CN104099683B - A kind of polymer/conductive filler/metal composite fiber and preparation method thereof - Google Patents
A kind of polymer/conductive filler/metal composite fiber and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of polymer/conductive filler/metal composite fiber. It comprises the polymer fiber that contains broken-staple metal fibre and conductive filler, and broken-staple metal fibre is as dispersed phase distribution in polymer fiber, and along the parallel distribution of polymer fiber axle, conductive filler is dispersed in polymer fiber and is distributed between broken-staple metal fibre; At described Polymer Processing temperature, there is not melting in described conductive 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 DEG C, and its fusing point is simultaneously lower than described Polymer Processing temperature; Broken-staple metal fibre and polymer fiber volume ratio are 0.01:100～20:100; The weight ratio of conductive filler and polymer is 0.1:100～30:100. Composite fibre of the present invention, in reducing specific insulation, reduces fracture of wire probability, and fiber surface is smooth. Preparation method is simple, and production cost is lower, is easy to industrialized mass.
Description
Technical field
The present invention relates to synthetic fibers field, say further, the present invention relates to a kind of polymer/conductive filler/Composite fibre of metal and preparation method thereof.
Background technology
The characteristics such as compare natural fiber, synthetic fibers have cheap, and the low and hydroscopicity of density is low, extensivelyBe applied to the field such as textile garment class, woven bag of daily productive life. But the electrical insulating property of synthetic fibersCan be good, resistivity is high, in use easily produces static, all can bring industrial production and people's livesHarm. And along with high-tech development, because static and Electrostatic Absorption dust are to cause hyundai electronics to be establishedOne of standby operational failure, short circuit, dropout, error code, immediate cause that yield rate is low. At stoneThe industries such as oil, chemical industry, precision optical machinery, colliery, food, medicine all have special wanting to the protection of staticAsk. Therefore, thus exploitation has the fiber of superior electrical property to be reduced the harm that brings of static and becomes very urgentProblem.
The nanoscale tubular structure of the similar curling graphite that CNT is made up of carbon hexatomic ring. Because carbon is receivedMitron has excellent electricity and mechanical property, is therefore widely used in polymer matrix composite or compound fibreDimension field. But because causing CNT, the high surface energy of nano particle self there is serious reuniting effect,Thereby loading and the cost of nano particle are increased. Meanwhile, a large amount of nano-particles filled is to the life of fiberProduce and also caused difficulty. How to reduce CNT consumption, reducing production difficulty is problem demanding prompt solution.
Adopting composite conducting conductive filler technology to add the 3rd component is effectively to improve Conductivity of Fiber electrical efficiency, reducesThe effective ways of content of carbon nanotubes. Patent CN102409421A discloses one and has prepared PP/Nano twoThe preparation method of tin dioxide/carbon nano tube composite fibre. Although this technology has reduced the resistivity of composite fibre,But the 3rd component adding is similarly nano particle, has increased the difficulty processing raw material, and fiber surface is coarse,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 goldBelong to using characteristics such as high conductivity, easy processing and be widely used in answering of polymer as a new conductive fillerCondensation material field. Patent CN102021671A disclose a kind of polymer/low-melting-point metal compound wire andManufacture method, patent CN102140707A discloses a kind of skin-core composite electromagnetic shielding fiber and system thereof simultaneouslyPreparation Method. Above-mentioned two technology utilize core-sheath technology to prepare polymer overmold low-melting-point metal wire or fibreThe method of dimension. But need special composite spinning machine in this technology, and as the sandwich layer metal proportion of fiberStrengthen, although ensured fiber low resistivity, need a large amount of metals that add, increased and be produced intoThis.
Summary of the invention
In order to there is the compound of low specific insulation and excellent handle with easy and method preparation cheaplyFiber, proposes the present invention.
An object of the present invention is to provide a kind of polymer/conductive filler/metal composite fiber, this compound fibreDimension has good antistatic property and feel.
Another object of the present invention is to provide the preparation method of above-mentioned polymer/conductive filler/metal composite fiber,The method adopts in-situ method to prepare polymer/conductive filler/metal composite fiber, prepares at polymer fiberIn journey, become the preparation method of broken-staple metal fibre by metallic particles stretcher strain as the low-melting-point metal of decentralized photo.Due to the existence of conductive filler in system, in Blending Processes the viscosity of system improve very large, fast in identical shearingsUnder the condition of rate, system is subject to larger shear action, thereby makes low-melting-point metal at macromolecular material baseIn body, disperse particle diameter to diminish, also reduced the probability that after metallic particles collision, generation merges again, make metalThe particle diameter of grain becomes less, and metallic particles is more, and between metallic particles, distance is less. So at metalParticle in-situ be deformed into metallic fiber time, make short fiber diameter less, between short fiber, distance is shorter; SeparatelyOn the one hand, conductive filler is dispersed in and between metallic fiber, also plays connection function, thereby realizes at lower metalIn the situation of loading, improve the object of resistant fiber antistatic property. Method of the present invention is at existing general fibreOn production equipment, realize, thereby make preparation method there is good applicability and lower equipment cost.
A kind of polymer/conductive filler/metal composite fiber of the present invention, comprises and contains conductive filler and metalThe polymer fiber of short fiber, its microstructure be broken-staple metal fibre as dispersed phase distribution at polymer fiberIn, and as the broken-staple metal fibre of decentralized photo along the parallel distribution of polymer fiber axle; Conductive filler dispersesIn polymer fiber, be distributed between broken-staple metal fibre. Because connection metal is played in the existence of conductive fillerThe effect of short fiber, more easily forms conductive network; Also make broken-staple metal fibre diameter less, short fiber simultaneouslyBetween distance shorter, the antistatic property of prepared composite fibre is improved, and keep fiberGood feel.
In a kind of polymer/conductive filler/metal composite fiber of the present invention, the polymer of described polymer fiberFor thermoplastic resin, be preferably fusing point at the thermoplastic resin of 90～450 DEG C, more preferably fusing point isThe thermoplastic resin of 100～290 DEG C. Most preferably in polyethylene, polypropylene, polyamide or polyester etc. oneKind. What wherein said polyamide comprised any kind in prior art can spinning poly acid amides, preferably nylon6, nylon 66, nylon 11 or nylon 12. Described polyester can be in prior art any can spinning poly-Ester, preferably polyethylene terephthalate (PET) or PTT (PTT).
Conductive filler described in a kind of polymer/conductive filler/metal composite fiber of the present invention is existing skillDisclosed various conductive fillers in art. The index of general available technology adopting powder resistance rate is distinguished non-leadingElectricity filler and conductive filler, wherein powder resistance rate is less than 1 × 109The filler of Ω CM is called conductive filler,Powder resistance rate is more than or equal to 1 × 109The filler of Ω CM is called non-conducting filler. Of the present invention leadingAt described Polymer Processing temperature, there is not the conductive filler of melting in electricity filler. In the present invention to described conductionThe shape of filler, without any restriction, can be the conductive 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 conductive fillers without anyRestriction, as long as can be dispersed in polymeric matrix and be less than the diameter of the fiber of final preparation, preferredOn 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 exist0 dimension, 1 dimension or 2 dimensions can reach the conductive filler of nano-scale, and preferably 1 dimension or 2 dimension sizes can reachThe conductive filler of nano-scale. Wherein 0 dimension nano-level conducting filler is that diameter is at nano level spherical or class ballThe conductive filler of shape; 1 dimension nano material is that radial dimension is shapes such as nano level line style, aciculiform, fiber shapesThe conductive filler of shape; 2 dimension nano materials are that thickness is the conductive filler of nano level sheet. So-called nanoscaleSize, generally refers to the size that is less than 100nm, but some known nano-sized filler in prior art, thanAs CNT, although its diameter dimension is from tens nanometers to hundreds of nanometer, be also usually calledNanoscale. So what the conductive filler of the present invention's nano-grade size herein referred to usually to think in prior art receivesMeter level conductive filler. Described nano-level conducting filler more preferably has at least one dimension to be less than on its three-dimensional dimension100nm, is most preferably less than 50nm.
Conductive filler in polymer/conductive filler/metal composite fiber of the present invention is preferably one pack system goldGenus, metal alloy, metal oxide, slaine, metal nitride, non-metal nitride, metal hydrogen-oxygenAt least one in compound, conducting polymer, conductive carbon material; More preferably gold, silver, copper, iron, goldAlloy, silver alloy, copper alloy, ferroalloy, titanium dioxide, di-iron trioxide, tri-iron tetroxide, oxidationAt least one in silver, zinc oxide, carbon black, CNT, Graphene and linear conductance polyaniline.
The weight of conductive filler and polymer fiber in polymer/conductive filler/metal composite fiber of the present inventionThan for 0.1:100～30:100, be preferably 0.5:100～10:100, more preferably 1:100～2:100.
Described in a kind of polymer/conductive filler/metal composite fiber of the present invention, the metal of broken-staple metal fibre isLow melting metal, fusing point, at 20～480 DEG C, is preferably 100～250 DEG C, more preferably the list of 120～230 DEG CAt least one in component metals and metal alloy, and its fusing point is simultaneously lower than described Polymer Processing temperatureDegree.
Preferably, the one pack system metal in described metal is gallium, caesium, rubidium, indium, tin, bismuth, cadmium, plumbous unitThe elemental metals of element; Metal alloy in described metal is gallium, caesium, rubidium, indium, tin, bismuth, cadmium, plumbous unitTwo or more metal alloy in element, or be in gallium, caesium, rubidium, indium, tin, bismuth, cadmium, lead elementThe metal alloy of at least one at least one and copper, silver, gold, iron or zinc element, or be gallium,In at least one in caesium, rubidium, indium, tin, bismuth, cadmium, lead element and copper, silver, gold, iron or zinc elementAt least one and element silicon and/or the alloy that forms of carbon.
The body of broken-staple metal fibre and polymer fiber in polymer/conductive filler/metal composite fiber of the present inventionLong-pending than for 0.01:100～20:100, be preferably 0.1:100～4:100, more preferably 0.5:100～2:100.
In a kind of polymer/conductive filler/metal composite fiber of the present invention, described in be dispersed in polymer fiberBroken-staple metal fibre, its diameter is preferably less than or equal to 12 μ m, is more preferably less than or equal to 8 μ m,Be preferably and be less than or equal to 3 μ m.
The preparation method of polymer/conductive filler/metal composite fiber of the present invention comprises the following steps:
Step 1, will comprise described thermoplastic resin, described conductive filler and described metal interior by described amountComponent carry out melt blending, obtain polymer/conductive filler/metal blend.
Wherein said melt blending is the processing conditions of common thermoplastic resin melt blending.
The microscopic pattern of polymer/conductive filler/metal blend of gained is: metal is even as decentralized photoBe distributed in the thermoplastic resin of continuous phase. Conductive filler is dispersed between metallic particles, owing to leading in systemThe viscosity that has co-mixing system of electricity filler improves very large, and under the condition of identical shear rate, system is subject toTo larger shear action, thereby make low-melting-point metal in polymeric matrix, disperse particle diameter to diminish, the opposing partyFace, has also reduced the probability that after metallic particles collision, generation merges again, and the particle diameter of metallic particles is become moreLittle, metallic particles is more, and between metallic particles, distance is less.
Step 2, resulting polymers/conductive filler in step 1/metal blend is spun on spinning equipmentSilk, obtains polymer/conductive filler/metal composite precursor.
Wherein said spinning equipment is spinning equipment general in prior art, at adopted thermoplastic resinUnder the common spinning condition of spinning, adopt common spray silk and rolling speed to carry out spinning. Conventionally rolling speed,Hurry up, the composite fibre diameter obtaining is thinner, and wherein broken-staple metal fibre diameter is less, causes finally obtainingThe electrical property of composite fibre is better.
Step 3, by the polymer/conductive filler of gained in step 2/metal composite precursor lower than adoptThe temperature of thermoplastic resin fusing point and temperature range greater than or equal to described low-melting-point metal fusing point in heatStretching obtains polymer/conductive filler/metal composite fiber.
The stretching ratio that wherein adds hot-stretch adopts common stretching ratio, preferably greater than or equal to 2 times,More preferably be more than or equal to 5 times, most preferably be and be more than or equal to 10 times. Along with the raising gold of stretching ratioThe diameter that belongs to short fiber is less, and the electrical property of composite fibre improves, simultaneously depositing due to conductive filler in system, the particle diameter of the decentralized photo metallic particles of resulting polymers/conductive filler in step 1/metal blend becomesLess, metallic particles is more, and between metallic particles, distance is less, so through step 2 and step 3In rear prepared composite fibre, broken-staple metal fibre diameter is less, and between broken-staple metal fibre, distance is shorter, makes multipleThe electrical property of condensating fiber is better.
In the preparation method's of polymer/conductive filler/metal composite fiber of the present invention step 1, gather describedThe method that compound, conductive filler and metal melting blend adopt is exactly common melt blending in rubber and plastic processingMethod, blending temperature is the common processing temperature of thermoplastic resin, should both ensure adopted thermoplastic shortlyProperty resin and the complete melting of metal can not make again adopted thermoplastic resin decompose scope in select. In addition,According to processing needs, can in blend material, add in right amount the conventional auxiliary agent of thermoplastic resin processing. In blendCan be by each components such as described thermoplastic resin, conductive filler and metals by modes such as metered charge in processAdd simultaneously and in melt blending equipment, carry out melt blending; Also general mixing apparatus can first be passed through, in advanceDescribed each component is 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, and banbury is singleScrew extruder, double screw extruder or torque rheometer etc. Described material mixing equipment is selected from existing skillHomogenizer in 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 anti-Oxygen agent, plasticizer and other processing aid etc. These conventional auxiliary dosages are conventional amount used, or according to realitySuitable adjustment is carried out in the requirement of border situation.
It is to ensure to obtain polymerization of the present invention that the present invention prepares the hot-stretch that adds of step 3 in the method for composite fibreThe necessary condition of thing/conductive filler/metal composite fiber, the existence due to conductive filler in system in step 1 is total toThe viscosity of mixed system improves very large, and under the condition of identical shear rate, system is subject to larger shearing and doesWith, thereby make low-melting-point metal in polymeric matrix, disperse particle diameter to diminish, on the other hand, also reduce goldAfter metal particles collision, again there is the probability merging, make the particle diameter of metallic particles become less, metallic particles numberMeasure manyly, between metallic particles, distance is less, and this is to obtain polymer/conductive filler/metal composite of the present inventionThe guarantee of fiber. The microscopic pattern of prepared like this polymer/conductive filler/metal composite fiber is: be goldBelong to short fiber as dispersed phase distribution in polymer fiber, and as the broken-staple metal fibre of decentralized photo alongThe parallel distribution of polymer fiber axle; Conductive filler is dispersed between broken-staple metal fibre, due to depositing of conductive fillerMaking, short fiber diameter is less, and between short fiber, distance is shorter, and conductive filler also plays connection function simultaneously,More easily form conductive network, the antistatic property of gained fiber is improved, and keep fiber goodGood feel; Meanwhile, because broken-staple metal fibre is arranged in polymer fiber inside, protection broken-staple metal fibre is notBy bending, stretch, infringement when folding, wearing and tearing and washing, solved layer on surface of metal oxidizable, easyCome off or metal dust is easily reunited, thus the problem that causes antistatic effect to decline; And due to metalAdd, solved the problem of polymer/conductive filler composite fiber spinning difficulty, spinning process is very smooth,Fracture of wire situation reduces in a large number.
Especially particularly, in the prior art, while preparing conductive fiber, along with stretching ratio improves, conductionDistance between filler increases, original conductive network destruction that is stretched. Therefore, constant at conductive fillerUnder condition, conductive fiber of the prior art is along with the raising of draw ratio, although the ultimate strength of fiber alsoImprove, but electrical property is on a declining curve. in the present invention, metal stretches at suitable temperature, metalLength can be more and more longer along with stretching, and in the axial plane of vertical fibers, along with carrying of draw ratioHeight, the distance of metallic fiber is ever-reduced; Also has the connection function of conductive filler, easier shape simultaneouslyBecome conductive network. This special structure causes the raising of composite fibre of the present invention along with draw ratio, itsInner conductive network obtains constantly perfect, thereby the electrical property of composite fibre of the present invention is improved constantly. ByThis, when composite fibre of the present invention improves along with tensile fiber multiplying power improves ultimate strength, its electrical property is notOnly be not affected, also improve on the contrary thereupon, thereby realized the mechanical property that makes composite fibre of the present inventionThe object that energy and electrical property improve simultaneously.
The present invention proposes to adopt general spinning equipment to prepare anti-electrostatic polymer/conductive filler/metal composite fibreDimension, significantly reduces costs, and has applicability widely. Polymer/conductive filler of the present invention/The selected low-melting-point metal of metal composite fiber can improve the fibre in processability and the spinning process of granulation processThe spinning properties of dimension, enhances productivity, and saves production cost; And can be by selecting fusing point to differ scopeLarge thermoplastic resin and metal arrange in pairs or groups to widen working condition, are 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 limit of these embodimentSystem, 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 for utilizing chemical solvent to remove profit after polymeric matrixUse ESEM.
(2) the specific insulation method of testing of composite fibre is as follows: the survey of composite fibre specific insulationMethod for testing is: 1, choose the composite fibre of 2cm left and right length, at two ends conducting resinlBe with adhesiving metal aluminium foil as test electrode, the length of the composite fibre between measurement electrode the innerDegree t; 2, measure the diameter d of composite fibre with optics fibrescope; 3, use Shanghai precisionThe PC-68 high resistant instrument of instrument and meter company is measured fiber volume resistance Rv; 4, according to asLower formula calculates the specific insulation ρ v of fiber samples,Measure 10After fiber, average.
Embodiment 1
The polymer of the present embodiment is that (fusing point is polypropylene for China Petrochemical Industry's Zhenhai Ningbo refinery, trade mark Z30S167 DEG C), metal alloy is sn-bi alloy (Beijing three He Dingxin high and new technology Development Co., Ltds, fusing point138 DEG C), (how scientific and technological sky, Beijing is, trade mark FT-9000, average diameter 11nm, average length for CNT10 μ m, multi-walled carbon nano-tubes), sn-bi alloy and polyacrylic volume ratio are 0.5:100, CNT is with poly-The weight ratio of propylene is 2:100, adds appropriate antioxidant 1010 (Switzerland's Ciba-Geigy is produced), antioxygenAgent 168(Switzerland Ciba-Geigy is produced) and zinc stearate (commercially available); Wherein taking polypropylene as 100 weightUmber meter, antioxidant 1010 is 0.5 part, and irgasfos 168 is 0.5 part, and zinc stearate is 1 part.
According to the raw material of above-mentioned polymer, CNT and metal alloy and proportioning in homogenizerMix. Use afterwards the German HAAKE PolymLab of company double screw extruder extruding pelletization, extruderEach section of temperature is: 190 DEG C, and 200 DEG C, 210 DEG C, 210 DEG C, 210 DEG C, 200 DEG C (head temperature). WillPellet adds in capillary rheometer spinning at 200 DEG C to obtain compound precursor, and velocity of plunger is5mm/min, rolling speed is 60m/min. Compound precursor is stretched under 150 DEG C of conditions to 5 times of former lengthAfter obtain polymer/carbon nano-tube/metal composite fiber, carry out every test, test result is listed in table 1. WithScanning electron microscope observation, in composite fibre, the diameter of broken-staple metal fibre is below 1.87 μ m. Length for be greater than or etc.In 6 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 gained is poly-Compound/CNT/metal composite fiber, carries out every test, and test result is listed in table 1. Use ESEMObservation, in composite fibre, the diameter of broken-staple metal fibre is below 2.15 μ m. Length is for being more than or equal to7.6 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 gained is poly-Compound/CNT/metal composite fiber, carries out every test, and test result is listed in table 1 and table 2. With sweepingRetouch electron microscopy observation, in composite fibre, the diameter of broken-staple metal fibre is below 3.46 μ m. Length is for being more than or equal to9 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, gained polypropylene/CNT fibreDimension, carries out every test, and test result is listed in table 1 and table 2. In spinning process, there is 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 10 times of former length, all the other are all identical with embodiment 3,Resulting polymers/CNT/metal composite fiber, carries out every test, and test result is listed in table 1 and table2. With scanning electron microscope observation, in composite fibre, the diameter of broken-staple metal fibre is below 1.45 μ m. Length is largeIn or equal 9 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, gained polypropylene/CNT fibreDimension, carries out every test, and test result is listed in table 1 and table 2. In spinning process, there is 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 15 times of former length, all the other are all identical with embodiment 3,Gained polypropylene/CNT/metal composite fiber, carries out every test, and test result is listed in table 1 and table2. With scanning electron microscope observation, in composite fibre, the diameter of broken-staple metal fibre is below 0.8 μ m. Length is for being greater thanOr equal 6 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, gained virgin pp/CNT fibreDimension, carries out every test, and test result is listed in table 1 and table 2. In spinning process, there is in a large number fracture of wire phenomenon,And the fiber surface obtaining is coarse.
Embodiment 6
The polymer of the present embodiment is that (fusing point is polypropylene for China Petrochemical Industry's Zhenhai Ningbo refinery, trade mark Z30S167 DEG C), metal alloy is sn-bi alloy (138 DEG C of fusing point), nano titanium oxide (the former dioxy of Japanese stoneChange titanium FT-3000, average diameter 270nm, average length 5.15 μ m), sn-bi alloy and polyacrylic bodyLong-pending than being 1:100, titanium dioxide and polyacrylic weight ratio are 10:100, add appropriate antioxidant1010(Switzerland Ciba-Geigy is produced), irgasfos 168 (Switzerland's Ciba-Geigy is produced) and zinc stearate (citySell); Wherein, taking polypropylene as 100 parts by weight, antioxidant 1010 is 0.5 part, and irgasfos 168 is0.5 part, zinc stearate is 1 part.
According to the raw material of above-mentioned polymer, titanium dioxide and metal alloy and proportioning in homogenizerMix. Use afterwards the German HAAKE PolymLab of company double screw extruder extruding pelletization, extruderEach section of temperature is: 190 DEG C, and 200 DEG C, 210 DEG C, 210 DEG C, 210 DEG C, 200 DEG C (head temperature). WillPellet adds in capillary rheometer spinning at 200 DEG C to obtain compound precursor, and velocity of plunger is5mm/min, rolling speed is 60m/min. Compound precursor is stretched under 150 DEG C of conditions to 5 times of former lengthAfter obtain polymer/titanium dioxide/metal composite fiber, carry out every test, test result is listed in table 1. WithScanning electron microscope observation, in composite fibre, the diameter of broken-staple metal fibre is below 4.46 μ m. Length for be greater than or etc.In 5 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, gained polypropylene/titanium dioxide fibreDimension, carries out every test, and test result is listed in table 1. In spinning process, there is in a large number fracture of wire phenomenon, andThe fiber surface obtaining is coarse.
Embodiment 7
Except being 30:100 by titanium dioxide and polyacrylic weight ratio, all the other are all identical with embodiment 6, instituteObtain polymer/titanium dioxide/metal composite fiber, carry out every test, test result is listed in table 1. With scanningElectron microscopy observation, in composite fibre, the diameter of broken-staple metal fibre is below 4.66 μ m. Length is for being more than or equal to5 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, gained polypropylene/titanium dioxide fibreDimension, carries out every test, and test result is listed in table 1. In spinning process, there is in a large number fracture of wire phenomenon, andThe fiber surface obtaining is coarse.
Embodiment 8
The polymer of the present embodiment is that (fusing point is polypropylene for China Petrochemical Industry's Zhenhai Ningbo refinery, trade mark Z30S167 DEG C), metal alloy is sn-bi alloy (138 DEG C of fusing point), (the brilliant prosperous electronic material in Ningbo is limited for silver powderCompany, high-density spherical silver powder, average grain diameter 500nm, 960 DEG C of fusing points, sn-bi alloy and polyacrylic bodyLong-pending than being 1:100, silver powder and polyacrylic weight ratio are 10:100, add appropriate antioxidant 1010 (auspiciousScholar's Ciba-Geigy is produced), irgasfos 168 (Switzerland Ciba-Geigy produce) 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,Zinc stearate is 1 part.
Mix in homogenizer according to the raw material of above-mentioned polymer, silver powder and metal alloy and proportioningEvenly. Use afterwards the German HAAKE PolymLab of company double screw extruder extruding pelletization, each section of extruderTemperature is: 190 DEG C, and 200 DEG C, 210 DEG C, 210 DEG C, 210 DEG C, 200 DEG C (head temperature). By pelletAdd in capillary rheometer spinning at 200 DEG C to obtain compound precursor, velocity of plunger is 5mm/min, receivesVolume speed is 60m/min. After compound precursor being stretched under 150 DEG C of conditions to 5 times of former length, obtain polymer/ silver powder/metal composite fiber, carries out every test, and test result is listed in table 1. With scanning electron microscope observation, multipleIn condensating fiber, the diameter of broken-staple metal fibre is below 3.46 μ m. Length is for being more than or equal to 7 μ m. Spinning processIn seldom there is 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/silver powder fiber, entersThe every test of row, test result is listed in table 1. In spinning process, there is in a large number fracture of wire phenomenon, and obtainFiber surface is coarse.
Embodiment 9
The polymer of the present embodiment is that (fusing point is polypropylene for China Petrochemical Industry's Zhenhai Ningbo refinery, trade mark Z30S167 DEG C), metal alloy is sn-bi alloy (138 DEG C of fusing point), stainless steel fibre (the limited public affairs of Beijing Jin FubangDepartment, shears short fiber, average diameter 8 μ m, 1350 DEG C of fusing points), sn-bi alloy and polyacrylic volume ratio are1:100, stainless steel fibre and polyacrylic weight ratio are 10:100, add appropriate antioxidant 1010 (auspiciousScholar's Ciba-Geigy is produced), irgasfos 168 (Switzerland Ciba-Geigy produce) 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,Zinc stearate is 1 part.
Mixed in homogenizer according to the raw material of above-mentioned polymer, stainless steel and metal alloy and proportioningClose evenly. Use afterwards the German HAAKE PolymLab of company double screw extruder extruding pelletization, extruder is eachDuan Wendu is: 190 DEG C, and 200 DEG C, 210 DEG C, 210 DEG C, 210 DEG C, 200 DEG C (head temperature). By grainMaterial adds in capillary rheometer spinning at 200 DEG C to obtain compound precursor, and velocity of plunger is 5mm/min,Rolling speed is 60m/min. After compound precursor being stretched under 150 DEG C of conditions to 5 times of former length, obtain polymerizationThing/stainless steel/metal composite fiber, carries out every test, and test result is listed in table 1. See with ESEMSurvey, in composite fibre, the diameter of broken-staple metal fibre is below 7.46 μ m. Length is for being more than or equal to 7 μ m. SpinIn silk 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 gained polypropylene/stainless steel fibre is multipleCondensating fiber, carries out every test, and test result is listed in table 1. In spinning process, there is in a large number fracture of wire phenomenon,And the fiber surface obtaining is coarse.
Embodiment 10
The polymer of the present embodiment is that (fusing point is polypropylene for China Petrochemical Industry's Zhenhai Ningbo refinery, trade mark Z30S167 DEG C), metal alloy is sn-bi alloy (138 DEG C of fusing point), polyaniline (Tianjin get Wang Maite new materialScience and Technology Ltd., polyaniline nano-line, average diameter 100nm, average length 10 μ m), sn-bi alloyWith polyacrylic volume ratio be 1:100, polyaniline and polyacrylic weight ratio are 10:100, add appropriate anti-Oxidant 1010(Switzerland Ciba-Geigy is produced), irgasfos 168 (Switzerland's Ciba-Geigy is produced) and hardResin acid zinc (commercially available); Wherein, taking polypropylene as 100 parts by weight, antioxidant 1010 is 0.5 part, anti-Oxygen agent 168 is 0.5 part, and zinc stearate is 1 part.
Mixed in homogenizer according to the raw material of above-mentioned polymer, polyaniline and metal alloy and proportioningClose evenly. Use afterwards the German HAAKE PolymLab of company double screw extruder extruding pelletization, extruder is eachDuan Wendu is: 190 DEG C, and 200 DEG C, 210 DEG C, 210 DEG C, 210 DEG C, 200 DEG C (head temperature). By grainMaterial adds in capillary rheometer spinning at 200 DEG C to obtain compound precursor, and velocity of plunger is 5mm/min,Rolling speed is 60m/min. After compound precursor being stretched under 150 DEG C of conditions to 5 times of former length, obtain polymerizationThing/polyaniline/metal composite fiber, carries out every test, and test result is listed in table 1. See with ESEMSurvey, in composite fibre, the diameter of broken-staple metal fibre is below 6.46 μ m. Length is for being more than or equal to 5 μ m. SpinIn silk process, seldom there is fracture of wire phenomenon.
Comparative example 8
Except not adding metal alloy, all the other are all identical with embodiment 10, gained polypropylene/polyaniline fiber,Carry out every test, test result is listed in table 1. In spinning process, there is in a large number fracture of wire phenomenon.
Embodiment 11
Polymer adopts polyamide 11(France A Kema, trade mark NaturalD40, fusing point is 179 DEG C),Metal alloy is sn-bi alloy (138 DEG C of fusing point), nano titanium oxide (the former titanium dioxide FT-3000 of Japanese stone,Average diameter 270nm, average length 5.15 μ m). The volume ratio of metal alloy and polymer is 2:100, twoThe volume ratio of titanium oxide and polymer is 10:100, adds appropriate antioxidant 1010 (Switzerland's Ciba-GeigyProduce), irgasfos 168 (Switzerland Ciba-Geigy produce) and zinc stearate (commercially available); Wherein with polyamidesAmine 11 is 100 parts by weight meters, and antioxidant 1010 is 0.5 part, and irgasfos 168 is 0.5 part, stearic acidZinc is 1 part.
According to the raw material of above-mentioned polymer, titanium dioxide and metal alloy and proportioning in homogenizerMix. Use afterwards the German HAAKE PolymLab of company double screw extruder extruding pelletization, extruderEach section of temperature is: 200 DEG C, and 210 DEG C, 220 DEG C, 220 DEG C, 220 DEG C, 210 DEG C (head temperature). WillPellet adds in capillary rheometer spinning at 200 DEG C to obtain compound precursor, and velocity of plunger is5mm/min, rolling speed is 60m/min. Compound precursor is stretched under 170 DEG C of conditions former factory 15Doubly, obtain polymer/titanium dioxide/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 1.30 μ m. Length isBe 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 9
Except not adding metal alloy, all the other are all identical with embodiment 7, the test of polyamide/titania fiberThe results are shown in table 1. In spinning process, occur in a large number fracture of wire phenomenon, and the fiber surface obtaining is coarse.Table 1
Table 2
From table 2, data can be found out, compound with respect to the polymer/carbon nano-tube that does not contain low-melting-point metalFiber, corresponding polymer/conductive filler of the present invention/low-melting-point metal composite fibre draws at identical precursorStretch and under multiplying power condition, there is larger hot strength and larger elongation at break. These data declarations with respect toPolymer/carbon nano-tube composite fibre, can realize the adding of a small amount of low-melting-point metal polymer/conductive filler/The synchronous raising of tensile break strength, elongation at break and the specific insulation of metal composite fiber.
Claims (25)
1. a polymer/conductive filler/metal composite fiber, it comprises the polymer fiber that contains broken-staple metal fibre and conductive 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, conductive 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 conductive 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 DEG C, and its fusing point is simultaneously lower than described Polymer Processing temperature; Described broken-staple metal fibre and the volume ratio of polymer fiber are 0.1:100～4:100.
2. polymer/conductive filler/metal composite fiber according to claim 1, is characterized in that, described broken-staple metal fibre and the volume ratio of polymer fiber are 0.5:100～2:100.
3. polymer/conductive filler/metal composite fiber according to claim 1, is characterized in that, described melting point metal is at 100～250 DEG C.
4. polymer/conductive filler/metal composite fiber according to claim 3, is characterized in that, described melting point metal is at 120～230 DEG C.
5. polymer/conductive 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.
6. polymer/conductive 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.
7. polymer/conductive filler/metal composite fiber according to claim 6, is characterized in that described broken-staple metal fibre diameter is less than or equal to 8 μ m.
8. polymer/conductive filler/metal composite fiber according to claim 7, is characterized in that described broken-staple metal fibre diameter is less than or equal to 3 μ m.
9. polymer/conductive filler/metal composite fiber according to claim 1, is characterized in that, described polymer is fusing point at the thermoplastic resin of 90～450 DEG C.
10. polymer/conductive filler/metal composite fiber according to claim 9, is characterized in that, described polymer is fusing point at the thermoplastic resin of 100～290 DEG C.
11. polymer/conductive filler/metal composite fibers according to claim 10, is characterized in that, described polymer is selected from the one in polyethylene, polypropylene, polyamide, polyester.
12. polymer/conductive filler/metal composite fibers according to claim 1, is characterized in that, described conductive filler and the weight ratio of polymer are 0.1:100～30:100.
13. polymer/conductive filler/metal composite fibers according to claim 12, is characterized in that, described conductive filler and the weight ratio of polymer are 0.5:100～10:100.
14. polymer/conductive filler/metal composite fibers according to claim 13, is characterized in that, described conductive filler and the weight ratio of polymer are 1:100～2:100.
15. polymer/conductive filler/metal composite fibers according to claim 1, is characterized in that, described conductive filler is at least less than 500 μ m in one dimension size on its three-dimensional dimension.
16. polymer/conductive filler/metal composite fibers according to claim 15, is characterized in that, described conductive filler is at least less than 300 μ m in one dimension size on its three-dimensional dimension.
17. polymer/conductive filler/metal composite fibers according to claim 1, it is characterized in that, described conductive filler is at least one in one pack system metal, metal alloy, metal oxide, slaine, metal nitride, non-metal nitride, metal hydroxides, conducting polymer, conductive carbon material.
18. polymer/conductive filler/metal composite fibers according to claim 1, it is characterized in that, described conductive filler is at least one in gold, silver, copper, iron, billon, silver alloy, copper alloy, ferroalloy, titanium dioxide, di-iron trioxide, tri-iron tetroxide, silver oxide, zinc oxide, carbon black, CNT, Graphene and linear conductance polyaniline.
19. according to the polymer/conductive filler/metal composite fiber one of claim 15～18 Suo Shu, it is characterized in that, described conductive filler is nano-level conducting filler.
20. polymer/conductive filler/metal composite fibers according to claim 19, is characterized in that, described nano-level conducting filler has at least one dimension to be less than 100nm on its three-dimensional dimension.
21. polymer/conductive filler/metal composite fibers according to claim 20, is characterized in that, described nano-level conducting filler has at least one dimension to be less than 50nm on its three-dimensional dimension.
22. 1 kinds according to the preparation method of the polymer/conductive filler/metal composite fiber described in claim 1～21 any one, comprises the steps:
Step 1, by described amount, described thermoplastic resin, conductive filler and the metal of comprising carried out to melt blending in interior component, obtain polymer/conductive filler/metal blend;
Step 2, by the spinning on spinning equipment of above resulting polymers/conductive filler/metal blend, obtain polymer/conductive filler/metal composite precursor;
Step 3, temperature by above resulting polymers/conductive 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/conductive filler/metal composite fiber.
The preparation method of 23. polymer/conductive filler/metal composite fibers according to claim 22, is characterized in that the stretching ratio that adds hot-stretch described in step 3 is more than or equal to 2 times.
The preparation method of 24. polymer/conductive filler/metal composite fibers according to claim 23, is characterized in that the stretching ratio that adds hot-stretch described in step 3 is more than or equal to 5 times.
The preparation method of 25. polymer/conductive filler/metal composite fibers according to claim 24, is characterized in that the stretching ratio that adds hot-stretch described in step 3 is more than or equal to 10 times.
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| KR1020157031983A KR101917257B1 (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 |
| 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 |
| JP2016506774A JP6434492B2 (en) | 2013-04-12 | 2014-04-11 | Polymer / filler / metal composite fiber and method for producing the same |
| EP14782688.7A EP2985370B1 (en) | 2013-04-12 | 2014-04-11 | Polymer/filler/metal composite fiber and preparation method thereof |
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| CN105177745B (en) * | 2015-08-31 | 2017-03-08 | 贵州省纤维检验局 | A kind of novel electromagnetic shielding nano-sized carbon conductive fiber material and preparation method thereof |
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