plunger speed of 5 mm/min and a winding speed of 60m/min.
  • the composite raw yarn was stretched at 150 ° C to 15 times the original length to obtain a polymer/silver powder/metal composite fiber, and each test was conducted.
  • the test results are shown in Table 1.
  • the diameter of the metal short fibers in the composite fiber was 3.46 ⁇ or less as observed by scanning electron microscopy.
  • the length is greater than or equal to 7.0 ⁇ m. There is little breakage in the spinning process, and the resulting fiber surface is smooth.
  • Example 12 Except that the metal alloy was not added, the same procedure as in Example 12 was carried out, and the obtained polypropylene/silver powder fibers were subjected to various tests, and the test results are shown in Table 1. A large number of broken filaments occur during the spinning process, and the resulting fiber surface is rough.
  • the polymer of this embodiment is polypropylene (Ningbo Ningbo Zhenhai Refining & Chemical Co., Ltd., grade Z30S, melting point is 167 ° C), the metal alloy is tin-bismuth alloy (melting point 138 ° C), silver powder (Ningbo Jingxin Electronic Material Co., Ltd., high Density spherical silver powder, average particle size 500nm, melting point 960 ° C, tin-bismuth alloy to polypropylene volume ratio of 1:100, silver powder to polypropylene weight ratio of 10:100, adding appropriate amount of antioxidant 1010 (Swiss steam Bajiaji production), antioxidant 168 (produced by Ciba Jiaji, Switzerland) and zinc stearate (commercially available); among them, 100 parts by weight of polypropylene, 0.5 parts of antioxidant 1010, antioxidant 168 is 0.5 parts, and zinc stearate is 1 part.
  • the raw materials and the ratio of the above-mentioned polymer, silver powder and metal alloy are uniformly mixed in a high-speed mixer. Then, it was extruded and pelletized by German HAAKE company PolymLab twin-screw extruder. The temperature of each section of the extruder was: 190 °C, 200 °C, 210 °C, 210 °C, 210 °C, 200 °C (head) temperature). The pellets were fed into a capillary rheometer and spun at 200 ° C to obtain a composite strand having a plunger speed of 5 mm/min and a winding speed of 60 m/min.
  • the composite raw yarn was stretched at 150 ° C to 5 times the original length to obtain a polymer/silver powder/metal composite fiber, and each test was conducted.
  • the test results are shown in Table 1.
  • the diameter of the short metal fibers in the composite fiber was 3.46 ⁇ m ⁇ or less as observed by scanning electron microscopy.
  • the length is greater than or equal to 7 ⁇ m. There is very little broken wire in the spinning process, and the obtained The fiber surface is smooth.
  • Example 13 Except that the metal alloy was not added, the same procedure as in Example 13 was carried out, and the obtained polypropylene/silver powder fibers were subjected to various tests, and the test results are shown in Table 1. A large number of broken filaments occur during the spinning process, and the resulting fiber surface is rough.
  • the polymer of this embodiment is polypropylene (Ningbo Ningbo Zhenhai Refining & Chemical Co., Ltd., grade Z30S, melting point is 167 ° C), the metal alloy is tin-bismuth alloy (melting point 138 ° C), stainless steel fiber (Beijing Jinfubang Co., Ltd., shearing) Short fiber, average diameter 8 ⁇ , melting point 1350 ° C), tin-bismuth alloy and polypropylene volume ratio of 2:100, stainless steel fiber to polypropylene weight ratio of 10:100, adding appropriate amount of antioxidant 1010 (Swiss steam Bajiaji production), antioxidant 168 (produced by Ciba Jiaji, Switzerland) and zinc stearate (commercially available); among them, 100 parts by weight of polypropylene, 0.5 parts of antioxidant 1010, antioxidant 168 is 0.5 parts, and zinc stearate is 1 part.
  • the raw materials and the ratio of the polymer, the stainless steel and the metal alloy are uniformly mixed in a high speed mixer. After that, it was extruded and pelletized by a German HAAKE company PolymLab twin-screw extruder. The temperature of each extruder was: 190 °C, 200 °C, 210 °C, 210 °C, 210 °C, 200 °C (head) temperature). The pellets were fed into a capillary rheometer and spun at 200 ° C to obtain a composite strand having a plunger speed of 5 mm/min and a winding speed of 60 m/min.
  • the composite raw yarn was stretched at 150 °C to 15 times the original length to obtain a polymer/stainless steel/metal composite fiber, and various tests were conducted.
  • the test results are shown in Table 1.
  • the diameter of the short metal fibers in the composite fiber was 2.46 ⁇ m ⁇ or less as observed by scanning electron microscopy.
  • the length is greater than or equal to 8.0 ⁇ . There is little breakage in the spinning process, and the resulting fiber surface is smooth.
  • the polypropylene/stainless steel fiber composite fibers obtained were tested in the same manner as in Example 14 except that the metal alloy was not added. The test results are shown in Table 1. Spinning A large number of broken filaments occurred during the process, and the obtained fiber surface was rough.
  • the polymer of this embodiment is polypropylene (Ningbo Ningbo Zhenhai Refining & Chemical Co., Ltd., grade Z30S, melting point is 167 ° C), the metal alloy is tin-bismuth alloy (melting point 138 ° C), stainless steel fiber (Beijing Jinfubang Co., Ltd., shearing) Short fiber, average diameter 8 ⁇ , melting point 1350 ° C), tin-bismuth alloy to polypropylene volume ratio of 1:100, stainless steel fiber to polypropylene weight ratio of 10:100, adding appropriate amount of antioxidant 1010 (Swiss steam Bajiaji production), antioxidant 168 (produced by Ciba Jiaji, Switzerland) and zinc stearate (commercially available); among them, 100 parts by weight of polypropylene, 0.5 parts of antioxidant 1010, antioxidant 168 is 0.5 parts, and zinc stearate is 1 part.
  • the raw materials and the ratio of the polymer, the stainless steel and the metal alloy are uniformly mixed in a high speed mixer. After that, it was extruded and pelletized by a German HAAKE company PolymLab twin-screw extruder. The temperature of each extruder was: 190 °C, 200 °C, 210 °C, 210 °C, 210 °C, 200 °C (head) temperature). The pellets were added to a capillary rheometer at 200. The composite yarn was obtained by spinning under C, the plunger speed was 5 mm/min, and the winding speed was 60 m/min.
  • the composite raw yarn was stretched at 150 ° C to 5 times the original length to obtain a polymer/stainless steel/metal composite fiber, and various tests were conducted.
  • the test results are shown in Table 1.
  • the diameter of the short metal fibers in the composite fiber was 7.46 ⁇ m ⁇ or less as observed by scanning electron microscopy.
  • the length is greater than or equal to 7 ⁇ . There is little breakage in the spinning process, and the resulting fiber surface is smooth.
  • Example 15 Except that the metal alloy was not added, the same procedure as in Example 15 was carried out, and the obtained polypropylene/stainless steel fiber composite fiber was subjected to various tests, and the test results are shown in Table 1. A large number of broken filaments occur during the spinning process, and the resulting fiber surface is rough.
  • the polymer of this embodiment is polypropylene (Sinbo, Ningbo Zhenhai Refining & Chemical Co., Ltd., grade Z30S, melting point is 167 ° C), and the metal alloy is tin-bismuth alloy (melting point 138 ° C).
  • Polyaniline (Tianjin Dewangmet New Material Technology Co., Ltd., polyaniline nanowire, average diameter lOOnm, average length ⁇ ), volume ratio of tin-bismuth alloy to polypropylene is 2:100, weight ratio of polyaniline to polypropylene For 10:100, add the right amount of antioxidant 1010 (produced by Ciba Giga, Switzerland), antioxidant 168 (produced by Ciba Giga, Switzerland) and zinc stearate (commercially available); In parts, the antioxidant 1010 was 0.5 part, the antioxidant 168 was 0.5 part, and the zinc stearate was 1 part.
  • antioxidant 1010 produced by Ciba Giga, Switzerland
  • antioxidant 168 produced by Ciba Giga, Switzerland
  • zinc stearate commercially available
  • the raw materials and the ratio of the above-mentioned polymer, polyaniline and metal alloy are uniformly mixed in a high-speed mixer. After that, it was extruded and pelletized by a German company PolymLab twin-screw extruder.
  • the temperatures of the extruder were: 190 °C, 200 °C, 210 °C, 210 °C, 210 °C, 200 °C (head) temperature).
  • the pellets were added to a capillary rheometer at 200.
  • the composite yarn was obtained by spinning under C, the plunger speed was 5 mm/min, and the winding speed was 60 m/min.
  • the composite raw yarn was stretched at 150 °C to 15 times the original length to obtain a polymer/polyaniline/metal composite fiber, and various tests were conducted.
  • the test results are shown in Table 1.
  • the diameter of the metal short fibers in the composite fiber was 3.46 ⁇ m ⁇ or less as observed by scanning electron microscopy.
  • the length is greater than or equal to 7.5 ⁇ . Broken filaments rarely occur during spinning.
  • the polypropylene/polyaniline fibers obtained were subjected to various tests except that the metal alloy was not added, and the test results are shown in Table 1. A large number of broken wires occur during the spinning process.
  • the polymer of this embodiment is polypropylene (Sinbo, Ningbo Zhenhai Refining & Chemical Co., Ltd., grade Z30S, melting point is 167 ° C), the metal alloy is tin-bismuth alloy (melting point 138 ° C), polyaniline (Tianjin Dewangmet new material technology) Ltd., polyaniline nanowires, average diameter lOOnm, average length ⁇ ), volume ratio of tin-bismuth alloy to polypropylene 1:100, weight ratio of polyaniline to polypropylene 10:100, adding appropriate amount of antioxidant 1010 (produced by Ciba Jiaji, Switzerland), antioxidant 168 (produced by Ciba Jiaji, Switzerland) and zinc stearate (commercially available); among them, 100 parts by weight of polypropylene, anti-oxidation
  • the agent 1010 was 0.5 part
  • the antioxidant 168 was 0.5 part
  • the zinc stearate was 1 part.
  • the raw materials and the ratio of the above-mentioned polymer, polyaniline and metal alloy are uniformly mixed in a high-speed mixer. After that, it was extruded and pelletized by a German HAAKE company PolymLab twin-screw extruder. The temperature of each extruder was: 190 °C, 200 °C, 210 °C, 210 °C, 210 °C, 200 °C (head) temperature). The pellets were fed into a capillary rheometer and spun at 200 ° C to obtain a composite strand having a plunger speed of 5 mm/min and a winding speed of 60 m/min.
  • the composite raw yarn was stretched at 150 ° C to 5 times the original length to obtain a polymer / polyaniline / metal composite fiber, and various tests were conducted.
  • the test results are shown in Table 1.
  • the diameter of the metal short fibers in the composite fiber was 6.46 ⁇ m ⁇ or less as observed by scanning electron microscopy.
  • the length is greater than or equal to 5 ⁇ . Broken filaments rarely occur during spinning.
  • the polypropylene/polyaniline fibers were subjected to various tests except that the metal alloy was not added, and the test results are shown in Table 1. A large number of broken wires occur during the spinning process.
  • the polymer of this embodiment is polypropylene (Ningbo Ningbo Zhenhai Refining & Chemical Co., Ltd., grade Z30S, melting point is 167 ° C), the metal alloy is tin-bismuth alloy (melting point 138 ° C), montmorillonite (American NanoCor, grade I.44PSS ).
  • the volume ratio of tin-bismuth alloy to polypropylene is 2:100, the weight ratio of montmorillonite to polypropylene is 2:100, the appropriate amount of antioxidant 1010 (produced by Ciba Giga, Switzerland), and antioxidant 168 (Switzerland) Cibajiaji production) and zinc stearate (commercially available); wherein 100 parts by weight of polypropylene, 0.5 parts of antioxidant 1010, 0.5 parts of antioxidant 168, and 1 part of zinc stearate .
  • the raw materials and the ratio of the above-mentioned polymer, montmorillonite and metal alloy are uniformly mixed in a high-speed mixer. After that, it was extruded and pelletized by a German HAAKE PolymLab twin-screw extruder. The temperature of each extruder was: 190 ° C, 200 ° C, 210 ° C, 210 ° C, 210 ° C, 200 ° C (head) temperature). The pellets were added to a capillary rheometer and spun at 200 ° C to obtain a composite strand with a plunger speed of 5 mm/min. It is 60m/min. The composite raw yarn was stretched at 150 ° C to 15 times the original length to obtain a polymer/montmorillonite/metal composite fiber, and various tests were carried out. The test results are shown in Table 1.
  • the diameter of the metal short fibers in the composite fiber was 1.46 ⁇ m ⁇ or less as observed by scanning electron microscopy.
  • the length is greater than or equal to 6.5 ⁇ . There is little breakage in the spinning process, and the resulting fiber surface is smooth.
  • the polypropylene/montmorillonite fibers obtained were subjected to various tests except that the metal alloy was not added, and the test results are shown in Table 1. A large number of broken filaments occur during the spinning process, and the resulting fiber surface is rough.
  • the polymer of this embodiment is polypropylene (Sinbo, Ningbo Zhenhai Refining & Chemical Co., Ltd., grade Z30S, melting point is 167 ° C), and the metal alloy is tin-bismuth alloy (Beijing Sanhe Dingxin High-tech Development Co., Ltd., melting point 138 ° C). Montmorillonite (NanoCor, USA I.44PSS). The volume ratio of tin-bismuth alloy to polypropylene is 0.5:100, the weight ratio of montmorillonite to polypropylene is 2:100, and an appropriate amount of antioxidant 1010 (produced by Ciba Giga, Switzerland) and antioxidant 168 (Switzerland) are added. Cibajiaji production) and zinc stearate (commercially available); wherein 100 parts by weight of polypropylene, 0.5 parts of antioxidant 1010, 0.5 parts of antioxidant 168, and 1 part of zinc stearate .
  • the raw materials and the ratio of the above-mentioned polymer, montmorillonite and metal alloy are uniformly mixed in a high-speed mixer. After that, it was extruded and pelletized by a German HAAKE company PolymLab twin-screw extruder. The temperature of each extruder was: 190 °C, 200 °C, 210 °C, 210 °C, 210 °C, 200 °C (head) temperature). The pellets were fed into a capillary rheometer and spun at 200 ° C to obtain a composite strand having a plunger speed of 5 mm/min and a winding speed of 60 m/min.
  • the composite raw yarn was stretched at 150 ° C to 15 times the original length to obtain a polymer/montmorillonite/metal composite fiber, and each test was conducted.
  • the test results are shown in Table 1.
  • the diameter of the short metal fibers in the composite fiber was 1.06 ⁇ m ⁇ or less as observed by scanning electron microscopy.
  • the length is greater than or equal to 7.5 ⁇ m. There is little breakage in the spinning process, and the resulting fiber surface is smooth.
  • the polymer/montmorillonite/metal composite fiber obtained was tested in the same manner as in Example 19 except that the volume ratio of the metal alloy to the polymer was 1:100, and the test results are shown in Table 1.
  • the diameter of the metal short fibers in the composite fiber was 2.15 ⁇ m ⁇ or less as observed by scanning electron microscopy.
  • the length is greater than or equal to 7.5 ⁇ . There is little breakage in the spinning process, and the resulting fiber surface is smooth.
  • the polymer/montmorillonite/metal composite fiber obtained was tested in the same manner as in Example 18 except that the composite raw yarn was stretched at 150 ° C to 5 times the original length, and the test results are shown in the table. 1.
  • the diameter of the short metal fibers in the composite fiber was observed to be 3.01 ⁇ m ⁇ or less by scanning electron microscopy.
  • the length is greater than or equal to 6.5 ⁇ . There is little breakage in the spinning process, and the resulting fiber surface is smooth.
  • the polypropylene/montmorillonite fibers obtained were subjected to various tests except that the metal alloy was not added, and the test results are shown in Table 1. A large number of broken filaments occur during the spinning process, and the resulting fiber surface is rough.
  • the polymer of this embodiment is polypropylene (Ningbo Ningbo Zhenhai Refining & Chemical Co., Ltd., grade Z30S, melting point is 167 ° C), the metal alloy is tin antimony alloy (melting point 138 ° C), siloxane modified montmorillonite (NanoCor, USA) , grade I.44PSS).
  • the volume ratio of tin-bismuth alloy to polypropylene is 0.5:100
  • the weight ratio of montmorillonite to polypropylene is 2:100, and an appropriate amount of antioxidant 1010 (produced by Ciba Giga, Switzerland) and antioxidant 168 (Rui) are added.
  • ⁇ ) and zinc stearate commercially available); wherein 100 parts by weight of polypropylene, 0.5 parts of antioxidant 1010, 0.5 parts of antioxidant 168, zinc stearate 1 Share.
  • the raw materials and the ratio of the above-mentioned polymer, montmorillonite and metal alloy are uniformly mixed in a high-speed mixer. After that, it was extruded and pelletized by a German HAAKE company PolymLab twin-screw extruder. The temperature of each extruder was: 190 °C, 200 °C, 210 °C, 210 °C, 210 °C, 200 °C (head) temperature). The pellets were fed into a capillary rheometer and spun at 200 ° C to obtain a composite strand having a plunger speed of 5 mm/min and a winding speed of 60 m/min. The composite raw yarn was stretched at 150 ° C to 5 times the original length to obtain a polymer / montmorillonite / metal composite fiber, and various tests were conducted. The test results are shown in Table 1.
  • the diameter of the short metal fibers in the composite fiber was 1.66 ⁇ m ⁇ or less as observed by scanning electron microscopy.
  • the length is greater than or equal to 5.5 ⁇ . There is little breakage in the spinning process, and the resulting fiber surface is smooth.
  • the polymer/montmorillonite/metal composite fiber obtained was tested in the same manner as in Example 22 except that the volume ratio of the metal alloy to the polymer was 1:100, and the test results are shown in Table 1.
  • the diameter of the metal short fibers in the composite fiber was 2.45 ⁇ m ⁇ or less as observed by scanning electron microscopy.
  • the length is greater than or equal to 6.5 ⁇ . There is little breakage in the spinning process, and the resulting fiber surface is smooth.
  • Example 21 Except that the composite raw yarn was stretched at 150 ° C to 10 times of the original length, the same as in Example 21, the obtained polymer / montmorillonite / metal composite fiber, various tests were carried out, and the test results are listed in the table. 1.
  • the diameter of the metal short fibers in the composite fiber was 1.67 ⁇ m ⁇ or less as observed by scanning electron microscopy.
  • the length is greater than or equal to 8.5 ⁇ m. There is little breakage in the spinning process.
  • the resulting fiber surface is smooth.
  • the polypropylene/montmorillonite fibers obtained were subjected to various tests except that the metal alloy was not added, and the test results are shown in Table 1. A large number of broken filaments occur during the spinning process, and the resulting fiber surface is rough.
  • Example 18 Except that the weight ratio of montmorillonite to polypropylene was 0.5:100, the same results as in Example 18 were carried out, and the obtained polymer/montmorillonite/metal composite fiber was subjected to various tests, and the test results are shown in Table 1.
  • the diameter of the short metal fibers in the composite fiber was 0.9 ⁇ m or less as observed by scanning electron microscopy.
  • the length is greater than or equal to 7.9 ⁇ . There is little breakage in the spinning process, and the resulting fiber surface is smooth.
  • Example 25 Except that the metal alloy was not added, the same procedure as in Example 25 was carried out, and the obtained polypropylene/montmorillonite fiber was subjected to various tests, and the test results are shown in Table 1. A large number of broken filaments occur during the spinning process, and the resulting fiber surface is rough.
  • the polymer/montmorillonite/metal composite fiber obtained was subjected to various tests except that the weight ratio of montmorillonite to polypropylene was 4:100, and the test results are shown in Table 1.
  • the diameter of the short metal fibers in the composite fiber was 1.09 ⁇ m ⁇ or less as observed by scanning electron microscopy.
  • the length is greater than or equal to 8.5 ⁇ . There is little breakage in the spinning process, and the resulting fiber surface is smooth.
  • the polypropylene/montmorillonite fibers obtained were subjected to various tests except that the metal alloy was not added, and the test results are shown in Table 1. A large number of broken filaments occur during the spinning process, and the resulting fiber surface is rough.
  • the polymer/montmorillonite/metal composite fiber obtained was subjected to various tests except that the weight ratio of montmorillonite to polypropylene was 8:100, and the test results are shown in Table 1.
  • the diameter of the short metal fibers in the composite fiber was 2.46 ⁇ m ⁇ or less as observed by scanning electron microscopy.
  • the length is greater than or equal to 8.6 ⁇ . There is little breakage in the spinning process, and the resulting fiber surface is smooth.
  • the polypropylene/montmorillonite fibers obtained were subjected to various tests except that the metal alloy was not added, and the test results are shown in Table 1. A large number of broken filaments occur during the spinning process, and the resulting fiber surface is rough.
  • the polymer of this embodiment is polypropylene (Ningbo Ningbo Zhenhai Refining & Chemical Co., Ltd., grade Z30S, melting point is 167 ° C), the metal alloy is tin-bismuth alloy (melting point 138 ° C), nano calcium carbonate (Henan Keli, grade NLY- 201, particle size range 30-50nm).
  • the volume ratio of tin-bismuth alloy to polypropylene is 2:100
  • the weight ratio of calcium carbonate to polypropylene is 10:100
  • an appropriate amount of antioxidant 1010 produced by Ciba Giga, Switzerland
  • antioxidant 168 antioxidant 168
  • Bajiaji production and zinc stearate (commercially available); wherein, in terms of 100 parts by weight of polypropylene, 0.5 parts of antioxidant 1010, 0.5 parts of antioxidant 168, and 1 part of zinc stearate.
  • the raw materials and the ratio of the above-mentioned polymer, calcium carbonate and metal alloy are uniformly mixed in a high-speed mixer. After that, it was extruded and pelletized by a German HAAKE company PolymLab twin-screw extruder. The temperature of each extruder was: 190 °C, 200 °C, 210 °C, 210 °C, 210 °C, 200 °C (head) temperature). The pellets were fed into a capillary rheometer and spun at 200 ° C to obtain a composite strand having a plunger speed of 5 mm/min and a winding speed of 60 m/min. The composite raw yarn was stretched at 150 °C to 15 times the original length to obtain a polymer/calcium carbonate/metal composite fiber, and various tests were carried out. The test results are listed in Table 1.
  • the diameter of the short metal fibers in the composite fiber was 2.06 ⁇ m ⁇ or less as observed by scanning electron microscopy.
  • the length is greater than or equal to 7.8 ⁇ . There is little breakage in the spinning process, and the resulting fiber surface is smooth.
  • the polypropylene/calcium carbonate fibers obtained were subjected to various tests except that the metal alloy was not added, and the test results are shown in Table 1. A large number of broken filaments occur during the spinning process, and the resulting fiber surface is rough.
  • the polymer/calcium carbonate/metal composite fiber obtained was subjected to various tests except that the weight ratio of calcium carbonate to polypropylene was 30:100, and the test results are shown in Table 1.
  • the diameter of the metal short fibers in the composite fiber was 2.09 ⁇ m ⁇ or less as observed by scanning electron microscopy.
  • the length is greater than or equal to 7.5 ⁇ . There is little breakage in the spinning process, and the resulting fiber surface is smooth.
  • the polypropylene/calcium carbonate fibers obtained were subjected to various tests except that the metal alloy was not added, and the test results are shown in Table 1. A large number of broken filaments occur during the spinning process, and the resulting fiber surface is rough.
  • the polymer of this embodiment is polypropylene (Ningbo Ningbo Zhenhai Refinery, grade Z30S, melting point is 167 ° C), the metal alloy is tin-bismuth alloy (melting point 138 ° C), calcium sulfate whisker (Zhengzhou Bokaili, brand nano Calcium sulfate whiskers, with an average diameter of 500 nm).
  • the volume ratio of tin-bismuth alloy to polypropylene is 2:100
  • the weight ratio of calcium sulfate to polypropylene is 10:100
  • antioxidant 1010 produced by Ciba Giga, Switzerland
  • antioxidant 168 Tins steam
  • the raw materials and the ratio of the above-mentioned polymer, calcium sulfate and metal alloy are uniformly mixed in a high-speed mixer. After that, it was extruded and pelletized by a German HAAKE company PolymLab twin-screw extruder. The temperature of each extruder was: 190 °C, 200 °C, 210 °C, 210 °C, 210 °C, 200 °C (head) temperature). The pellets were fed into a capillary rheometer and spun at 200 ° C to obtain a composite strand having a plunger speed of 5 mm/min and a winding speed of 60 m/min. The composite strand is at 150.
  • the polymer/calcium sulfate/metal composite fiber was obtained by stretching to 15 times the original length under C conditions, and various tests were carried out. The test results are shown in Table 1.
  • the diameter of the metal short fibers in the composite fiber was 3.06 ⁇ m ⁇ or less as observed by scanning electron microscopy.
  • the length is greater than or equal to 8 ⁇ . There is little breakage in the spinning process, and the resulting fiber surface is smooth.
  • the polypropylene/calcium sulfate fibers obtained were subjected to various tests except that the metal alloy was not added, and the test results are shown in Table 1. A large number of broken filaments occur during the spinning process, and the resulting fiber surface is rough.
  • Polymer ⁇ polyamide 11 (Arkema, France, grade D40, melting point 179 ° C), metal alloy is tin-bismuth alloy (melting point 138 ° C), carbon nanotubes (Beijing Tiannai Technology, grade FT-9000 , average diameter llnm, average length ⁇ , multi-walled carbon nanotubes).
  • the volume ratio of metal alloy to polymer is 2:100
  • the weight ratio of carbon nanotube to polymer is 2:100
  • the appropriate amount of antioxidant 1010 produced by Ciba Giga, Switzerland
  • antioxidant 168 Tins steam
  • the raw materials and the ratio of the above-mentioned polymer, carbon nanotubes and metal alloy are uniformly mixed in a high-speed mixer. Then use the German company PolymLab double
  • the extruder is extruded and granulated.
  • the temperatures of the extruder are: 200 °C, 210 °C, 220 °C, 220 °C, 220 °C, 210 °C (head temperature).
  • the pellets were fed into a capillary rheometer and spun at 200 ° C to obtain a composite strand having a plunger speed of 5 mm/min and a winding speed of 60 m/min.
  • the composite raw yarn was stretched at 170 ° C to 15 times the original length to obtain a polymer/carbon nanotube/metal composite fiber, and various tests were carried out. The test results are shown in Table 1.
  • the diameter of the metal short fibers in the composite fiber was 1.40 ⁇ m or less as observed by a scanning electron microscope.
  • the length is greater than or equal to 8.1 ⁇ . Broken yarns rarely occur during the spinning process, and the resulting fiber surface is smooth.
  • Example 31 The results were the same as in Example 31 except that no metal alloy was added.
  • the test results of the polyamide/carbon nanotube fibers are shown in Table 1. A large number of broken filaments occur during the spinning process, and the resulting fiber surface is rough.
  • the polymer is made of polyamide 11 (Arkema, France, grade D40, melting point is 179 ° C), the metal alloy is tin-bismuth alloy (melting point 138 ° C), silicone modified montmorillonite (NanoCor, USA) .44PSS ).
  • the volume ratio of metal alloy to polymer is 2:100, the weight ratio of montmorillonite to polymer is 2:100, the appropriate amount of antioxidant 1010 (produced by Ciba Giga, Switzerland), and antioxidant 168 (Swiss steam) Bajiaji production) and zinc stearate (commercially available); wherein the polyamide 11 is 100 parts by weight, the antioxidant 1010 is 0.5 parts, the antioxidant 168 is 0.5 parts, and the zinc stearate is 1 part. .
  • the raw materials and the ratio of the above-mentioned polymer, montmorillonite and metal alloy are uniformly mixed in a high-speed mixer. After that, it was extruded and pelletized by a German HAAKE company PolymLab twin-screw extruder. The temperature of each extruder was: 200 ° C, 210 ° C, 220 ° C, 220 ° C, 220 ° C, 210 ° C (head) temperature). The pellets were added to a capillary rheometer at 200. Spinning under C to obtain composite raw yarn, plunger speed is 5mm/min, winding speed It is 60m/min. The composite raw yarn was stretched at 170 ° C to 15 times the original length to obtain a polymer/montmorillonite/metal composite fiber, and various tests were carried out. The test results are shown in Table 1.
  • the diameter of the short metal fibers in the composite fiber was 1.90 ⁇ m ⁇ or less as observed by scanning electron microscopy.
  • the length is greater than or equal to 5.1 ⁇ . There is little breakage in the spinning process, and the resulting fiber surface is smooth.
  • Example 32 The rest were the same as in Example 32 except that no metal alloy was added.
  • the polyamide/montmorillonite fiber test results are shown in Table 1. A large number of broken filaments occur during the spinning process, and the resulting fiber surface is rough.
  • the diameter of the metal short fibers in the composite fiber was 2.50 ⁇ m ⁇ or less as observed by scanning electron microscopy.
  • the length is greater than or equal to 4.51 ⁇ . There is little breakage in the spinning process, and the resulting fiber surface is smooth.
  • Example 33 The rest were the same as in Example 33 except that no metal alloy was added.
  • the polyamide/montmorillonite fiber test results are shown in Table 1. A large number of broken filaments occur during the spinning process, and the resulting fiber surface is rough.
  • the polymer is made of polyamide 11 (Arkema, France, grade D40, melting point is 179 ° C), the metal alloy is tin-bismuth alloy (melting point 138 ° C), nano-titanium dioxide (Japan Ishihara titanium dioxide FT-3000, average diameter 270 nm, The average length is 5.15 ⁇ ).
  • the volume ratio of metal alloy to polymer is 2:100, the weight ratio of titanium dioxide to polymer is 10:100, and the appropriate amount of antioxidant 1010 is added (Swiss Ciba Jiaji) Production), antioxidant 168 (produced by Ciba Giga, Switzerland) and zinc stearate (commercially available); wherein, in terms of polyamide 11 as 100 parts by weight, antioxidant 1010 is 0.5 part, and antioxidant 168 is 0.5 parts, zinc stearate is 1 part.
  • the raw materials and the ratio of the above-mentioned polymer, titanium oxide and metal alloy are uniformly mixed in a high-speed mixer. Afterwards, it was extruded and pelletized by German HAAKE PolymLab twin-screw extruder. The temperature of each section of the extruder was: 200 °C, 210 °C, 220 °C, 220 °C, 220 °C, 210 °C (head) temperature). The pellets were fed into a capillary rheometer and spun at 200 ° C to obtain a composite strand having a plunger speed of 5 mm/min and a winding speed of 60 m/min. The composite raw yarn was stretched at 170 °C to 15 times the original length to obtain a polymer/titania/metal composite fiber, and various tests were conducted. The test results are shown in Table 1.
  • the diameter of the short metal fibers in the composite fiber was 1.30 ⁇ m ⁇ or less as observed by scanning electron microscopy.
  • the length is greater than or equal to 7.1 ⁇ . There is little breakage in the spinning process, and the resulting fiber surface is smooth.
  • Example 34 The rest were the same as in Example 34 except that no metal alloy was added.
  • the polyamide/titania fiber test results are shown in Table 1. A large number of broken filaments occur during the spinning process, and the resulting fiber surface is rough.
  • the polymer is made of polyamide 11 (Arkema, France, grade D40, melting point is 179 ° C), the metal alloy is tin-bismuth alloy (melting point 138 ° C), nano-calcium carbonate (Henan Keli, grade NLY-201, grain The diameter range is 30-50nm).
  • the volume ratio of metal alloy to polymer is 2:100, the weight ratio of calcium carbonate to polymer is 10:100, the appropriate amount of antioxidant 1010 (produced by Ciba Giga, Switzerland), and antioxidant 168 (Swiss Ciba) Manufactured by KGI and zinc stearate (commercially available); wherein, in terms of 100 parts by weight of the polyamide 11, 0.5 parts of the antioxidant 1010, 0.5 parts of the antioxidant 168, and 1 part of the zinc stearate.
  • the raw materials and the ratio of the above-mentioned polymer, calcium carbonate and metal alloy are uniformly mixed in a high-speed mixer. After that, it was extruded and granulated by a German HAAKE PolymLab twin-screw extruder.
  • the temperatures of the extruder were: 200 °C, 210 °C, 220 °C, 220 °C, 220 °C, 210 °C (head) temperature).
  • the pellets were fed into a capillary rheometer and spun at 200 ° C to obtain a composite strand having a plunger speed of 5 mm/min and a winding speed of 60 m/min.
  • the composite raw yarn was stretched at 170 ° C to 15 times the original length to obtain a polymer/calcium carbonate/metal composite fiber, and various tests were conducted. The test results are shown in Table 1.
  • the diameter of the short metal fibers in the composite fiber was 1.50 ⁇ m ⁇ or less as observed by scanning electron microscopy.
  • the length is greater than or equal to 7.1 ⁇ . There is little breakage in the spinning process, and the resulting fiber surface is smooth.
  • Example 35 The rest were the same as in Example 35 except that no metal alloy was added.
  • the polyamide/calcium carbonate fiber test results are shown in Table 1. A large number of broken filaments occur during the spinning process, and the resulting fiber surface is rough.
  • the corresponding polymer/filler/low melting point metal composite fiber of the present invention has the same strand stretching ratio with respect to the polymer/filler composite fiber not containing the low melting point metal. Greater tensile strength and greater elongation at break. These data indicate that the addition of a small amount of low melting point metal allows for simultaneous increase in tensile strength at break, elongation at break, and volume resistivity of the polymer/filler/metal composite fiber relative to the polymer/filler composite fiber.

Abstract

本发明涉及一种聚合物/填料/金属复合纤维，其包括含有金属短纤维和填料的聚合物纤维，金属短纤维作为分散相分布在聚合物纤维中，并沿着聚合物纤维轴平行分布，填料分散在聚合物纤维内并分布在金属短纤维之间；所述填料在所述聚合物加工温度下不发生熔融；所述金属为低熔点金属，选自单组分金属和金属合金中的至少一种，其熔点在20～480℃，并且其熔点同时低于所述聚合物加工温度；金属短纤维和聚合物纤维体积比为0.01∶100～20∶100；填料和聚合物的重量比为0.1∶100～30∶100。本发明复合纤维在降低体积电阻率的同时，降低断丝几率，纤维表面光滑。制备方法简单，生产成本较低，易于工业化大批量生产。

Description

一种聚合物 /填料 /金属复合纤维及其制备方法 技术领域
本发明涉及合成纤维领域， 进一步地说， 本发明涉及一种聚 合物 /填料 /金属的复合纤维及其制备方法， 并且涉及相应的聚合 物 /填料 /金属共混物。 背景技术
相较天然纤维， 合成纤维具有价格低廉， 密度低和吸湿率低 等特性， 广泛应用于日常生产生活的纺织服装类、编织袋等领域。 但是合成纤维的电绝缘性能好， 电阻率高， 在使用过程中易产生 静电， 对工业生产和人民生活都会带来危害。 并且随着高科技的 发展， 静电以及静电吸附尘埃是导致现代电子设备运转故障、 电 路短路、 信号丢失、 误码、 成品率低的直接原因之一。 在石油、 化工、 精密机械、 煤矿、 食品、 医药等行业均对静电的防护有特 殊的要求。 因此， 开发具有优越电性能的纤维从而减少静电带来 的危害成为十分迫切的课题。
碳纳米管是由碳六元环组成的类似卷曲石墨的纳米级管状结 构。 由于碳纳米管具有优异的电学和力学性能， 因此被广泛用于 聚合物基复合材料或复合纤维领域。 但是由于纳米粒子自身的高 表面能导致碳纳米管具有严重的团聚效应， 从而增加了纳米粒子 的填充量和成本。 同时， 大量的纳米粒子填充给纤维的生产也造 成了困难。 如何降低碳纳米管用量， 减少生产困难是亟待解决的 问题。
采用复合导电填料技术加入第三组分是有效提高纤维导电效 率， 降低碳纳米管含量的有效方法。 专利 CN102409421A公开了 一种制备聚丙烯 /纳米二氧化锡 /碳纳米管复合纤维的制备方法。 该技术虽然降低了复合纤维的电阻率， 但是加入的第三组分同样 为纳米粒子， 增加了加工原料的难度， 纤维表面粗糙， 手感差， 力学性能下降， 生产中容易断丝等现象。
近年来， 国内外聚合物 /低熔点金属复合材料领域出现新的发 展。 低熔点金属以高电导率、 易加工等特性作为一种新的填料被 广泛应用于聚合物的复合材料领域。 专利 CN102021671A公开了 一种聚合物 /低熔点金属复合导线及其制造方法， 同时专利 CN102140707A 公开了一种皮芯复合电磁屏蔽纤维及其制备方 法。 上述两项技术利用皮芯复合技术制备聚合物包覆低熔点金属 导线或纤维的方法。 但是该技术中需要特殊的复合纺丝机， 且作 为纤维的芯层金属比重加大， 虽然保证了纤维较低电阻率， 但是 需要大量添加金属， 增加了生产成本。 发明内容
为了能够以简便和低成本的方法制备具有低体积电阻率和良 好手感 （纤维表面光滑） 的复合纤维， 提出本发明。
本发明的一个目的是提供一种聚合物 /填料 /金属复合纤维， 该复合纤维具有良好的抗静电性能和手感。
本发明的另一目的是提供上述聚合物 /填料 /金属复合纤维的 制备方法， 该方法采用原位法制备聚合物 /填料 /金属复合纤维， 即在聚合物纤维制备过程中作为分散相的低熔点金属由金属颗粒 拉伸变形成金属短纤维的制备方法。 由于体系中填料的存在， 共 混过程中体系的粘度提高很大， 在相同剪切速率的条件之下， 体 系受到更大的剪切作用， 从而使低熔点金属在高分子材料基体中 分散粒径变小， 另一方面， 也降低了金属颗粒碰撞后重新发生合 并的概率， 使金属颗粒的粒径变得更小， 金属颗粒数量更多， 金 属颗粒之间距离更小，所以在金属颗粒原位地变形为金属纤维时， 使短纤维直径更小，短纤维之间距离更短； 另外，在导电填料（例 如碳纳米管） 的情况下， 分散在金属纤维之间的导电填料也起到 连接作用； 从而实现在较低金属填充量的情况下提高纤维抗静电 性能的目的。 本发明的方法是在现有普通纤维生产设备上实现， 从而使制备方法具有良好的适用性和较低设备成本。
本发明的一种聚合物 /填料 /金属复合纤维， 包括含有填料和 金属短纤维的聚合物纤维， 其微观结构为金属短纤维作为分散相 分布在聚合物纤维中， 而且作为分散相的金属短纤维沿着聚合物 纤维轴平行分布； 填料分散在聚合物纤维内， 分布在金属短纤维 之间。 由于填料的存在使短纤维直径更小，短纤维之间距离更短； 另外， 在导电填料（例如碳纳米管） 的情况下， 由于导电填料的 存在也起到连接金属短纤维的作用， 更容易形成导电网络； 使得 所制备的复合纤维的抗静电性能得到提高， 并且保持纤维良好的 手感。
在本发明范围内， 所述"平行分布，，是指金属短纤维沿着聚合 物纤维轴的方向平行取向， 但是由于复合纤维的制备工艺 （例如 拉伸工艺） 所决定， 有可能会有少部分金属短纤维的取向与聚合 物纤维轴的方向成一定角度， 本发明中所述 "平行分布，，也包括这 样的情况。
本发明的一种聚合物 /填料 /金属复合纤维中， 所述聚合物纤 维的聚合物为热塑性树脂， 优选为熔点在 90~450°C 的热塑性树 脂，更优选为熔点为 100~290°C的热塑性树脂。最优选自聚乙烯、 聚丙烯、 聚酰胺或聚酯等中的一种。 其中所述的聚酰胺包括现有 技术中任何种类的可纺丝聚酰胺， 优选尼龙 6、 尼龙 66、 尼龙 11 或尼龙 12。 所述的聚酯可以为现有技术中任何可纺丝的聚酯， 优 选聚对苯二曱酸乙二醇酯 （PET ) 或聚对苯二曱酸丙二醇酯 ( PTT ) 。 本发明的一种聚合物 /填料 /金属复合纤维中所述的填料为在 所述聚合物加工温度下不发生熔融的填料。 本发明中对所述填料 的形状没有任何限制， 可以为任何形状的填料， 可以为球形或类 球形、 椭球形、 线型、 针形、 纤维形、 棒状、 片状等； 这些填料 的尺寸没有任何限制， 只要可以分散在聚合物基体中并小于最终 制备的纤维的直径即可， 优选在其三维尺寸中至少一维尺寸小于
500μιη, 优选小于 300μιη的填料； 更优选现有技术中纳米级的填 料， 即在 0维、 1维或 2维可以达到纳米尺寸的填料， 优选 1维 或 2维尺寸可以达到纳米尺寸的填料。 其中 0维纳米级填料即直 径优选在纳米级的球形或类球形的填料； 1 维纳米材料即径向尺 寸在纳米级的线型、 针形、 纤维形等形状的填料； 2 维纳米材料 即厚度为纳米级的片状填料。 所谓的纳米级尺寸， 一般是指小于 lOOnm的尺寸， 但是现有技术中某些已知纳米级填料， 比如碳纳 米管， 虽然其直径尺寸从几十纳米到几百纳米之间， 但是也惯常 称其为纳米级； 又比如纳米硫酸钙晶须一般平均直径可在几百纳 米， 但是也惯常称其为纳米级。 故此本发明此处的纳米级尺寸的 填料指现有技术中惯常认为的纳米级填料。 所述的纳米级填料更 优选在其三维尺寸中至少有一维尺寸小于 lOOnm , 最优选小于 50nm。
本发明的聚合物 /填料 /金属复合纤维中所述的填料可以是导 电填料和 /或非导电填料。所述导电填料和非导电填料可以为现有 技术中公开的各种导电填料和非导电填料。 一般现有技术中采用 粉体电阻率的指标来区分非导电填料和导电填料， 其中粉体电阻 率小于 1χ109Ω·«η的填料称为导电填料，粉体电阻率大于或等于 1χ109Ω·«η的填料称为非导电填料。
本发明所述聚合物 /填料 /金属复合纤维中的导电填料优选为 单组分金属、 金属合金、 金属氧化物、 金属盐、 金属氮化物、 非 金属氮化物、 金属氢氧化物、 导电聚合物、 导电碳材料中的至少 一种； 更优选为金、 银、 铜、 铁、 金合金、 银合金、 铜合金、 铁 合金、 二氧化钛、 三氧化二铁、 四氧化三铁、 氧化银、 氧化锌、 炭黑、 碳纳米管、 石墨烯和线性导电聚苯胺中的至少一种。
在一种实施方案中， 本发明的聚合物 /填料 /金属复合纤维中 所述的填料是碳纳米管。 所述碳纳米管为现有技术中各种碳纳米 管， 一般选自单壁碳纳米管、 双壁碳纳米管、 多壁碳纳米管中的 至少一种， 优选自多壁碳纳米管。 所述的碳纳米管的直径为
0.4~500nm、 长度为 0.1~1000m、 长径比为 0.25~2.5xl06， 优选为 直径为 l~50nm、 长度为 l~50m、 长径比为 1~1χ103。
本发明所述聚合物 /填料 /金属复合纤维中的非导电填料优选 为非导电的金属盐、金属氮化物、 非金属氮化物、 非金属碳化物、 金属氢氧化物、 金属氧化物、 非金属氧化物、 天然矿石中的至少 一种； 更优选为碳酸钙、 硫酸钡、 硫酸钙、 氯化银、 氢氧化铝、 氢氧化镁、 氧化铝、 氧化镁、 二氧化硅、 石棉、 滑石、 高岭土、 云母、 长石、 硅灰石、 蒙脱土中的至少一种。
在一种实施方案中， 本发明的聚合物 /填料 /金属复合纤维中 所述的填料为蒙脱土。 所述蒙脱土为现有技术中所公开的各种蒙 脱土，一般包括现有技术中的非改性纯蒙脱土和 /或有机改性蒙脱 土， 优选为有机改性蒙脱土。
所述的非改性纯蒙脱土可根据蒙脱土分散于水中的悬浮液的 pH值不同而划分的非酸性蒙脱土和酸性蒙脱土。 本发明所述的 非改性纯蒙脱土优选钠基非改性纯蒙脱土、钙基非改性纯蒙脱土、 镁基非改性纯蒙脱土、 酸性钙基非改性纯蒙脱土、 铝基非改性纯 蒙脱土、 钠钙基非改性纯蒙脱土、 钙钠基非改性纯蒙脱土、 钠镁 基非改性纯蒙脱土、 镁钠基非改性纯蒙脱土、 钠铝基非改性纯蒙 脱土、 铝钠基非改性纯蒙脱土、 镁钙基非改性纯蒙脱土、 钙镁基 非改性纯蒙脱土、 钙铝基非改性纯蒙脱土、 铝钙基非改性纯蒙脱 土、 镁铝基非改性纯蒙脱土、 铝镁基非改性纯蒙脱土、 钙镁铝基 非改性纯蒙脱土、 镁钙铝基非改性纯蒙脱土、 钠镁钙基非改性纯 蒙脱土、 钙镁钠基非改性纯蒙脱土中至少一种。
所述的有机改性蒙脱土选自使用阳离子表面活性剂与黏土片 层间的可交换性阳离子进行离子交换反应后得到的有机改性蒙脱 土和 /或使用改性剂与黏土表面活性羟基进行接枝反应后得到的 有机改性蒙脱土， 优选有机季铵盐改性蒙脱土、 季鳞盐改性蒙脱 土、 有机硅改性蒙脱土、 硅氧烷改性蒙脱土， 胺类改性蒙脱土中 至少一种。
本发明的聚合物 /填料 /金属复合纤维中填料和聚合物纤维的 重量比为 0.1:100~30:100， 优选为 0.5:100~10:100， 更优选为 1:100~2:100。
本发明的一种聚合物 /填料 /金属复合纤维中所述金属短纤维 的金属为低熔金属， 即熔点在 20~480°C， 优选为 100~250°C， 更 优选为 120~230。C的单组分金属和金属合金中的至少一种， 并且 其熔点同时低于所述聚合物加工温度。
优选地， 作为所述金属的单组分金属为镓、 铯、 铷、 铟、 锡、 铋、 镉、 铅元素的单质金属； 作为所述金属的金属合金为镓、 铯、 铷、 铟、 锡、 铋、 镉、 铅元素中两种以上的金属合金， 例如锡铋 合金， 或者为镓、 铯、 铷、 铟、 锡、 铋、 镉、 铅元素中的至少一 种与铜、 银、 金、 铁或锌元素中的至少一种的金属合金， 或者为 镓、 铯、 铷、 铟、 锡、 铋、 镉、 铅元素中的至少一种与铜、 银、 金、 铁或锌元素中的至少一种和选自硅元素和碳元素中的至少一 种形成的合金。
本发明的聚合物 /填料 /金属复合纤维中金属短纤维和聚合物 纤维的体积比为 0.01:100~20:100， 优选为 0.1:100~4:100， 更优选 为 0·5:100~2:100。
本发明的一种聚合物 /填料 /金属复合纤维中， 所述分散在聚 合物纤维中的金属短纤维的直径优选小于或等于 12μιη， 更优选 为小于或等于 8μιη， 最优选为小于或等于 3μιη。
本发明的聚合物 /填料 /金属复合纤维的制备方法包括以下步 骤：
步骤一、 按给定量将包括所述聚合物、 所述填料与所述金属 在内的组分进行熔融共混， 得到聚合物 /填料 /金属共混物。
其中所述熔融共混采用通常热塑性树脂熔融共混的加工条 件。
所得的聚合物 /填料 /金属共混物的微观形态为： 金属作为分 散相均句分布在作为连续相的聚合物基体（热塑性树脂） 中。 填 料分散在金属颗粒之间， 由于体系中填料的存在， 共混体系的粘 度提高很大， 在相同剪切速率的条件之下， 体系受到更大的剪切 作用， 从而使低熔点金属在聚合物基体中分散粒径变小， 另一方 面， 也降低了金属颗粒碰撞后重新发生合并的概率， 使金属颗粒 的粒径变得更小， 金属颗粒数量更多， 金属颗粒之间距离更小。
步骤二、 将步骤一中所得聚合物 /填料 /金属共混物在纺丝设 备上纺丝， 得到聚合物 /填料 /金属复合原丝。
其中所述纺丝设备是现有技术中通用的纺丝设备， 在所采用 的热塑性树脂纺丝的通常纺丝条件下， 采用通常的喷丝和收卷速 度来纺丝。 通常， 收卷速度越快， 得到的复合纤维直径越细， 其 中金属短纤维直径越小，导致最后得到的复合纤维的电性能越好。
步骤三、 将步骤二中所得的聚合物 /填料 /金属复合原丝在低 于所采用的聚合物熔点的温度和高于或等于所述低熔点金属熔点 的温度范围内加热拉伸得到聚合物 /填料 /金属复合纤维。
其中加热拉伸的拉伸倍率采用通常拉伸倍率即可， 优选大于 或等于 2倍， 更优选为大于或等于 5倍， 最优选为大于或等于 10 倍。 随着拉伸倍率的提高， 金属短纤维的直径变小， 复合纤维的 电性能提高， 同时由于体系中填料的存在， 在步骤一中所得聚合 物 /填料 /金属共混物的分散相金属颗粒的粒径变得更小， 金属颗 粒数量更多， 金属颗粒之间距离更小， 所以经过步骤二和步骤三 后所制备的复合纤维中金属短纤维直径更小， 金属短纤维之间距 离更短， 使复合纤维的电性能更好。
本发明所述聚合物 /填料 /金属复合纤维的制备方法的步骤一 中将所述聚合物、 填料与金属熔融共混所采用的方法就是橡塑加 工中通常的熔融共混法，共混温度即热塑性树脂的通常加工温度， 即应该在既保证所采用的热塑性树脂和金属完全熔融又不会使所 采用的热塑性树脂分解的范围内选择。 此外， 根据加工需要， 可 在共混物料中适量加入热塑性树脂加工的常规助剂。 在共混过程 中可以将所述热塑性树脂、 填料与金属等各组分通过计量加料等 方式同时加入熔融共混设备中进行熔融共混； 也可以先通过通用 的混合设备， 预先将所述各个组分混合均句， 然后再经过橡塑共 混设备熔融共混。
在制备方法的步骤一中所使用的橡塑共混设备可以是开炼 机、 密炼机、 单螺杆挤出机、 双螺杆挤出机或转矩流变仪等。 所 述的物料混合设备选自现有技术中的高速搅拌机， 捏合机等等机 械混合设备。
在制备方法的步骤一的原料中还可含有塑料加工领域中常用 的助剂。 比如抗氧剂， 增塑剂及其它加工助剂等。 这些常用的助 剂用量为常规用量， 或根据实际情况的要求来进行适当的调整。
本发明制备复合纤维的方法中步骤三的加热拉伸是保证得到 本发明的聚合物 /填料 /金属复合纤维的必要条件， 步骤一中由于 体系中填料的存在， 共混体系的粘度提高很大， 在相同剪切速率 的条件之下， 体系受到更大的剪切作用， 从而使低熔点金属在聚 合物基体中分散粒径变小， 另一方面， 也降低了金属颗粒碰撞后 重新发生合并的概率， 使金属颗粒的粒径变得更小， 金属颗粒数 量更多， 金属颗粒之间距离更小， 这是得到本发明的聚合物 /填料 /金属复合纤维的保证。 这样所制备的聚合物 /填料 /金属复合纤维 的微观形态为： 金属短纤维作为分散相分布在聚合物纤维中， 而 且作为分散相的金属短纤维沿着聚合物纤维轴平行分布； 填料分 散在金属短纤维之间， 由于填料的存在使短纤维直径更小， 短纤 维之间距离更短； 另外， 在导电填料（例如碳纳米管）的情况下， 导电填料额外起到连接作用， 更容易形成导电网络； 使得制得纤 维的抗静电性能得到提高， 并且保持纤维良好的手感； 同时， 由 于金属短纤维排布在聚合物纤维内部，保护金属短纤维不受弯曲、 拉伸、折叠、磨损以及洗涤时的损害， 解决了金属层表面易氧化、 易脱落或者金属粉末易团聚， 从而导致抗静电效果下降的问题； 并且由于金属的加入，解决了聚合物 /填料复合纤维纺丝困难的问 题， 纺丝过程十分顺利， 断丝情况大量减少。
尤其特别是， 在现有技术中， 制备导电纤维时， 随着拉伸倍 率提高，导电填料之间的距离增大，原有的导电网络被拉伸破坏。 因此， 在导电填料不变的条件下， 现有技术中的导电纤维随着拉 伸倍数的提高， 虽然纤维的断裂强度也提高,但电性能是呈下降趋 势。 在本发明中， 金属在适当的温度下拉伸， 金属的长度会随着 拉伸越来越长， 而且在垂直纤维轴向的平面上， 随着拉伸倍数的 提高， 金属纤维的距离是不断减小的； 另外， 在导电填料（例如 碳纳米管） 的情况下， 导电填料也有连接作用， 更容易形成导电 网络。 这种特殊的结构导致本发明的复合纤维随着拉伸倍数的提 高， 其内部导电网络得到不断完善， 从而使本发明的复合纤维的 电性能不断提高。 由此，本发明的复合纤维随着纤维拉伸倍率提高 断裂强度提高的同时， 其电性能不仅没有受到影响， 反而也随之 提高， 从而实现了使本发明的复合纤维的力学性能和电性能同时 提高的目的。
本发明提出采用通用纺丝设备制备抗静电聚合物 /填料 /金属 复合纤维， 大幅度降低成本， 并且有广泛的适用性。 本发明所述 的聚合物 /填料 /金属复合纤维所选用的低熔点金属可改善造粒过 程的加工性和纺丝过程中的纤维的纺丝性能， 提高生产效率， 节 约生产成本； 并且可通过选择熔点相差范围大的热塑性树脂与金 属搭配来扩宽生产条件， 易于生产。 附图说明
图 1是实施例 5所制备的聚合物 /碳纳米管 /金属复合纤维的 纳米 X射线断层扫描成像 (Nano-CT)照片。 采用透射模式， 图中 黑色长条形物质为金属纤维，灰白色的圓柱状物质是聚合物纤维。 金属纤维沿着复合纤维拉伸方向平行排布。 具体实施方式
下面结合实施例进一步描述本发明。 本发明的范围不受这些 实施例的限制， 本发明的范围在所附的权利要求书中提出。
实施例中实验数据用以下仪器设备及测定方法测定：
1. 金属短纤维的直径和长度的测试方法为， 利用化学溶剂 从复合纤维中去除聚合物基体后， 利用环境扫描电镜（XL-30场 发射环境扫描电镜， 美国 FEI公司生产）观察测定。
2. 复合纤维的拉伸断裂强度及断裂伸长率测试标准为 GB/T 14337-2008。
3. 复合纤维的体积电阻率测试方法如下： 1、 选取 2cm左 右长度的复合纤维， 在两端用导电胶带粘附金属铝箔作为测试电 极， 测量电极内端间的复合纤维的长度 t; 2、 用光学显微镜测量 复合纤维的直径 d; 3、使用上海精密仪器仪表公司的 PC-68高阻 仪测量纤维体积电阻 Rv; 4、 根据如下公式计算纤维试样的体积 电阻率 ρν， Ρν =τ?ν·^ At1。 测量 10根纤维后取平均值。
实施例 1
本实施例的聚合物为聚丙烯 （中石化宁波镇海炼化， 牌号
Z30S, 熔点为 167°C ) ， 金属合金为锡铋合金（北京三禾鼎鑫高 新科技发展有限公司， 熔点 138°C ) ， 碳纳米管 （北京天奈科技， 牌号 FT-9000,平均直径 llnm,平均长度 ΙΟμιη,多壁碳纳米管）。 锡铋合金与聚丙烯的体积比为 0.5:100，碳纳米管与聚丙烯的重量 比为 2:100， 加入适量的抗氧剂 1010 (瑞士汽巴嘉基生产） 、 抗 氧剂 168 (瑞士汽巴嘉基生产） 以及硬脂酸锌（市售） ； 其中以 聚丙烯为 100重量份数计， 抗氧剂 1010为 0.5份， 抗氧剂 168为 0.5份， 硬脂酸锌为 1份。
按照上述的聚合物、 碳纳米管和金属合金的原料以及配比在 高速搅拌机中混合均匀。 之后用德国 ΗΑΑΚΕ公司 PolymLab双 螺杆挤出机挤出造粒，挤出机各段温度为： 190 °C， 200 °C , 210°C , 210°C , 210°C , 200°C (机头温度）。将粒料加入毛细管流变仪（英 国马尔文 RH70型毛细管流变仪） 中在 200°C下纺丝得到复合原 丝， 柱塞速度为 5mm/min， 收卷速度为 60m/min。 将复合原丝在 150°C条件下拉伸 （美国 INSTRON公司的 3326型万能材料试验 机） 至原长的 5 倍后得到聚合物 /碳纳米管 /金属复合纤维， 进行 各项测试， 测试结果列于表 1。
用扫描电镜观测， 复合纤维中金属短纤维的直径为 1.87μιη 以下。 长度为大于或等于 6μιη。 纺丝过程中很少出现断丝现象， 得到的纤维表面光滑。
实施例 2
除金属合金与聚合物的体积比按 1:100外， 其余均与实施例 1相同， 所得聚合物 /碳纳米管 /金属复合纤维， 进行各项测试， 测 试结果列于表 1。 用扫描电镜观测， 复合纤维中金属短纤维的直 径为 2.15μιη以下。长度为大于或等于 7.6μιη。 纺丝过程中很少出 现断丝现象， 得到的纤维表面光滑。
实施例 3
除金属合金与聚合物的体积比按 2:100外， 其余均与实施例 1相同， 所得聚合物 /碳纳米管 /金属复合纤维， 进行各项测试， 测 试结果列于表 1及表 2。 用扫描电镜观测， 复合纤维中金属短纤 维的直径为 3.46μιη以下。 长度为大于或等于 9μιη。 纺丝过程中 很少出现断丝现象， 得到的纤维表面光滑。
对比例 1
除不加入金属合金外， 其余均与实施例 1相同， 所得聚丙烯 / 碳纳米管纤维， 进行各项测试， 测试结果列于表 1及表 2。 纺丝 过程中大量出现断丝现象， 并且得到的纤维表面粗糙。
实施例 4
除将复合原丝在 150°C下拉伸至原长的 10倍外， 其余均与实 施例 3相同， 所得聚合物 /碳纳米管 /金属复合纤维， 进行各项测 试， 测试结果列于表 1及表 2。 用扫描电镜观测， 复合纤维中金 属短纤维的直径为 1.45μιη以下。 长度为大于或等于 9μιη。 纺丝 过程中很少出现断丝现象， 得到的纤维表面光滑。
对比例 2
除不加入金属合金外， 其余均与实施例 4相同， 所得聚丙烯 / 碳纳米管纤维， 进行各项测试， 测试结果列于表 1及表 2。 纺丝 过程中大量出现断丝现象， 并且得到的纤维表面粗糙。 实施例 5
除将复合原丝在 150°C下拉伸至原长的 15倍外， 其余均与实 施例 3相同， 所得聚丙烯 /碳纳米管 /金属复合纤维， 进行各项测 试， 测试结果列于表 1及表 2。 用扫描电镜观测， 复合纤维中金 属短纤维的直径为 0.8μιη以下。 长度为大于或等于 6μιη。 纺丝过 程中很少出现断丝现象， 得到的纤维表面光滑。
对比例 3
除不加入金属合金外， 其余均与实施例 5相同， 所得聚丙烯 / 碳纳米管纤维， 进行各项测试， 测试结果列于表 1及表 2。 纺丝 过程中大量出现断丝现象， 并且得到的纤维表面粗糙。
实施例 6
除将碳纳米管与聚丙烯的重量比为 1:100外， 其余均与实施 例 3相同， 所得聚合物 /碳纳米管 /金属复合纤维， 进行各项测试， 测试结果列于表 1。
用扫描电镜观测， 复合纤维中金属短纤维的直径为 2.46μιη 以下。 长度为大于或等于 5μιη。 纺丝过程中很少出现断丝现象， 得到的纤维表面光滑。
实施例 7
除将碳纳米管与聚丙烯的重量比为 4:100外， 其余均与实施 例 3相同， 所得聚合物 /碳纳米管 /金属复合纤维， 进行各项测试， 测试结果列于表 1。
用扫描电镜观测， 复合纤维中金属短纤维的直径为 1.46μιη 以下。 长度为大于或等于 7μιη。 纺丝过程中很少出现断丝现象， 得到的纤维表面光滑。
对比例 4
除不加入金属合金外， 其余均与实施例 6相同， 所得聚丙烯 / 碳纳米管纤维， 进行各项测试， 测试结果列于表 1。 纺丝过程中 大量出现断丝现象， 并且得到的纤维表面粗糙。
实施例 8
本实施例的聚合物为聚丙烯 （中石化宁波镇海炼化， 牌号 Z30S, 熔点为 167°C ) ， 金属合金为锡铋合金（熔点 138°C ) ， 纳米二氧化钛 (日本石原二氧化钛 FT-3000, 平均直径 270nm， 平均长度 5.15μιη ) ， 锡铋合金与聚丙烯的体积比为 2:100， 二氧 化钛与聚丙烯的重量比为 10:100， 加入适量的抗氧剂 1010 (瑞士 汽巴嘉基生产） 、 抗氧剂 168 (瑞士汽巴嘉基生产） 以及硬脂酸 锌（市售） ； 其中以聚丙烯为 100重量份数计， 抗氧剂 1010为 0.5份， 抗氧剂 168为 0.5份， 硬脂酸锌为 1份。
按照上述的聚合物、 二氧化钛和金属合金的原料以及配比在 高速搅拌机中混合均匀。 之后用德国 ΗΑΑΚΕ公司 PolymLab双 螺杆挤出机挤出造粒，挤出机各段温度为： 190 °C， 200 °C , 210°C , 210°C , 210°C , 200 °C (机头温度）。 将粒料加入毛细管流变仪中 在 200 °C下纺丝得到复合原丝， 柱塞速度为 5mm/min， 收卷速度 为 60m/min。 将复合原丝在 150 °C条件下拉伸至原长的 15倍后得 到聚合物 /二氧化钛 /金属复合纤维， 进行各项测试， 测试结果列 于表 1。用扫描电镜观测，复合纤维中金属短纤维的直径为 2.46μιη 以下。 长度为大于或等于 5.9μιη。 纺丝过程中很少出现断丝现象， 得到的纤维表面光滑。
对比例 5
除不加入金属合金外， 其余均与实施例 8相同， 所得聚丙烯 / 二氧化钛纤维， 进行各项测试， 测试结果列于表 1。 纺丝过程中 大量出现断丝现象， 并且得到的纤维表面粗糙。
实施例 9
除将二氧化钛与聚丙烯的重量比为 30:100外，其余均与实施 例 8相同， 所得聚合物 /二氧化钛 /金属复合纤维， 进行各项测试， 测试结果列于表 1。 用扫描电镜观测， 复合纤维中金属短纤维的 直径为 4.66μιη以下。长度为大于或等于 5.3μιη。纺丝过程中很少 出现断丝现象， 得到的纤维表面光滑。
对比例 6
除不加入金属合金外， 其余均与实施例 9相同， 所得聚丙烯 / 二氧化钛纤维， 进行各项测试， 测试结果列于表 1。 纺丝过程中 大量出现断丝现象， 并且得到的纤维表面粗糙。
实施例 10
本实施例的聚合物为聚丙烯 （中石化宁波镇海炼化， 牌号 Z30S, 熔点为 167°C ) ， 金属合金为锡铋合金（熔点 138°C ) ， 纳米二氧化钛 (日本石原二氧化钛 FT-3000, 平均直径 270nm， 平均长度 5.15μιη ) ， 锡铋合金与聚丙烯的体积比为 1:100， 二氧 化钛与聚丙烯的重量比为 10:100， 加入适量的抗氧剂 1010 (瑞士 汽巴嘉基生产） 、 抗氧剂 168 (瑞士汽巴嘉基生产） 以及硬脂酸 锌（市售） ； 其中以聚丙烯为 100重量份数计， 抗氧剂 1010为 0.5份， 抗氧剂 168为 0.5份， 硬脂酸锌为 1份。
按照上述的聚合物、 二氧化钛和金属合金的原料以及配比在 高速搅拌机中混合均匀。 之后用德国 ΗΑΑΚΕ公司 PolymLab双 螺杆挤出机挤出造粒，挤出机各段温度为： 190 °C， 200 °C , 210°C , 210°C , 210°C , 200 °C (机头温度）。 将粒料加入毛细管流变仪中 在 200 °C下纺丝得到复合原丝， 柱塞速度为 5mm/min， 收卷速度 为 60m/min。 将复合原丝在 150°C条件下拉伸至原长的 5倍后得 到聚合物 /二氧化钛 /金属复合纤维， 进行各项测试， 测试结果列 于表 1。用扫描电镜观测，复合纤维中金属短纤维的直径为 4.46μιη 以下。 长度为大于或等于 5μιη。 纺丝过程中很少出现断丝现象， 得到的纤维表面光滑。
对比例 7 除不加入金属合金外，其余均与实施例 10相同， 所得聚丙烯 /二氧化钛纤维， 进行各项测试， 测试结果列于表 1。 纺丝过程中 大量出现断丝现象， 并且得到的纤维表面粗糙。
实施例 11
除将二氧化钛与聚丙烯的重量比为 30:100外，其余均与实施 例 10相同，所得聚合物 /二氧化钛 /金属复合纤维，进行各项测试， 测试结果列于表 1。 用扫描电镜观测， 复合纤维中金属短纤维的 直径为 4.66μιη以下。 长度为大于或等于 5μιη。 纺丝过程中很少 出现断丝现象， 得到的纤维表面光滑。
对比例 8
除不加入金属合金外，其余均与实施例 11相同， 所得聚丙烯 /二氧化钛纤维， 进行各项测试， 测试结果列于表 1。 纺丝过程中 大量出现断丝现象， 并且得到的纤维表面粗糙。
实施例 12
本实施例的聚合物为聚丙烯 （中石化宁波镇海炼化， 牌号 Z30S, 熔点为 167°C ) ， 金属合金为锡铋合金（熔点 138°C ) ， 银粉（宁波晶鑫电子材料有限公司， 高密度球形银粉， 平均粒径 500nm, 熔点 960°C ) ， 锡铋合金与聚丙烯的体积比为 2:100， 银 粉与聚丙烯的重量比为 10:100， 加入适量的抗氧剂 1010 (瑞士汽 巴嘉基生产） 、 抗氧剂 168 (瑞士汽巴嘉基生产） 以及硬脂酸锌 (市售） ； 其中以聚丙烯为 100重量份数计， 抗氧剂 1010为 0.5 份， 抗氧剂 168为 0.5份， 硬脂酸锌为 1份。
按照上述的聚合物、 银粉和金属合金的原料以及配比在高速 搅拌机中混合均匀。 之后用德国 HAAKE公司 PolymLab双螺杆 挤出机挤出造粒，挤出机各段温度为： 190°C， 200 "C， 210°C， 210°C， 210°C , 200 °C (机头温度）。 将粒料加入毛细管流变仪中在 200°C 下纺丝得到复合原丝， 柱塞速度为 5mm/min， 收卷速度为 60m/min。 将复合原丝在 150°C条件下拉伸至原长的 15倍后得到 聚合物 /银粉 /金属复合纤维， 进行各项测试， 测试结果列于表 1。 用扫描电镜观测， 复合纤维中金属短纤维的直径为 3.46μιη以下。 长度为大于或等于 7.0μιη。 纺丝过程中很少出现断丝现象， 得到 的纤维表面光滑。
对比例 9
除不加入金属合金外，其余均与实施例 12相同， 所得聚丙烯 /银粉纤维， 进行各项测试， 测试结果列于表 1。 纺丝过程中大量 出现断丝现象， 并且得到的纤维表面粗糙。
实施例 13
本实施例的聚合物为聚丙烯 （中石化宁波镇海炼化， 牌号 Z30S, 熔点为 167°C ) ， 金属合金为锡铋合金（熔点 138°C ) ， 银粉（宁波晶鑫电子材料有限公司， 高密度球形银粉， 平均粒径 500nm, 熔点 960°C， 锡铋合金与聚丙烯的体积比为 1:100， 银粉 与聚丙烯的重量比为 10:100， 加入适量的抗氧剂 1010 (瑞士汽巴 嘉基生产）、 抗氧剂 168 (瑞士汽巴嘉基生产）以及硬脂酸锌（市 售） ； 其中以聚丙烯为 100重量份数计， 抗氧剂 1010为 0.5份， 抗氧剂 168为 0.5份， 硬脂酸锌为 1份。
按照上述的聚合物、 银粉和金属合金的原料以及配比在高速 搅拌机中混合均匀。 之后用德国 HAAKE公司 PolymLab双螺杆 挤出机挤出造粒，挤出机各段温度为： 190 °C， 200 °C， 210°C， 210°C， 210°C , 200 °C (机头温度）。 将粒料加入毛细管流变仪中在 200°C 下纺丝得到复合原丝， 柱塞速度为 5mm/min， 收卷速度为 60m/min。将复合原丝在 150°C条件下拉伸至原长的 5倍后得到聚 合物 /银粉 /金属复合纤维， 进行各项测试， 测试结果列于表 1。 用 扫描电镜观测， 复合纤维中金属短纤维的直径为 3.46μιη 以下。 长度为大于或等于 7μιη。 纺丝过程中很少出现断丝现象， 得到的 纤维表面光滑。
对比例 10
除不加入金属合金外，其余均与实施例 13相同， 所得聚丙烯 /银粉纤维， 进行各项测试， 测试结果列于表 1。 纺丝过程中大量 出现断丝现象， 并且得到的纤维表面粗糙。
实施例 14
本实施例的聚合物为聚丙烯 （中石化宁波镇海炼化， 牌号 Z30S, 熔点为 167°C ) ， 金属合金为锡铋合金（熔点 138°C ) ， 不锈钢纤维（北京金富邦有限公司， 剪切短纤维， 平均直径 8μιη， 熔点 1350°C ) ， 锡铋合金与聚丙烯的体积比为 2:100， 不锈钢纤 维与聚丙烯的重量比为 10:100， 加入适量的抗氧剂 1010 (瑞士汽 巴嘉基生产） 、 抗氧剂 168 (瑞士汽巴嘉基生产） 以及硬脂酸锌 (市售） ； 其中以聚丙烯为 100重量份数计， 抗氧剂 1010为 0.5 份， 抗氧剂 168为 0.5份， 硬脂酸锌为 1份。
按照上述的聚合物、 不锈钢和金属合金的原料以及配比在高 速搅拌机中混合均匀。 之后用德国 HAAKE公司 PolymLab双螺 杆挤出机挤出造粒， 挤出机各段温度为： 190 °C， 200°C , 210°C , 210°C , 210°C , 200 °C (机头温度）。 将粒料加入毛细管流变仪中 在 200 °C下纺丝得到复合原丝， 柱塞速度为 5mm/min， 收卷速度 为 60m/min。 将复合原丝在 150 °C条件下拉伸至原长的 15倍后得 到聚合物 /不锈钢 /金属复合纤维， 进行各项测试， 测试结果列于 表 1。 用扫描电镜观测， 复合纤维中金属短纤维的直径为 2.46μιη 以下。 长度为大于或等于 8.0μιη。 纺丝过程中很少出现断丝现象， 得到的纤维表面光滑。
对比例 11
除不加入金属合金外，其余均与实施例 14相同， 所得聚丙烯 /不锈钢纤维复合纤维， 进行各项测试， 测试结果列于表 1。 纺丝 过程中大量出现断丝现象， 并且得到的纤维表面粗糙。
实施例 15
本实施例的聚合物为聚丙烯 （中石化宁波镇海炼化， 牌号 Z30S, 熔点为 167°C ) ， 金属合金为锡铋合金（熔点 138°C ) ， 不锈钢纤维 (北京金富邦有限公司， 剪切短纤维， 平均直径 8μιη， 熔点 1350°C)， 锡铋合金与聚丙烯的体积比为 1:100， 不锈钢纤维 与聚丙烯的重量比为 10:100， 加入适量的抗氧剂 1010 (瑞士汽巴 嘉基生产）、 抗氧剂 168 (瑞士汽巴嘉基生产）以及硬脂酸锌（市 售） ； 其中以聚丙烯为 100重量份数计， 抗氧剂 1010为 0.5份， 抗氧剂 168为 0.5份， 硬脂酸锌为 1份。
按照上述的聚合物、 不锈钢和金属合金的原料以及配比在高 速搅拌机中混合均匀。 之后用德国 HAAKE公司 PolymLab双螺 杆挤出机挤出造粒， 挤出机各段温度为： 190 °C， 200°C , 210°C , 210°C , 210°C , 200 °C (机头温度）。 将粒料加入毛细管流变仪中 在 200。C下纺丝得到复合原丝，柱塞速度为 5mm/min， 收卷速度 为 60m/min。 将复合原丝在 150°C条件下拉伸至原长的 5倍后得 到聚合物 /不锈钢 /金属复合纤维， 进行各项测试， 测试结果列于 表 1。 用扫描电镜观测， 复合纤维中金属短纤维的直径为 7.46μιη 以下。 长度为大于或等于 7μιη。 纺丝过程中很少出现断丝现象， 得到的纤维表面光滑。
对比例 12
除不加入金属合金外，其余均与实施例 15相同， 所得聚丙烯 /不锈钢纤维复合纤维， 进行各项测试， 测试结果列于表 1。 纺丝 过程中大量出现断丝现象， 并且得到的纤维表面粗糙。
实施例 16
本实施例的聚合物为聚丙烯 （中石化宁波镇海炼化， 牌号 Z30S, 熔点为 167°C ) ， 金属合金为锡铋合金（熔点 138°C ) ， 聚苯胺（天津得旺迈特新材料科技有限公司， 聚苯胺纳米线， 平 均直径 lOOnm, 平均长度 ΙΟμιη ) ， 锡铋合金与聚丙烯的体积比 为 2:100， 聚苯胺与聚丙烯的重量比为 10:100， 加入适量的抗氧 剂 1010 (瑞士汽巴嘉基生产）、 抗氧剂 168 (瑞士汽巴嘉基生产） 以及硬脂酸锌 （市售） ； 其中以聚丙烯为 100重量份数计， 抗氧 剂 1010为 0.5份， 抗氧剂 168为 0.5份， 硬脂酸锌为 1份。
按照上述的聚合物、 聚苯胺和金属合金的原料以及配比在高 速搅拌机中混合均匀。 之后用德国 ΗΑΑΚΕ公司 PolymLab双螺 杆挤出机挤出造粒， 挤出机各段温度为： 190 °C， 200°C , 210°C , 210°C , 210°C , 200 °C (机头温度）。 将粒料加入毛细管流变仪中 在 200。C下纺丝得到复合原丝，柱塞速度为 5mm/min， 收卷速度 为 60m/min。 将复合原丝在 150 °C条件下拉伸至原长的 15倍后得 到聚合物 /聚苯胺 /金属复合纤维， 进行各项测试， 测试结果列于 表 1。 用扫描电镜观测， 复合纤维中金属短纤维的直径为 3.46μιη 以下。 长度为大于或等于 7.5μιη。 纺丝过程中很少出现断丝现象。
对比例 13
除不加入金属合金外，其余均与实施例 16相同， 所得聚丙烯 /聚苯胺纤维， 进行各项测试， 测试结果列于表 1。 纺丝过程中大 量出现断丝现象。
实施例 17
本实施例的聚合物为聚丙烯 （中石化宁波镇海炼化， 牌号 Z30S, 熔点为 167°C ) ， 金属合金为锡铋合金（熔点 138°C ) ， 聚苯胺（天津得旺迈特新材料科技有限公司， 聚苯胺纳米线， 平 均直径 lOOnm, 平均长度 ΙΟμιη ) ， 锡铋合金与聚丙烯的体积比 为 1:100， 聚苯胺与聚丙烯的重量比为 10:100， 加入适量的抗氧 剂 1010 (瑞士汽巴嘉基生产）、 抗氧剂 168 (瑞士汽巴嘉基生产） 以及硬脂酸锌 （市售） ； 其中以聚丙烯为 100重量份数计， 抗氧 剂 1010为 0.5份， 抗氧剂 168为 0.5份， 硬脂酸锌为 1份。
按照上述的聚合物、 聚苯胺和金属合金的原料以及配比在高 速搅拌机中混合均匀。 之后用德国 HAAKE公司 PolymLab双螺 杆挤出机挤出造粒， 挤出机各段温度为： 190 °C， 200°C , 210°C , 210°C , 210°C , 200 °C (机头温度）。 将粒料加入毛细管流变仪中 在 200 °C下纺丝得到复合原丝， 柱塞速度为 5mm/min， 收卷速度 为 60m/min。 将复合原丝在 150°C条件下拉伸至原长的 5倍后得 到聚合物 /聚苯胺 /金属复合纤维， 进行各项测试， 测试结果列于 表 1。 用扫描电镜观测， 复合纤维中金属短纤维的直径为 6.46μιη 以下。 长度为大于或等于 5μιη。 纺丝过程中很少出现断丝现象。
对比例 14
除不加入金属合金外，其余均与实施例 17相同， 所得聚丙烯 /聚苯胺纤维， 进行各项测试， 测试结果列于表 1。 纺丝过程中大 量出现断丝现象。
实施例 18
本实施例的聚合物为聚丙烯 （中石化宁波镇海炼化， 牌号 Z30S, 熔点为 167°C ) ， 金属合金为锡铋合金（熔点 138°C ) ， 蒙脱土 （美国 NanoCor, 牌号 I.44PSS ) 。 锡铋合金与聚丙烯的 体积比为 2:100， 蒙脱土与聚丙烯的重量比为 2:100， 加入适量的 抗氧剂 1010 (瑞士汽巴嘉基生产） 、 抗氧剂 168 (瑞士汽巴嘉基 生产）以及硬脂酸锌（市售）； 其中以聚丙烯为 100重量份数计， 抗氧剂 1010为 0.5份， 抗氧剂 168为 0.5份， 硬脂酸锌为 1份。
按照上述的聚合物、 蒙脱土和金属合金的原料以及配比在高 速搅拌机中混合均匀。 之后用德国 HAAKE公司 PolymLab双螺 杆挤出机挤出造粒， 挤出机各段温度为： 190°C， 200°C , 210°C , 210°C , 210°C , 200 °C (机头温度）。 将粒料加入毛细管流变仪中 在 200 °C下纺丝得到复合原丝， 柱塞速度为 5mm/min， 收卷速度 为 60m/min。 将复合原丝在 150 °C条件下拉伸至原长的 15倍后得 到聚合物 /蒙脱土 /金属复合纤维， 进行各项测试， 测试结果列于 表 1。
用扫描电镜观测， 复合纤维中金属短纤维的直径为 1.46μιη 以下。 长度为大于或等于 6.5μιη。 纺丝过程中很少出现断丝现象， 得到的纤维表面光滑。
对比例 15
除不加入金属合金外，其余均与实施例 18相同， 所得聚丙烯 /蒙脱土纤维， 进行各项测试， 测试结果列于表 1。 纺丝过程中大 量出现断丝现象， 并且得到的纤维表面粗糙。
实施例 19
本实施例的聚合物为聚丙烯 （中石化宁波镇海炼化， 牌号 Z30S, 熔点为 167°C ) ， 金属合金为锡铋合金（北京三禾鼎鑫高 新科技发展有限公司， 熔点 138°C ) ， 蒙脱土 （美国 NanoCor, 牌号 I.44PSS ) 。 锡铋合金与聚丙烯的体积比为 0.5:100， 蒙脱土 与聚丙烯的重量比为 2:100， 加入适量的抗氧剂 1010 (瑞士汽巴 嘉基生产）、 抗氧剂 168 (瑞士汽巴嘉基生产）以及硬脂酸锌（市 售） ； 其中以聚丙烯为 100重量份数计， 抗氧剂 1010为 0.5份， 抗氧剂 168为 0.5份， 硬脂酸锌为 1份。
按照上述的聚合物、 蒙脱土和金属合金的原料以及配比在高 速搅拌机中混合均匀。 之后用德国 HAAKE公司 PolymLab双螺 杆挤出机挤出造粒， 挤出机各段温度为： 190 °C， 200°C , 210°C , 210°C , 210°C , 200 °C (机头温度）。 将粒料加入毛细管流变仪中 在 200 °C下纺丝得到复合原丝， 柱塞速度为 5mm/min， 收卷速度 为 60m/min。 将复合原丝在 150°C条件下拉伸至原长的 15倍后得 到聚合物 /蒙脱土 /金属复合纤维， 进行各项测试， 测试结果列于 表 1。 用扫描电镜观测， 复合纤维中金属短纤维的直径为 1.06μιη 以下。 长度为大于或等于 7.5μιη。 纺丝过程中很少出现断丝现象， 得到的纤维表面光滑。
实施例 20
除金属合金与聚合物的体积比按 1:100外，其余均与实施例 19 相同， 所得聚合物 /蒙脱土 /金属复合纤维， 进行各项测试， 测试 结果列于表 1。
用扫描电镜观测， 复合纤维中金属短纤维的直径为 2.15μιη 以下。 长度为大于或等于 7.5μιη。 纺丝过程中很少出现断丝现象， 得到的纤维表面光滑。
实施例 21
除将复合原丝在 150°C下拉伸至原长的 5倍外， 其余均与实 施例 18相同，所得聚合物 /蒙脱土 /金属复合纤维，进行各项测试， 测试结果列于表 1。
用扫描电镜观测， 复合纤维中金属短纤维的直径为 3.01μιη 以下。 长度为大于或等于 6.5μιη。 纺丝过程中很少出现断丝现象， 得到的纤维表面光滑。
对比例 16
除不加入金属合金外，其余均与实施例 21相同， 所得聚丙烯 /蒙脱土纤维， 进行各项测试， 测试结果列于表 1。 纺丝过程中大 量出现断丝现象， 并且得到的纤维表面粗糙。
实施例 22
本实施例的聚合物为聚丙烯 （中石化宁波镇海炼化， 牌号 Z30S, 熔点为 167°C ) ， 金属合金为锡铋合金（熔点 138°C ) ， 硅氧烷改性蒙脱土 （美国 NanoCor, 牌号 I.44PSS ) 。 锡铋合金 与聚丙烯的体积比为 0.5:100，蒙脱土与聚丙烯的重量比为 2:100， 加入适量的抗氧剂 1010 (瑞士汽巴嘉基生产） 、 抗氧剂 168 (瑞 士汽巴嘉基生产） 以及硬脂酸锌（市售） ； 其中以聚丙烯为 100 重量份数计， 抗氧剂 1010为 0.5份， 抗氧剂 168为 0.5份， 硬脂 酸锌为 1份。
按照上述的聚合物、 蒙脱土和金属合金的原料以及配比在高 速搅拌机中混合均匀。 之后用德国 HAAKE公司 PolymLab双螺 杆挤出机挤出造粒， 挤出机各段温度为： 190 °C， 200°C , 210°C , 210°C , 210°C , 200 °C (机头温度）。 将粒料加入毛细管流变仪中 在 200 °C下纺丝得到复合原丝， 柱塞速度为 5mm/min， 收卷速度 为 60m/min。 将复合原丝在 150°C条件下拉伸至原长的 5倍后得 到聚合物 /蒙脱土 /金属复合纤维， 进行各项测试， 测试结果列于 表 1。
用扫描电镜观测， 复合纤维中金属短纤维的直径为 1.66μιη 以下。 长度为大于或等于 5.5μιη。 纺丝过程中很少出现断丝现象， 得到的纤维表面光滑。
实施例 23
除金属合金与聚合物的体积比按 1:100外，其余均与实施例 22 相同， 所得聚合物 /蒙脱土 /金属复合纤维， 进行各项测试， 测试 结果列于表 1。
用扫描电镜观测， 复合纤维中金属短纤维的直径为 2.45μιη 以下。 长度为大于或等于 6.5μιη。 纺丝过程中很少出现断丝现象， 得到的纤维表面光滑。
实施例 24
除将复合原丝在 150°C下拉伸至原长的 10倍外， 其余均与 实施例 21相同， 所得聚合物 /蒙脱土 /金属复合纤维， 进行各项测 试， 测试结果列于表 1。
用扫描电镜观测， 复合纤维中金属短纤维的直径为 1.67μιη 以下。 长度为大于或等于 8.5μιη。 纺丝过程中很少出现断丝现象， 得到的纤维表面光滑。
对比例 17
除不加入金属合金外，其余均与实施例 24相同， 所得聚丙烯 /蒙脱土纤维， 进行各项测试， 测试结果列于表 1。 纺丝过程中大 量出现断丝现象， 并且得到的纤维表面粗糙。
实施例 25
除将蒙脱土与聚丙烯的重量比为 0.5:100 外， 其余均与实施 例 18相同， 所得聚合物 /蒙脱土 /金属复合纤维， 进行各项测试， 测试结果列于表 1。
用扫描电镜观测， 复合纤维中金属短纤维的直径为 0.9μιη以 下。 长度为大于或等于 7.9μιη。 纺丝过程中很少出现断丝现象， 得到的纤维表面光滑。
对比例 18
除不加入金属合金外，其余均与实施例 25相同， 所得聚丙烯 /蒙脱土纤维， 进行各项测试， 测试结果列于表 1。 纺丝过程中大 量出现断丝现象， 并且得到的纤维表面粗糙。
实施例 26
除将蒙脱土与聚丙烯的重量比为 4:100外， 其余均与实施例 18相同， 所得聚合物 /蒙脱土 /金属复合纤维， 进行各项测试， 测 试结果列于表 1。
用扫描电镜观测， 复合纤维中金属短纤维的直径为 1.09μιη 以下。 长度为大于或等于 8.5μιη。 纺丝过程中很少出现断丝现象， 得到的纤维表面光滑。
对比例 19
除不加入金属合金外，其余均与实施例 26相同， 所得聚丙烯 /蒙脱土纤维， 进行各项测试， 测试结果列于表 1。 纺丝过程中大 量出现断丝现象， 并且得到的纤维表面粗糙。 除将蒙脱土与聚丙烯的重量比为 8:100外， 其余均与实施例 18相同， 所得聚合物 /蒙脱土 /金属复合纤维， 进行各项测试， 测 试结果列于表 1。
用扫描电镜观测， 复合纤维中金属短纤维的直径为 2.46μιη 以下。 长度为大于或等于 8.6μιη。 纺丝过程中很少出现断丝现象， 得到的纤维表面光滑。
对比例 20
除不加入金属合金外，其余均与实施例 27相同， 所得聚丙烯 /蒙脱土纤维， 进行各项测试， 测试结果列于表 1。 纺丝过程中大 量出现断丝现象， 并且得到的纤维表面粗糙。
实施例 28
本实施例的聚合物为聚丙烯 （中石化宁波镇海炼化， 牌号 Z30S, 熔点为 167°C ) ， 金属合金为锡铋合金（熔点 138°C ) ， 纳米碳酸钙 （河南科力， 牌号 NLY-201 , 粒径范围 30-50nm ) 。 锡铋合金与聚丙烯的体积比为 2:100， 碳酸钙与聚丙烯的重量比 为 10:100， 加入适量的抗氧剂 1010 (瑞士汽巴嘉基生产）、 抗氧 剂 168 (瑞士汽巴嘉基生产） 以及硬脂酸锌（市售） ； 其中以聚 丙烯为 100重量份数计，抗氧剂 1010为 0.5份，抗氧剂 168为 0.5 份， 硬脂酸锌为 1份。
按照上述的聚合物、 碳酸钙和金属合金的原料以及配比在高 速搅拌机中混合均匀。 之后用德国 HAAKE公司 PolymLab双螺 杆挤出机挤出造粒， 挤出机各段温度为： 190 °C， 200°C , 210°C , 210°C , 210°C , 200 °C (机头温度）。 将粒料加入毛细管流变仪中 在 200 °C下纺丝得到复合原丝， 柱塞速度为 5mm/min， 收卷速度 为 60m/min。 将复合原丝在 150 °C条件下拉伸至原长的 15倍后得 到聚合物 /碳酸钙 /金属复合纤维， 进行各项测试， 测试结果列于 表 1。
用扫描电镜观测， 复合纤维中金属短纤维的直径为 2.06μιη 以下。 长度为大于或等于 7.8μιη。 纺丝过程中很少出现断丝现象， 得到的纤维表面光滑。
对比例 21
除不加入金属合金外，其余均与实施例 28相同， 所得聚丙烯 /碳酸钙纤维， 进行各项测试， 测试结果列于表 1。 纺丝过程中大 量出现断丝现象， 并且得到的纤维表面粗糙。
实施例 29
除将碳酸钙与聚丙烯的重量比为 30:100外，其余均与实施例 24相同， 所得聚合物 /碳酸钙 /金属复合纤维， 进行各项测试， 测 试结果列于表 1。
用扫描电镜观测， 复合纤维中金属短纤维的直径为 2.09μιη 以下。 长度为大于或等于 7.5μιη。 纺丝过程中很少出现断丝现象， 得到的纤维表面光滑。
对比例 22
除不加入金属合金外，其余均与实施例 29相同， 所得聚丙烯 /碳酸钙纤维， 进行各项测试， 测试结果列于表 1。 纺丝过程中大 量出现断丝现象， 并且得到的纤维表面粗糙。
实施例 30
本实施例的聚合物为聚丙烯 （中石化宁波镇海炼化， 牌号 Z30S, 熔点为 167°C ) ， 金属合金为锡铋合金（熔点 138°C ) ， 硫酸钙晶须 （郑州博凯利， 牌号纳米硫酸钙晶须， 平均直径 500nm )。 锡铋合金与聚丙烯的体积比为 2:100， 硫酸钙与聚丙烯 的重量比为 10:100， 加入适量的抗氧剂 1010 (瑞士汽巴嘉基生 产） 、 抗氧剂 168 (瑞士汽巴嘉基生产） 以及硬脂酸锌（市售） ； 其中以聚丙烯为 100重量份数计， 抗氧剂 1010为 0.5份， 抗氧剂 168为 0.5份， 硬脂酸锌为 1份。
按照上述的聚合物、 硫酸钙和金属合金的原料以及配比在高 速搅拌机中混合均匀。 之后用德国 HAAKE公司 PolymLab双螺 杆挤出机挤出造粒， 挤出机各段温度为： 190 °C， 200°C , 210°C , 210°C , 210°C , 200 °C (机头温度）。 将粒料加入毛细管流变仪中 在 200 °C下纺丝得到复合原丝， 柱塞速度为 5mm/min， 收卷速度 为 60m/min。 将复合原丝在 150。C条件下拉伸至原长的 15倍后 得到聚合物 /硫酸钙 /金属复合纤维， 进行各项测试， 测试结果列 于表 1。
用扫描电镜观测， 复合纤维中金属短纤维的直径为 3.06μιη 以下。 长度为大于或等于 8μιη。 纺丝过程中很少出现断丝现象， 得到的纤维表面光滑。
对比例 23
除不加入金属合金外，其余均与实施例 30相同， 所得聚丙烯 /硫酸钙纤维， 进行各项测试， 测试结果列于表 1。 纺丝过程中大 量出现断丝现象， 并且得到的纤维表面粗糙。
实施例 31
聚合物釆用聚酰胺 11 (法国阿科玛， 牌号 Natural D40, 熔 点为 179°C )，金属合金为锡铋合金（熔点 138°C )，碳纳米管（北 京天奈科技， 牌号 FT-9000, 平均直径 llnm, 平均长度 ΙΟμιη, 多壁碳纳米管） 。 金属合金与聚合物的体积比为 2:100， 碳纳米 管与聚合物的重量比为 2:100， 加入适量的抗氧剂 1010 (瑞士汽 巴嘉基生产） 、 抗氧剂 168 (瑞士汽巴嘉基生产） 以及硬脂酸锌 (市售） ； 其中以聚酰胺 11为 100重量份数计， 抗氧剂 1010为 0.5份， 抗氧剂 168为 0.5份， 硬脂酸锌为 1份。
按照上述的聚合物、 碳纳米管和金属合金的原料以及配比在 高速搅拌机中混合均匀。 之后用德国 ΗΑΑΚΕ公司 PolymLab双 螺杆挤出机挤出造粒，挤出机各段温度为： 200 °C， 210°C , 220 °C , 220 °C , 220 °C , 210°C (机头温度）。 将粒料加入毛细管流变仪中 在 200 °C下纺丝得到复合原丝， 柱塞速度为 5mm/min， 收卷速度 为 60m/min。 将复合原丝在 170 °C条件下拉伸至原长的 15倍后得 到聚合物 /碳纳米管 /金属复合纤维， 进行各项测试， 测试结果列 于表 1。
用扫描电子显微镜观测， 复合纤维中金属短纤维的直径为 1.40μιη以下。 长度为大于或等于 8.1μιη。 纺丝过程中很少出现断 丝现象， 得到的纤维表面光滑。
对比例 24
除不加入金属合金外， 其余均与实施例 31相同， 聚酰胺 /碳 纳米管纤维测试结果列于表 1。 纺丝过程中大量出现断丝现象， 并且得到的纤维表面粗糙。
实施例 32
聚合物采用聚酰胺 11 (法国阿科玛， 牌号 Natural D40, 熔 点为 179°C ) ， 金属合金为锡铋合金（熔点 138°C ) ， 硅氧烷改性 蒙脱土 （美国 NanoCor, 牌号 I.44PSS ) 。 金属合金与聚合物的 体积比为 2:100， 蒙脱土与聚合物的重量比为 2:100， 加入适量的 抗氧剂 1010 (瑞士汽巴嘉基生产） 、 抗氧剂 168 (瑞士汽巴嘉基 生产）以及硬脂酸锌（市售）； 其中以聚酰胺 11为 100重量份数 计， 抗氧剂 1010为 0.5份， 抗氧剂 168为 0.5份， 硬脂酸锌为 1 份。
按照上述的聚合物、 蒙脱土和金属合金的原料以及配比在高 速搅拌机中混合均匀。 之后用德国 HAAKE公司 PolymLab双螺 杆挤出机挤出造粒， 挤出机各段温度为： 200°C， 210°C , 220 °C , 220 °C , 220 °C , 210°C (机头温度）。 将粒料加入毛细管流变仪中 在 200。C下纺丝得到复合原丝，柱塞速度为 5mm/min， 收卷速度 为 60m/min。 将复合原丝在 170 °C条件下拉伸至原长的 15倍后得 到聚合物 /蒙脱土 /金属复合纤维， 进行各项测试， 测试结果列于 表 1。
用扫描电镜观测， 复合纤维中金属短纤维的直径为 1.90μιη 以下。 长度为大于或等于 5.1μιη。 纺丝过程中很少出现断丝现象， 得到的纤维表面光滑。
对比例 25
除不加入金属合金外， 其余均与实施例 32相同， 聚酰胺 /蒙 脱土纤维测试结果列于表 1。 纺丝过程中大量出现断丝现象， 并 且得到的纤维表面粗糙。
实施例 33
除将硅氧烷改性蒙脱土改为钠基非改性纯蒙脱土 （浙江丰虹 新材料股份有限公司） 外， 其余均与实施例 32相同， 聚酰胺 /蒙 脱土 /金属纤维测试结果列于表 1。
用扫描电镜观测， 复合纤维中金属短纤维的直径为 2.50μιη 以下。长度为大于或等于 4.51μιη。纺丝过程中很少出现断丝现象， 得到的纤维表面光滑。
对比例 26
除不加入金属合金外， 其余均与实施例 33相同， 聚酰胺 /蒙 脱土纤维测试结果列于表 1。 纺丝过程中大量出现断丝现象， 并 且得到的纤维表面粗糙。
实施例 34
聚合物采用聚酰胺 11 (法国阿科玛， 牌号 Natural D40, 熔 点为 179°C ) ， 金属合金为锡铋合金（熔点 138°C ) ， 纳米二氧化 钛（日本石原二氧化钛 FT-3000, 平均直径 270nm， 平均长度 5.15μιη ) 。 金属合金与聚合物的体积比为 2:100， 二氧化钛与聚 合物的重量比为 10:100， 加入适量的抗氧剂 1010 (瑞士汽巴嘉基 生产）、抗氧剂 168 (瑞士汽巴嘉基生产）以及硬脂酸锌（市售）； 其中以聚酰胺 11为 100重量份数计， 抗氧剂 1010为 0.5份， 抗 氧剂 168为 0.5份， 硬脂酸锌为 1份。
按照上述的聚合物、 二氧化钛和金属合金的原料以及配比在 高速搅拌机中混合均匀。 之后用德国 HAAKE公司 PolymLab双 螺杆挤出机挤出造粒，挤出机各段温度为： 200 °C， 210°C , 220 °C , 220 °C , 220 °C , 210°C (机头温度）。 将粒料加入毛细管流变仪中 在 200 °C下纺丝得到复合原丝， 柱塞速度为 5mm/min， 收卷速度 为 60m/min。 将复合原丝在 170 °C条件下拉伸至原长的 15倍后得 到聚合物 /二氧化钛 /金属复合纤维， 进行各项测试， 测试结果列 于表 1。
用扫描电镜观测， 复合纤维中金属短纤维的直径为 1.30μιη 以下。 长度为大于或等于 7.1μιη。 纺丝过程中很少出现断丝现象， 得到的纤维表面光滑。
对比例 27
除不加入金属合金外， 其余均与实施例 34相同， 聚酰胺 /二 氧化钛纤维测试结果列于表 1。 纺丝过程中大量出现断丝现象， 并且得到的纤维表面粗糙。
实施例 35
聚合物采用聚酰胺 11 (法国阿科玛， 牌号 Natural D40, 熔 点为 179°C ) ， 金属合金为锡铋合金（熔点 138°C ) ， 纳米碳酸钙 (河南科力， 牌号 NLY-201, 粒径范围 30-50nm ) 。 金属合金与 聚合物的体积比为 2:100， 碳酸钙与聚合物的重量比为 10:100， 加入适量的抗氧剂 1010 (瑞士汽巴嘉基生产） 、 抗氧剂 168 (瑞 士汽巴嘉基生产） 以及硬脂酸锌 （市售） ； 其中以聚酰胺 11 为 100重量份数计， 抗氧剂 1010为 0.5份， 抗氧剂 168为 0.5份， 硬脂酸锌为 1份。 按照上述的聚合物、 碳酸钙和金属合金的原料以及配比在高 速搅拌机中混合均匀。 之后用德国 HAAKE公司 PolymLab双螺 杆挤出机挤出造粒， 挤出机各段温度为： 200 °C， 210°C , 220 °C , 220 °C , 220 °C , 210°C (机头温度）。 将粒料加入毛细管流变仪中 在 200 °C下纺丝得到复合原丝， 柱塞速度为 5mm/min， 收卷速度 为 60m/min。 将复合原丝在 170 °C条件下拉伸至原长的 15倍后得 到聚合物 /碳酸钙 /金属复合纤维， 进行各项测试， 测试结果列于 表 1。
用扫描电镜观测， 复合纤维中金属短纤维的直径为 1.50μιη 以下。 长度为大于或等于 7.1μιη。 纺丝过程中很少出现断丝现象， 得到的纤维表面光滑。
对比例 28
除不加入金属合金外， 其余均与实施例 35相同， 聚酰胺 /碳 酸钙纤维测试结果列于表 1。 纺丝过程中大量出现断丝现象， 并 且得到的纤维表面粗糙。
1
Figure imgf000035_0001
表 2
Figure imgf000036_0001
从表 2中数据可以看出，相对于未含有低熔点金属的聚合物 / 填料复合纤维， 相应的本发明的聚合物 /填料 /低熔点金属复合纤 维在相同的原丝拉伸倍率条件下具有更大的拉伸强度和更大的断 裂伸长率。 这些数据说明， 相对于聚合物 /填料复合纤维， 少量低 熔点金属的加入可以实现聚合物 /填料 /金属复合纤维的拉伸断裂 强度、 断裂伸长率和体积电阻率的同时提高。

Claims

权 利 要 求
1、 一种聚合物 /填料 /金属复合纤维， 其包括含有金属短纤维和 填料的聚合物纤维， 其微观结构为金属短纤维作为分散相分布在 聚合物纤维中， 而且作为分散相的金属短纤维沿着聚合物纤维轴 平行分布， 填料分散在聚合物纤维内， 分布在金属短纤维之间； 所述聚合物为热塑性树脂； 所述填料在所述聚合物加工温度下不 发生熔融； 所述金属为低熔点金属， 选自单组分金属和金属合金 中的至少一种， 其熔点在 20~480°C， 并且其熔点同时低于所述聚 合物的加工温度。
2、 根据权利要求 1所述的聚合物 /填料 /金属复合纤维， 其特征 在于， 所述的金属短纤维和聚合物纤维的体积比为 0.01:100~20:100，优选为 0.1:100~4:100，更优选为 0.5:100~2:100。
3、 根据权利要求 1或 2所述的聚合物 /填料 /金属复合纤维， 其 特征在于， 所述的金属熔点在 100~250°C， 优选在 120~230° (。
4、 根据权利要求 1-3中任一项所述的聚合物 /填料 /金属复合纤 维， 其特征在于， 作为所述金属的单组分金属为镓、 铯、 铷、 铟、 锡、 铋、 镉、 铅元素的单质金属； 作为所述金属的金属合金为镓、 铯、 铷、 铟、 锡、 铋、 镉、 铅元素中两种以上的金属合金， 或者 为镓、 铯、 铷、 铟、 锡、 铋、 镉、 铅元素中的至少一种与铜、 银、 金、 铁或锌元素中的至少一种的金属合金， 或者为镓、 铯、 铷、 铟、 锡、 铋、 镉、 铅元素中的至少一种与铜、 银、 金、 铁或锌元 素中的至少一种和选自硅元素和碳元素中的至少一种形成的合 金。
5、 根据权利要求 1-4中任一项所述的聚合物 /填料 /金属复合纤 维， 其特征在于所述的金属短纤维的直径小于或等于 12μιη， 优 选小于或等于 8μιη， 更优选小于或等于 3μιη。
6、 根据权利要求 1-5中任一项所述的聚合物 /填料 /金属复合纤 维， 其特征在于， 所述的聚合物为熔点在 90~450°C， 优选在 100~290°C的热塑性树脂。
7、 根据权利要求 6所述的聚合物 /填料 /金属复合纤维， 其特征 在于， 所述的聚合物选自聚乙烯、 聚丙烯、 聚酰胺、 聚酯中的一 种。
8、 根据权利要求 1-7中任一项所述的聚合物 /填料 /金属复合纤 维， 其特征在于， 所述的填料与聚合物的重量比为 0.1:100-30:100, 优选为 0.5:100~10:100， 更优选为 1:100~2:100。
9、 根据权利要求 1-8中任一项所述的聚合物 /填料 /金属复合纤 维， 其特征在于， 所述填料的三维尺寸中的至少一维尺寸小于 500μιη, 优选小于 300μιη。
10、 根据权利要求 1-9中任一项所述的聚合物 /填料 /金属复合纤 维， 其特征在于， 所述填料是非导电填料和 /或导电填料。
11、 根据权利要求 10 所述的聚合物 /填料 /金属复合纤维， 其特 征在于， 所述非导电填料为非导电的金属盐、 金属氮化物、 非金 属氮化物、 非金属碳化物、 金属氢氧化物、 金属氧化物、 非金属 氧化物、 天然矿石中的至少一种。
12、 根据权利要求 10 所述的聚合物 /填料 /金属复合纤维， 其特 征在于， 所述非导电填料为碳酸钙、 硫酸钡、 硫酸钙、 氯化银、 氢氧化铝、 氢氧化镁、 氧化铝、 氧化镁、 二氧化硅、 石棉、 滑石、 高岭土、 云母、 长石、 硅灰石、 蒙脱土中的至少一种。
13、 根据权利要求 12 所述的聚合物 /填料 /金属复合纤维， 其特 征在于， 所述蒙脱土为非改性纯蒙脱土和有机改性蒙脱土中的至 少一种。
14、 根据权利要求 13 所述的聚合物 /填料 /金属复合纤维， 其特 征在于，所述的有机改性蒙脱土选自有机季铵盐改性蒙脱土、季磷 盐改性蒙脱土、 有机硅改性蒙脱土、 硅氧烷改性蒙脱土， 胺类改 性蒙脱土中至少一种。
15、 根据权利要求 10 所述的聚合物 /填料 /金属复合纤维， 其特 征在于， 所述的导电填料为单组分金属、金属合金、金属氧化物、 金属盐、 金属氮化物、 非金属氮化物、 金属氢氧化物、 导电聚合 物、 导电碳材料中的至少一种。
16、 根据权利要求 10 所述的聚合物 /填料 /金属复合纤维， 其特 征在于， 所述的导电填料为金、 银、 铜、 铁、 金合金、 银合金、 铜合金、 铁合金、 二氧化钛、 三氧化二铁、 四氧化三铁、 氧化银、 氧化锌、 炭黑、 碳纳米管、 石墨烯和线性导电聚苯胺中的至少一 种。
17、 根据权利要求 9-16中任一项所述的聚合物 /填料 /金属复合纤 维， 其特征在于， 所述的填料为纳米级填料。
18、 根据权利要求 17 所述的聚合物 /填料 /金属复合纤维， 其特 征在于， 所述的纳米级填料的三维尺寸中的至少一维尺寸小于 100腿， 优选小于 50腿。
19、 根据权利要求 16 所述的聚合物 /填料 /金属复合纤维， 其特 征在于， 所述的碳纳米管选自单壁碳纳米管、 双壁碳纳米管、 多 壁碳纳米管中的至少一种。
20、 根据权利要求 1-19中任一项所述的聚合物 /填料 /金属复合纤 维， 其特征在于， 所述复合纤维由包括如下步骤的方法制备： 步骤一、 按给定量将所述包括所述聚合物、 填料与金属在内 的组分进行熔融共混， 得到聚合物 /填料 /金属共混物；
步骤二、将步骤一中所得聚合物 /填料 /金属共混物在纺丝设备 上纺丝， 得到聚合物 /填料 /金属复合原丝；
步骤三、将步骤二中所得聚合物 /填料 /金属复合原丝在低于所 采用的聚合物熔点的温度， 且高于或等于所采用的低熔点金属熔 点的温度范围内加热拉伸得到聚合物 /填料 /金属复合纤维。
21、 根据权利要求 20 所述的聚合物 /填料 /金属复合纤维， 其特 征在于，所述步骤三所述的加热拉伸的拉伸倍率大于或等于 2倍， 优选为大于或等于 5倍， 更优选为大于或等于 10倍。
22、 一种制备根据权利要求 1-19任一项所述的聚合物 /填料 /金属 复合纤维的方法， 包括如下步骤：
步骤一、 按给定量将所述包括所述聚合物、 填料与金属在内 的组分进行熔融共混， 得到聚合物 /填料 /金属共混物；
步骤二、将步骤一中所得聚合物 /填料 /金属共混物在纺丝设备 上纺丝， 得到聚合物 /填料 /金属复合原丝；
步骤三、将步骤二中所得聚合物 /填料 /金属复合原丝在低于所 采用的聚合物熔点的温度， 且高于或等于所采用的低熔点金属熔 点的温度范围内加热拉伸得到聚合物 /填料 /金属复合纤维。
23、 根据权利要求 22所述的方法， 其特征在于步骤三所述的加 热拉伸的拉伸倍率大于或等于 2倍， 优选为大于或等于 5倍， 更 优选为大于或等于 10倍。
24、 一种聚合物 /填料 /低熔点金属共混物， 其微观形态为所述低 熔点金属作为分散相均匀分布在作为连续相的聚合物基体中， 所 述填料分散在所述低熔点金属颗粒之间， 其中所述聚合物为热塑 性树脂； 所述填料在所述聚合物加工温度下不发生熔融； 所述低 熔点金属选自单组分金属和金属合金中的至少一种并且其熔点在 20~480。C， 并且其熔点同时低于所述聚合物的加工温度。
25、 根据权利要求 24 所述的聚合物 /填料 /金属共混物， 其特征 在于， 所述的金属和聚合物的体积比为 0.01:100~20:100， 优选为 0.1:100-4:100, 更优选为 0.5:100~2:100。
26、 根据权利要求 24或 25所述的聚合物 /填料 /金属共混物， 其 特征在于， 所述的金属熔点在 100~250°C， 优选在 120~230° (。
27、 根据权利要求 24-26中任一项所述的聚合物 /填料 /金属共混 物， 其特征在于， 作为所述金属的单组分金属为镓、 铯、 铷、 铟、 锡、 铋、 镉、 铅元素的单质金属； 作为所述金属的金属合金为镓、 铯、 铷、 铟、 锡、 铋、 镉、 铅元素中两种以上的金属合金， 或者 为镓、 铯、 铷、 铟、 锡、 铋、 镉、 铅元素中的至少一种与铜、 银、 金、 铁或锌元素中的至少一种的金属合金， 或者为镓、 铯、 铷、 铟、 锡、 铋、 镉、 铅元素中的至少一种与铜、 银、 金、 铁或锌元 素中的至少一种和选自硅元素和碳元素中的至少一种形成的合 金。
28、 根据权利要求 24-27中任一项所述的聚合物 /填料 /金属共混 物， 其特征在于， 所述的聚合物为熔点在 90~450°C， 优选在 100~290°C的热塑性树脂。
29、 根据权利要求 28 所述的聚合物 /填料 /金属共混物， 其特征 在于， 所述的聚合物选自聚乙烯、 聚丙烯、 聚酰胺、 聚酯中的一 种。
30、 根据权利要求 24-29中任一项所述的聚合物 /填料 /金属共混 物， 其特征在于， 所述的填料与聚合物的重量比为 0.1:100-30:100, 优选为 0.5:100~10:100， 更优选为 1:100~2:100。
31、 根据权利要求 24-30中任一项所述的聚合物 /填料 /金属共混 物， 其特征在于， 所述填料的三维尺寸中的至少一维尺寸小于 500μιη, 优选小于 300μιη。
32、 根据权利要求 24-31中任一项所述的聚合物 /填料 /金属共混 物， 其特征在于， 所述填料是非导电填料和 /或导电填料。
33、 根据权利要求 32 所述的聚合物 /填料 /金属共混物， 其特征 在于， 所述非导电填料为非导电的金属盐、 金属氮化物、 非金属 氮化物、 非金属碳化物、 金属氢氧化物、 金属氧化物、 非金属氧 化物、 天然矿石中的至少一种。
34、 根据权利要求 32 所述的聚合物 /填料 /金属共混物， 其特征 在于， 所述非导电填料为碳酸钙、 硫酸钡、 硫酸钙、 氯化银、 氢 氧化铝、 氢氧化镁、 氧化铝、 氧化镁、 二氧化硅、 石棉、 滑石、 高岭土、 云母、 长石、 硅灰石、 蒙脱土中的至少一种。
35、 根据权利要求 34 所述的聚合物 /填料 /金属共混物， 其特征 在于， 所述蒙脱土为非改性纯蒙脱土和有机改性蒙脱土中的至少 一种。
36、 根据权利要求 35 所述的聚合物 /填料 /金属共混物， 其特征 在于，所述的有机改性蒙脱土选自有机季铵盐改性蒙脱土、季镇盐 改性蒙脱土、 有机硅改性蒙脱土、 硅氧烷改性蒙脱土， 胺类改性 蒙脱土中至少一种。
37、 根据权利要求 32 所述的聚合物 /填料 /金属共混物， 其特征 在于， 所述的导电填料为单组分金属、 金属合金、 金属氧化物、 金属盐、 金属氮化物、 非金属氮化物、 金属氢氧化物、 导电聚合 物、 导电碳材料中的至少一种。
38、 根据权利要求 32 所述的聚合物 /填料 /金属共混物， 其特征 在于， 所述的导电填料为金、 银、 铜、 铁、 金合金、 银合金、 铜 合金、 铁合金、 二氧化钛、 三氧化二铁、 四氧化三铁、 氧化银、 氧化锌、 炭黑、 碳纳米管、 石墨烯和线性导电聚苯胺中的至少一 种。
39、 根据权利要求 32~38中任一项所述的聚合物 /填料 /金属共混 物， 其特征在于， 所述的填料为纳米级填料。
40、 根据权利要求 39 所述的聚合物 /填料 /金属共混物， 其特征 在于， 所述的纳米级填料的三维尺寸中的至少一维尺寸小于 100腿， 优选小于 50腿。
41、 根据权利要求 38 所述的聚合物 /填料 /金属共混物， 其特征 在于， 所述的碳纳米管选自单壁碳纳米管、 双壁碳纳米管、 多壁 碳纳米管中的至少一种。
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