CN104099680A - Polymer/nonconductive filling material/metal composite fiber and preparation method thereof - Google Patents
Polymer/nonconductive filling material/metal composite fiber and preparation method thereof Download PDFInfo
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Abstract
The invention relates to polymer/nonconductive filling material/metal composite fibers which include polymer fibers containing metal short fibers and a nonconductive filling material, wherein the metal short fibers, as a dispersed phase, are distributed in the polymer fibers and are distributed in the direction of an axis of the polymer fibers in parallel; and the nonconductive filling material is dispersed in the polymer fibers and is distributed among the metal short fibers. The nonconductive filling material is not melted at a processing temperature of the polymer. The metal is a low-melting-point metal and is selected from at least one of a single-component metal and a metal alloy. A melting point of the metal ranges from 20-480 DEG C and meanwhile is lower than the processing temperature of the polymer. A volume ratio of the metal short fibers to the polymer fibers ranges from 0.01:100-20:100 and a weight ratio of the nonconductive filling material to the polymer ranges from 0.1-100-30:100. By means of the composite fibers, a volume resistivity can be reduced, a wire fracturing rate is reduced and the fibers are smooth in surfaces. A preparation method is simple, is low in cost and is easy to carry out in industrially large-scale production.
Description
Technical field
The present invention relates to synthetic fiber field, say further, the present invention relates to composite fibre of a kind of polymer/non-conducting filler/metal and preparation method thereof.
Background technology
The characteristics such as compare natural fabric, synthetic fiber have cheap, and the low and hydroscopicity of density is low, are widely used in the field such as textile garment class, woven bag of daily productive life.But the electrical insulation capability of synthetic fiber is good, and resistivity is high, in use easily produce static, all can bring harm to industrial production and people's lives.And along with high-tech development, because static and Electrostatic Absorption dust are to cause one of modern electronic equipment operational failure, short circuit, dropout, error code, immediate cause that yield rate is low.All the protection of static is had to special requirement in industries such as oil, chemical industry, precision optical machinery, colliery, food, medicine.Therefore, thus exploitation has the fiber of superior electrical property to be reduced the harm that brings of static and becomes very urgent problem.
The nanoscale tubular structure of the similar curling graphite that CNT is made up of carbon hexatomic ring.Because CNT has excellent electricity and mechanical property, be therefore widely used in polymer matrix composite or composite fibre field.But there is serious reuniting effect because the high surface energy of nano particle self causes CNT, thereby increased loading and the cost of nano particle.Meanwhile, a large amount of nano-particles filled has also caused difficulty to the production of fiber.How to reduce CNT consumption, reducing production difficulty is problem demanding prompt solution.
Adopting composite conducting non-conducting filler technology to add the 3rd component is effectively to improve Conductivity of Fiber electrical efficiency, reduces the effective ways of content of carbon nanotubes.Patent CN102409421A discloses a kind of preparation method who prepares PP/Nano tin ash/carbon nano tube composite fibre.Although this technology has reduced the resistivity of composite fibre, the 3rd component adding is similarly nano particle, has increased the difficulty processing raw material, and fiber surface is coarse, and feel is poor, mechanical properties decrease, the easy phenomenon such as fracture of wire in production.
In recent years, there is new development in polymer/low-melting-point metal field of compound material both at home and abroad.Low-melting-point metal is widely used in the field of compound material of polymer as a new non-conducting filler using characteristics such as high conductivity, easy processing.Patent CN102021671A discloses a kind of polymer/low-melting-point metal compound wire and manufacture method thereof, and patent CN102140707A discloses a kind of skin-core composite electromagnetic shielding fiber and preparation method thereof simultaneously.Above-mentioned two technology utilize core-sheath technology to prepare the method for polymer overmold low-melting-point metal wire or fiber.But in this technology, need special composite spinning machine, and strengthen as the sandwich layer metal proportion of fiber, although ensured fiber low resistivity, need a large amount of metals that add, increased production cost.
Summary of the invention
In order to there is with easy and method preparation cheaply the composite fibre of low specific insulation and excellent handle, the present invention is proposed.
An object of the present invention is to provide a kind of polymer/non-conducting filler/metal composite fiber, this composite fibre has good antistatic property and feel.
Another object of the present invention is to provide the preparation method of above-mentioned polymer/non-conducting filler/metal composite fiber, the method adopts in-situ method to prepare polymer/non-conducting filler/metal composite fiber, in polymer fiber preparation process, is become by metallic particles stretcher strain the preparation method of broken-staple metal fibre as the low-melting-point metal of decentralized photo.Due to the existence of non-conducting filler in system, in Blending Processes, the viscosity of system improves very large, under the condition of identical shear rate, system is subject to larger shear action, thereby make low-melting-point metal disperse particle diameter to diminish in macromolecular material matrix, on the other hand, also reduced the probability that after metallic particles collision, generation merges again, make the particle diameter of metallic particles become less, metallic particles is more, between metallic particles, distance is less, so metallic particles original position be deformed into metal fibre time, make staple fibre diameter less, between staple fibre, distance is shorter, thereby realize the object that improves resistant fiber antistatic property in the situation that of lower metal filled amount.Method of the present invention is to realize on existing general fibre production equipment, thereby makes preparation method have good applicability and lower equipment cost.
A kind of polymer/non-conducting filler/metal composite fiber of the present invention, comprise the polymer fiber that contains non-conducting filler and broken-staple metal fibre, its microstructure be broken-staple metal fibre as dispersed phase distribution in polymer fiber, and as the broken-staple metal fibre of decentralized photo along the parallel distribution of polymer fiber axle; Non-conducting filler is dispersed in polymer fiber, is distributed between broken-staple metal fibre.Because the existence of non-conducting filler makes staple fibre diameter less, between staple fibre, distance is shorter, and the antistatic property of prepared composite fibre is improved, and keeps the good feel of fiber.
In a kind of polymer/non-conducting filler/metal composite fiber of the present invention, the polymer of described polymer fiber is thermoplastic resin, is preferably the thermoplastic resin of fusing point at 90～450 ° of C, and more preferably fusing point is the thermoplastic resin of 100～290 ° of C.The most preferably one in polyethylene, polypropylene, polyamide or polyester etc.What wherein said polyamide comprised any kind in prior art can spinning poly acid amides, preferably nylon 6, nylon 66, nylon 11 or nylon 12.Described polyester can be any polyester that can spinning, preferably polyethylene terephthalate (PET) or polytrimethylene terephthalate (PTT) in prior art.
Non-conducting filler described in a kind of polymer/non-conducting filler/metal composite fiber of the present invention is disclosed various non-conducting fillers in prior art.The index of general available technology adopting powder resistance rate is distinguished non-conducting filler and conductive filler, and wherein powder resistance rate is less than 1 × 10
9the filler of Ω CM is called conductive filler, and powder resistance rate is more than or equal to 1 × 10
9the filler of Ω CM is called non-conducting filler.At described Polymer Processing temperature, there is not melting in non-conducting filler of the present invention.In the present invention to the shape of described non-conducting filler without any restriction, can be the non-conducting filler of any shape, can be spherical or class is spherical, elliposoidal, line style, aciculiform, fiber shape, bar-shaped, sheet etc.; The size of these non-conducting fillers is without any restriction, as long as can be dispersed in polymeric matrix and be less than the diameter of the composite fibre of final preparation, preferably on its three-dimensional dimension, at least one dimension size is less than 500 μ m, is preferably less than the filler of 300 μ m; More preferably nano level non-conducting filler in prior art.Can reach the non-conducting filler of nano-scale in 0 dimension, 1 dimension or 2 dimensions, preferably 1 dimension or 2 dimension sizes can reach the non-conducting filler of nano-scale.Wherein 0 diameter that dimension nanoscale non-conducting filler is preferred spherical or class is spherical is at nano level non-conducting filler; 1 dimension nano material is the non-conducting filler of radial dimension in shapes such as nano level line style, aciculiform, fiber shapes; 2 dimension nano materials are that thickness is nano level sheet non-conducting filler.So-called nano-grade size, generally refers to the size that is less than 100nm, but some known nano-sized filler in prior art, such as nanometer calcium sulfate whisker average diameter can, in hundreds of nanometer, be still also usually called nanoscale.So the non-conducting filler of the present invention's nano-scale herein refers to the nanoscale non-conducting filler of usually thinking in prior art.Described nanoscale non-conducting filler more preferably has at least one dimension to be less than 100nm on its three-dimensional dimension, is most preferably less than 50nm.
Non-conducting filler in polymer/non-conducting filler/metal composite fiber of the present invention is preferably at least one in non-conductive slaine, metal nitride, non-metal nitride, non-metallic carbide, metal hydroxides, metal oxide, nonmetal oxide, natural crystal; More preferably at least one in calcium carbonate, barium sulfate, calcium sulfate, silver chlorate, aluminium hydroxide, magnesium hydroxide, aluminium oxide, magnesia, silica, asbestos, talcum, kaolin, mica, feldspar, wollastonite, imvite.
In polymer/non-conducting filler/metal composite fiber of the present invention, the weight ratio of non-conducting filler and polymer fiber is 0.1:100～30:100, is preferably 0.5:100～10:100, more preferably 1:100～2:100.
Described in a kind of polymer/non-conducting filler/metal composite fiber of the present invention, the metal of broken-staple metal fibre is low melting metal, be that fusing point is at 20～480 ° of C, be preferably 100～250 ° of C, more preferably at least one in one pack system metal and the metal alloy of 120～230 ° of C, and its fusing point is simultaneously lower than described Polymer Processing temperature.
Preferably, the one pack system metal in described metal is the elemental metals of gallium, caesium, rubidium, indium, tin, bismuth, cadmium, lead element; Metal alloy in described metal is metal alloy two or more in gallium, caesium, rubidium, indium, tin, bismuth, cadmium, lead element, or be at least one the metal alloy at least one and copper, silver, gold, iron or the zinc element in gallium, caesium, rubidium, indium, tin, bismuth, cadmium, lead element, or be the alloy that at least one and element silicon at least one and copper, silver, gold, iron or the zinc element in gallium, caesium, rubidium, indium, tin, bismuth, cadmium, lead element and/or carbon form.
In polymer/non-conducting filler/metal composite fiber of the present invention, the volume ratio of broken-staple metal fibre and polymer fiber is 0.01:100～20:100, is preferably 0.1:100～4:100, more preferably 0.5:100～2:100.
In a kind of polymer/non-conducting filler/metal composite fiber of the present invention, described in be dispersed in the broken-staple metal fibre in polymer fiber, its preferred diameter is less than or equal to 12 μ m, is more preferably less than or equal to 8 μ m, most preferably is and is less than or equal to 3 μ m.
The preparation method of polymer/non-conducting filler/metal composite fiber of the present invention comprises the following steps:
Step 1, carry out melt blending by comprising described thermoplastic resin, described non-conducting filler and described metal in interior component by described amount, obtain polymer/non-conducting filler/metal blend.
Wherein said melt blending is the processing conditions of common thermoplastic resin melt blending.
The microscopic pattern of polymer/non-conducting filler/metal blend of gained is: metal is evenly distributed in the thermoplastic resin of continuous phase as decentralized photo.Non-conducting filler is dispersed between metallic particles, because the viscosity that has co-mixing system of non-conducting filler in system improves very large, under the condition of identical shear rate, system is subject to larger shear action, thereby makes low-melting-point metal in polymeric matrix, disperse particle diameter to diminish, on the other hand, also reduced the probability that after metallic particles collision, generation merges again, make the particle diameter of metallic particles become less, metallic particles is more, and between metallic particles, distance is less.
Step 2, by the spinning on spinning equipment of resulting polymers/non-conducting filler in step 1/metal blend, obtain polymer/non-conducting filler/metal composite precursor.
Wherein said spinning equipment is spinning equipment general in prior art, under the common spinning condition of adopted thermoplastic resin spinning, adopts common spray silk and rolling speed to carry out spinning.Conventionally, rolling speed is faster, and the fibre diameter obtaining is thinner, and wherein broken-staple metal fibre diameter is less, causes the electrical property of the composite fibre finally obtaining better.
Step 3, the polymer/non-conducting filler of gained in step 2/metal composite precursor is added to hot-stretch in the temperature of the thermoplastic resin fusing point lower than adopted and the temperature range greater than or equal to described low-melting-point metal fusing point obtain polymer/non-conducting filler/metal composite fiber.
The stretching ratio that wherein adds hot-stretch adopts common stretching ratio, preferably greater than or equal to 2 times, is more preferably more than or equal to 5 times, most preferably is and is more than or equal to 10 times.Along with the diameter of the raising broken-staple metal fibre of stretching ratio is less, the electrical property of composite fibre improves, while is due to the existence of non-conducting filler in system, the particle diameter of the decentralized photo metallic particles of resulting polymers/non-conducting filler in step 1/metal blend becomes less, metallic particles is more, between metallic particles, distance is less, so in prepared composite fibre, broken-staple metal fibre diameter is less after step 2 and step 3, between broken-staple metal fibre, distance is shorter, makes the electrical property of composite fibre better.
The method in the preparation method's of polymer/non-conducting filler/metal composite fiber of the present invention step 1, described polymer, non-conducting filler and metal melting blend being adopted is exactly common melt-blending process in rubber and plastic processing, blending temperature is the common processing temperature of thermoplastic resin, should in the scope that not only ensures adopted thermoplastic resin and the complete melting of metal but also can not make adopted thermoplastic resin decompose, select shortly.In addition,, according to processing needs, can in blend material, add in right amount the conventional auxiliary agent of thermoplastic resin processing.In Blending Processes, each components such as described thermoplastic resin, non-conducting filler and metal can be added simultaneously and in melt blending equipment, carried out melt blending by modes such as metered charge; Also can first pass through general mixing device, in advance described each component be mixed, and then through rubber plastic blend equipment melt blending.
The rubber plastic blend equipment using in preparation method's step 1 can be mill, banbury, single screw extrusion machine, double screw extruder or torque rheometer etc.Described material mixing equipment is selected from homogenizer of the prior art, kneader etc. mechanical mixing equipment.
Conventional auxiliary agent also can contain field of plastics processing in the raw material of preparation method's step 1 in.Such as antioxidant, plasticizer and other processing aid etc.These conventional auxiliary dosages are conventional amount used, or carry out suitable adjustment according to the requirement of actual conditions.
It is the necessary condition that ensures to obtain polymer/non-conducting filler/metal composite fiber of the present invention that the present invention prepares the hot-stretch that adds of step 3 in the method for composite fibre, the viscosity that has co-mixing system due to non-conducting filler in system in step 1 improves very large, under the condition of identical shear rate, system is subject to larger shear action, thereby make low-melting-point metal in polymeric matrix, disperse particle diameter to diminish, on the other hand, also reduced the probability that after metallic particles collision, generation merges again, make the particle diameter of metallic particles become less, metallic particles is more, between metallic particles, distance is less, this is the guarantee that obtains polymer/non-conducting filler/metal composite fiber of the present invention.The microscopic pattern of prepared like this polymer/non-conducting filler/metal composite fiber is: for broken-staple metal fibre as dispersed phase distribution in polymer fiber, and as the broken-staple metal fibre of decentralized photo along the parallel distribution of polymer fiber axle; Non-conducting filler is dispersed between broken-staple metal fibre, and because the existence of non-conducting filler makes staple fibre diameter less, between staple fibre, distance is shorter, and the antistatic property of prepared fiber is improved, and keeps the good feel of fiber; Simultaneously, because broken-staple metal fibre is arranged in polymer fiber inside, protection broken-staple metal fibre not by bending, stretch, infringement when folding, wearing and tearing and washing, solved layer on surface of metal oxidizable, easily come off or metal dust is easily reunited, thereby the problem that causes antistatic effect to decline; And due to adding of metal, solved the problem of polymer/non-conducting filler fibre spinning difficulty, spinning process is very smooth, and fracture of wire situation reduces in a large number.
The present invention proposes to adopt general spinning equipment to prepare anti-electrostatic polymer/non-conducting filler/metal composite fiber, significantly reduces costs, and has applicability widely.The selected low-melting-point metal of polymer/non-conducting filler/metal composite fiber of the present invention can improve the spinning properties of the fiber in processability and the spinning process of granulation process, enhances productivity, and saves production cost; And can arrange in pairs or groups to widen working condition by selecting fusing point to differ thermoplastic resin and the metal that scope is large, be easy to produce.
Detailed description of the invention
Further describe the present invention below in conjunction with embodiment.Scope of the present invention is not subject to the restriction of these embodiment, and scope of the present invention proposes in the appended claims.
in embodiment, experimental data is measured with following instrument and equipment and assay method:
(1) method of testing of the diameter of broken-staple metal fibre is utilized ESEM after utilizing chemical solvent to remove polymeric matrix.
(2) the specific insulation method of testing of composite fibre is as follows: the method for testing of composite fibre specific insulation is: the composite fibre of 1, choosing 2cm left and right length, use conductive tape adhesiving metal aluminium foil as test electrode at two ends, the length t of the composite fibre between measurement electrode the inner; 2, measure the diameter d of composite fibre with optics fibrescope; 3, use the PC-68 high resistant instrument of Shanghai precision instrumentation company to measure fiber volume resistance R
v; 4, calculate the specific insulation ρ of fiber sample according to following formula
v,
after measuring 10 fibers, average.
Embodiment 1
The polymer of the present embodiment is polypropylene (fusing point is 167 DEG C for China Petrochemical Industry's Zhenhai Ningbo refinery, trade mark Z30S), metal alloy is sn-bi alloy (Beijing three He Dingxin high and new technology Development Co., Ltds, 138 DEG C of fusing points), imvite (U.S. NanoCor, the trade mark is I.44PSS).Sn-bi alloy and polyacrylic volume ratio are 0.5:100, and imvite and polyacrylic weight ratio are 2:100, add appropriate antioxidant 1010 (Switzerland's Ciba-Geigy is produced), irgasfos 168 (Switzerland's Ciba-Geigy is produced) and zinc stearate (commercially available); Wherein, taking polypropylene as 100 parts by weight, antioxidant 1010 is 0.5 part, and irgasfos 168 is 0.5 part, and zinc stearate is 1 part.
Mix in homogenizer according to the raw material of above-mentioned polymer, imvite and metal alloy and proportioning.Use afterwards the German HAAKE PolymLab of company double screw extruder extruding pelletization, each section of temperature of extruder is: 190 DEG C, and 200 DEG C, 210 DEG C, 210 DEG C, 210 DEG C, 200 DEG C (head temperature).Add in capillary rheometer spinning at 200 DEG C to obtain compound precursor pellet, velocity of plunger is 5mm/min, and rolling speed is 60m/min.After compound precursor being stretched under 150 DEG C of conditions to 15 times of former length, obtain polymer-montmorillonoid/metal composite fiber, carry out every test, test result is listed in table 1.
With flying-spot microscope observation, in composite fibre, the diameter of broken-staple metal fibre is below 1.06 μ m.Length is for being more than or equal to 7.5 μ m.In spinning process, seldom occur fracture of wire phenomenon, the fiber surface obtaining is smooth.
Embodiment 2
Except the volume ratio of metal alloy and polymer is pressed 1:100, all the other are all identical with embodiment 1, and resulting polymers/imvite/metal composite fiber carries out every test, and test result is listed in table 1.
With flying-spot microscope observation, in composite fibre, the diameter of broken-staple metal fibre is below 2.15 μ m.Length is for being more than or equal to 7.5 μ m.In spinning process, seldom occur fracture of wire phenomenon, the fiber surface obtaining is smooth.
Embodiment 3
Except the volume ratio of metal alloy and polymer is pressed 2:100, all the other are all identical with embodiment 1, and resulting polymers/imvite/metal composite fiber carries out every test, and test result is listed in table 1.
With flying-spot microscope observation, in composite fibre, the diameter of broken-staple metal fibre is below 2.46 μ m.Length is for being more than or equal to 7.5 μ m.In spinning process, seldom occur fracture of wire phenomenon, the fiber surface obtaining is smooth.
Comparative example 1
Except not adding metal alloy, all the other are all identical with embodiment 1, and gained level polypropylene/montmorillonoid fiber, carries out every test, and test result is listed in table 1.In spinning process, occur in a large number fracture of wire phenomenon, and the fiber surface obtaining is coarse.
Embodiment 4
Except compound precursor being stretched at 150 DEG C 5 times of former length, all the other are all identical with embodiment 3, and resulting polymers/imvite/metal composite fiber carries out every test, and test result is listed in table 1.
With flying-spot microscope observation, in composite fibre, the diameter of broken-staple metal fibre is below 3.01 μ m.Length is for being more than or equal to 6.5 μ m.In spinning process, seldom occur fracture of wire phenomenon, the fiber surface obtaining is smooth.
Comparative example 2
Except not adding metal alloy, all the other are all identical with embodiment 4, and gained level polypropylene/montmorillonoid fiber, carries out every test, and test result is listed in table 1.In spinning process, occur in a large number fracture of wire phenomenon, and the fiber surface obtaining is coarse.
Embodiment 5
Except compound precursor being stretched at 150 DEG C 10 times of former length, all the other are all identical with embodiment 3, and resulting polymers/imvite/metal composite fiber carries out every test, and test result is listed in table 1.
With flying-spot microscope observation, in composite fibre, the diameter of broken-staple metal fibre is below 2.05 μ m.Length is for being more than or equal to 8.5 μ m.In spinning process, seldom occur fracture of wire phenomenon, the fiber surface obtaining is smooth.
Comparative example 3
Except not adding metal alloy, all the other are all identical with embodiment 5, and gained level polypropylene/montmorillonoid fiber, carries out every test, and test result is listed in table 1.In spinning process, occur in a large number fracture of wire phenomenon, and the fiber surface obtaining is coarse.
Embodiment 6
The polymer of the present embodiment is polypropylene (fusing point is 167 DEG C for China Petrochemical Industry's Zhenhai Ningbo refinery, trade mark Z30S), and metal alloy is sn-bi alloy (138 DEG C of fusing point), nano-calcium carbonate (Henan section power, trade mark NLY-201, particle size range 30-50nm).Sn-bi alloy and polyacrylic volume ratio are 2:100, and calcium carbonate and polyacrylic weight ratio are 10:100, add appropriate antioxidant 1010 (Switzerland's Ciba-Geigy is produced), irgasfos 168 (Switzerland's Ciba-Geigy is produced) and zinc stearate (commercially available); Wherein, taking polypropylene as 100 parts by weight, antioxidant 1010 is 0.5 part, and irgasfos 168 is 0.5 part, and zinc stearate is 1 part.
Mix in homogenizer according to the raw material of above-mentioned polymer, calcium carbonate and metal alloy and proportioning.Use afterwards the German HAAKE PolymLab of company double screw extruder extruding pelletization, each section of temperature of extruder is: 190 DEG C, and 200 DEG C, 210 DEG C, 210 DEG C, 210 DEG C, 200 DEG C (head temperature).Add in capillary rheometer spinning at 200 DEG C to obtain compound precursor pellet, velocity of plunger is 5mm/min, and rolling speed is 60m/min.After compound precursor being stretched under 150 DEG C of conditions to 15 times of former length, obtain polymer/calcium carbonate/metal composite fiber, carry out every test, test result is listed in table 1.
With flying-spot microscope observation, in composite fibre, the diameter of broken-staple metal fibre is below 2.06 μ m.Length is for being more than or equal to 7.8 μ m.In spinning process, seldom occur fracture of wire phenomenon, the fiber surface obtaining is smooth.
Comparative example 4
Except not adding metal alloy, all the other are all identical with embodiment 6, and gained polypropylene/calcium carbonate fiber, carries out every test, and test result is listed in table 1.In spinning process, occur in a large number fracture of wire phenomenon, and the fiber surface obtaining is coarse.
Embodiment 7
Except being 30:100 by calcium carbonate and polyacrylic weight ratio, all the other are all identical with embodiment 5, and resulting polymers/calcium carbonate/metal composite fiber carries out every test, and test result is listed in table 1.
With flying-spot microscope observation, in composite fibre, the diameter of broken-staple metal fibre is below 2.09 μ m.Length is for being more than or equal to 7.5 μ m.In spinning process, seldom occur fracture of wire phenomenon, the fiber surface obtaining is smooth.
Comparative example 5
Except not adding metal alloy, all the other are all identical with embodiment 7, and gained polypropylene/calcium carbonate fiber, carries out every test, and test result is listed in table 1.In spinning process, occur in a large number fracture of wire phenomenon, and the fiber surface obtaining is coarse.
Embodiment 8
The polymer of the present embodiment is polypropylene (fusing point is 167 DEG C for China Petrochemical Industry's Zhenhai Ningbo refinery, trade mark Z30S), and metal alloy is sn-bi alloy (138 DEG C of fusing point), calcium sulfate crystal whiskers (Zhengzhou Bo Kaili, trade mark nanometer calcium sulfate whisker, average diameter 500nm).Sn-bi alloy and polyacrylic volume ratio are 2:100, and calcium sulfate and polyacrylic weight ratio are 10:100, add appropriate antioxidant 1010 (Switzerland's Ciba-Geigy is produced), irgasfos 168 (Switzerland's Ciba-Geigy is produced) and zinc stearate (commercially available); Wherein, taking polypropylene as 100 parts by weight, antioxidant 1010 is 0.5 part, and irgasfos 168 is 0.5 part, and zinc stearate is 1 part.
Mix in homogenizer according to the raw material of above-mentioned polymer, calcium sulfate and metal alloy and proportioning.Use afterwards the German HAAKE PolymLab of company double screw extruder extruding pelletization, each section of temperature of extruder is: 190 DEG C, and 200 DEG C, 210 DEG C, 210 DEG C, 210 DEG C, 200 DEG C (head temperature).Add in capillary rheometer spinning at 200 DEG C to obtain compound precursor pellet, velocity of plunger is 5mm/min, and rolling speed is 60m/min.After compound precursor being stretched under 150 DEG C of conditions to 15 times of former length, obtain polymer/calcium sulfate crystal whiskers/metal composite fiber, carry out every test, test result is listed in table 1.
With flying-spot microscope observation, in composite fibre, the diameter of broken-staple metal fibre is below 3.06 μ m.Length is for being more than or equal to 8 μ m.In spinning process, seldom occur fracture of wire phenomenon, the fiber surface obtaining is smooth.
Comparative example 6
Except not adding metal alloy, all the other are all identical with embodiment 8, and gained polypropylene/calcium sulfate crystal whiskers fiber, carries out every test, and test result is listed in table 1.In spinning process, occur in a large number fracture of wire phenomenon, and the fiber surface obtaining is coarse.
Embodiment 9
Polymer adopts polyamide 11(France A Kema, trade mark Natural D40, fusing point is 179 DEG C), metal alloy is sn-bi alloy (138 DEG C of fusing point), nano-calcium carbonate (Henan section power, trade mark NLY-201, particle size range 30-50nm).The volume ratio of metal alloy and polymer is 2:100, and the volume ratio of calcium carbonate and polymer is 10:100, adds appropriate antioxidant 1010 (Switzerland's Ciba-Geigy is produced), irgasfos 168 (Switzerland's Ciba-Geigy is produced) and zinc stearate (commercially available); Wherein, taking polyamide 11 as 100 parts by weight, antioxidant 1010 is 0.5 part, and irgasfos 168 is 0.5 part, and zinc stearate is 1 part.
Mix in homogenizer according to the raw material of above-mentioned polymer, calcium carbonate and metal alloy and proportioning.Use afterwards the German HAAKE PolymLab of company double screw extruder extruding pelletization, each section of temperature of extruder is: 200 DEG C, and 210 DEG C, 220 DEG C, 220 DEG C, 220 DEG C, 210 DEG C (head temperature).Add in capillary rheometer spinning at 200 DEG C to obtain compound precursor pellet, velocity of plunger is 5mm/min, and rolling speed is 60m/min.Compound precursor is stretched under 170 DEG C of conditions former factory 15 times after obtain polymer/calcium carbonate/metal composite fiber, carry out every test, test result is listed in table 1.
With flying-spot microscope observation, in composite fibre, the diameter of broken-staple metal fibre is below 1.50 μ m.Length is for being more than or equal to 7.1 μ m.In spinning process, seldom occur fracture of wire phenomenon, the fiber surface obtaining is smooth.
Comparative example 7
Except not adding metal alloy, all the other are all identical with embodiment 9, and polyamide/calcium carbonate fiber test result is listed in table 1.In spinning process, occur in a large number fracture of wire phenomenon, and the fiber surface obtaining is coarse.
Table 1
Claims (15)
1. a polymer/non-conducting filler/metal composite fiber, it comprises the polymer fiber that contains broken-staple metal fibre and non-conducting filler, its microstructure be broken-staple metal fibre as dispersed phase distribution in polymer fiber, and as the broken-staple metal fibre of decentralized photo along the parallel distribution of polymer fiber axle, non-conducting filler is dispersed in polymer fiber, is distributed between broken-staple metal fibre; Described polymer is thermoplastic resin; At described Polymer Processing temperature, there is not melting in described non-conducting filler; Described metal is low-melting-point metal, is selected from least one in one pack system metal and metal alloy, and its fusing point is at 20～480 ° of C, and its fusing point is simultaneously lower than described Polymer Processing temperature.
2. polymer/non-conducting filler/metal composite fiber according to claim 1, it is characterized in that, described broken-staple metal fibre and the volume ratio of polymer fiber are 0.01:100～20:100, are preferably 0.1:100～4:100, more preferably 0.5:100～2:100.
3. polymer/non-conducting filler/metal composite fiber according to claim 1, is characterized in that, described melting point metal is at 100～250 ° of C, preferably at 120～230 ° of C.
4. polymer/non-conducting filler/metal composite fiber according to claim 1, is characterized in that, the one pack system metal in described metal is the elemental metals of gallium, caesium, rubidium, indium, tin, bismuth, cadmium, lead element; Metal alloy in described metal is metal alloy two or more in gallium, caesium, rubidium, indium, tin, bismuth, cadmium, lead element, or be at least one the metal alloy at least one and copper, silver, gold, iron or the zinc element in gallium, caesium, rubidium, indium, tin, bismuth, cadmium, lead element, or be the alloy that at least one and element silicon at least one and copper, silver, gold, iron or the zinc element in gallium, caesium, rubidium, indium, tin, bismuth, cadmium, lead element and/or carbon form.
5. polymer/non-conducting filler/metal composite fiber according to claim 1, is characterized in that described broken-staple metal fibre diameter is less than or equal to 12 μ m, is preferably less than or equal to 8 μ m, is more preferably less than or equals 3 μ m.
6. polymer/non-conducting filler/metal composite fiber according to claim 1, is characterized in that, described polymer is that fusing point is at 90～450 DEG C, preferably at the thermoplastic resin of 100～290 DEG C.
7. polymer/non-conducting filler/metal composite fiber according to claim 6, is characterized in that, described polymer is selected from the one in polyethylene, polypropylene, polyamide, polyester.
8. polymer/non-conducting filler/metal composite fiber according to claim 1, is characterized in that, described non-conducting filler and the weight ratio 0.1:100～30:100 of polymer, be preferably 0.5:100～10:100, more preferably 1:100～2:100.
9. polymer/non-conducting filler/metal composite fiber according to claim 1, is characterized in that, described non-conducting filler is at least less than 500 μ m in one dimension size on its three-dimensional dimension, is preferably less than 300 μ m.
10. polymer/non-conducting filler/metal composite fiber according to claim 1, it is characterized in that, described non-conducting filler is at least one in non-conductive slaine, metal nitride, non-metal nitride, non-metallic carbide, metal hydroxides, metal oxide, nonmetal oxide, natural crystal.
11. polymer/non-conducting filler/metal composite fibers according to claim 1, it is characterized in that, described non-conducting filler is at least one in calcium carbonate, barium sulfate, calcium sulfate, silver chlorate, aluminium hydroxide, magnesium hydroxide, aluminium oxide, magnesia, silica, asbestos, talcum, kaolin, mica, feldspar, wollastonite, imvite.
12. according to the polymer/non-conducting filler/metal composite fiber one of claim 9～11 Suo Shu, it is characterized in that, described non-conducting filler is nanoscale non-conducting filler.
13. polymer/non-conducting filler/metal composite fibers according to claim 12, is characterized in that, described nanoscale non-conducting filler has at least one dimension to be less than 100nm on its three-dimensional dimension, is preferably less than 50nm.
14. 1 kinds according to the preparation method of the polymer/non-conducting filler/metal composite fiber described in claim 1～13 any one, comprises the steps:
Step 1, by described amount, described thermoplastic resin, non-conducting filler and the metal of comprising carried out to melt blending in interior component, obtain polymer/non-conducting filler/metal blend;
Step 2, by the spinning on spinning equipment of above resulting polymers/non-conducting filler/metal blend, obtain polymer/non-conducting filler/metal composite precursor;
Step 3, temperature by above resulting polymers/non-conducting filler/metal composite precursor at the thermoplastic resin fusing point lower than adopted, and in temperature range greater than or equal to adopted low-melting-point metal fusing point, add hot-stretch and obtain polymer/non-conducting filler/metal composite fiber.
The preparation method of 15. polymer/non-conducting filler/metal composite fibers according to claim 14, it is characterized in that the stretching ratio that adds hot-stretch described in step 3 is more than or equal to 2 times, be preferably more than or equal 5 times, being more preferably more than or equal to 10 times.
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| CN201310127922.4A CN104099680B (en) | 2013-04-12 | 2013-04-12 | A kind of polymer/non-conducting filler/metal composite fiber and preparation method thereof |
| EP14782688.7A EP2985370B1 (en) | 2013-04-12 | 2014-04-11 | Polymer/filler/metal composite fiber and preparation method thereof |
| TW103113454A TWI647263B (en) | 2013-04-12 | 2014-04-11 | Polymer/filler/metal composite fiber and preparation method thereof |
| KR1020157031983A KR101917257B1 (en) | 2013-04-12 | 2014-04-11 | Polymer/filler/metal composite fiber and preparation method thereof |
| PCT/CN2014/075168 WO2014166420A1 (en) | 2013-04-12 | 2014-04-11 | Polymer/filler/metal composite fiber and preparation method thereof |
| CA2909301A CA2909301C (en) | 2013-04-12 | 2014-04-11 | Polymer/filler/metal composite fiber and preparation process thereof |
| US14/783,813 US10787754B2 (en) | 2013-04-12 | 2014-04-11 | Polymer/filler/metal composite fiber and preparation method thereof |
| JP2016506774A JP6434492B2 (en) | 2013-04-12 | 2014-04-11 | Polymer / filler / metal composite fiber and method for producing the same |
| ES14782688T ES2981960T3 (en) | 2013-04-12 | 2014-04-11 | Polymer/filler/metal composite fiber and preparation method thereof |
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| CN105131545A (en) * | 2015-09-18 | 2015-12-09 | 安徽创业机电设备有限公司 | High-strength and high-ductility bristle |
| CN106192050A (en) * | 2016-08-23 | 2016-12-07 | 孟玲 | Anti-electrostatic polymer composite fibre |
| CN108986949A (en) * | 2018-06-15 | 2018-12-11 | 北京梦之墨科技有限公司 | A kind of conducing composite material and preparation method thereof |
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| JP2004316029A (en) * | 2003-04-17 | 2004-11-11 | Kanebo Ltd | Method for producing conductive fiber, conductive fiber produced thereby and conductive fiber structure produced by using the same |
| CN1914694A (en) * | 2003-12-12 | 2007-02-14 | 西门子公司 | Metal/plastic hybrid and shaped body produced therefrom |
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| JP2004316029A (en) * | 2003-04-17 | 2004-11-11 | Kanebo Ltd | Method for producing conductive fiber, conductive fiber produced thereby and conductive fiber structure produced by using the same |
| CN1914694A (en) * | 2003-12-12 | 2007-02-14 | 西门子公司 | Metal/plastic hybrid and shaped body produced therefrom |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105131545A (en) * | 2015-09-18 | 2015-12-09 | 安徽创业机电设备有限公司 | High-strength and high-ductility bristle |
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