CN104099680B - A kind of polymer/non-conducting filler/metal composite fiber and preparation method thereof - Google Patents
A kind of polymer/non-conducting filler/metal composite fiber and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of polymer/non-conducting filler/metal composite fiber.It comprises the polymer fiber containing broken-staple metal fibre and non-conducting filler, broken-staple metal fibre as dispersed phase distribution in polymer fiber, and along the parallel distribution of polymer fiber axle, non-conducting filler to be dispersed in polymer fiber and to be distributed between broken-staple metal fibre; Melting is there is not in described non-conducting filler under described polymer process temperature; Described metal is low-melting-point metal, is selected from least one in single component metal and metal alloy, and its fusing point is at 20 ~ 480 ° of C, and its fusing point is simultaneously lower than described polymer process temperature; Broken-staple metal fibre and polymer fiber volume ratio are 0.01:100 ~ 20:100; The weight ratio of non-conducting filler and polymer is 0.1:100 ~ 30:100.Composite fibre of the present invention is while reduction specific insulation, and reduce fracture of wire probability, 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 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 produces electrostatic, all harm can be brought to industrial production and people's lives.And along with high-tech development, because electrostatic and Electrostatic Absorption dust cause one of immediate cause that modern electronic equipment operational failure, short circuit, dropout, error code, yield rate are low.All special requirement is had to the protection of electrostatic in industries such as oil, chemical industry, precision optical machinery, colliery, food, medicine.Therefore, exploitation has the fiber of superior electrical property thus reduces the harm that brings of electrostatic and become 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 the high surface energy due to nano particle self causes CNT to have serious reuniting effect, thus add loading and the cost of nano particle.Meanwhile, a large amount of nano-particles filled also result in 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 three components is effectively improve Conductivity of Fiber electrical efficiency, reduces the effective ways of content of carbon nanotubes.Patent CN102409421A discloses a kind of preparation method preparing PP/Nano tin ash/carbon nano tube composite fibre.Although this technology reduces the resistivity of composite fibre, the three components added is similarly nano particle, and add the difficulty processed raw material, fiber surface is coarse, and feel is poor, mechanical properties decrease, the phenomenon such as easy fracture of wire in production.
In recent years, there is new development in domestic and international polymer/low-melting-point metal field of compound material.Low-melting-point metal is widely used in the field of compound material of polymer using characteristics such as high conductivity, easily processing as a new non-conducting filler.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 need special composite spinning machine in this technology, and strengthen as the sandwich layer metal proportion of fiber, although ensure that fiber low resistivity, need to add metal in a large number, add production cost.
Summary of the invention
In order to have the composite fibre of low specific insulation and excellent handle with method preparation that is easy and low cost, 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, namely 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 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, thus make low-melting-point metal disperse particle diameter to diminish in macromolecular material matrix, on the other hand, also reduce the probability that metallic particles collision rift occurs to merge again, the particle diameter of metallic particles is made to become less, metallic particles is more, the spacing of metallic particles is less, so metallic particles original position be deformed into metal fibre time, make staple fibre diameter less, the spacing of staple fibre is shorter, thus realize the object improving resistant fiber antistatic property when lower metal filled amount.Method of the present invention realizes on existing general fibre production equipment, thus make 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 containing 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.Existence due to non-conducting filler makes staple fibre diameter less, and the spacing of staple fibre is shorter, and the antistatic property of prepared composite fibre is improved, and the feel keeping fiber good.
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 fusing point at the thermoplastic resin of 90 ~ 450 ° of C, is more preferably the thermoplastic resin that fusing point is 100 ~ 290 ° of C.One most preferably in polyethylene, polypropylene, polyamide or polyester etc.What wherein said polyamide comprised any kind in prior art can spinning poly acid amides, preferred nylon 6, nylon66 fiber, nylon 11 or nylon 12.Described polyester can be any in prior art can polyester, preferred polyethylene terephthalate (PET) or the polytrimethylene terephthalate (PTT) of spinning.
Non-conducting filler described in a kind of polymer/non-conducting filler/metal composite fiber of the present invention is non-conducting filler various disclosed in prior art.Adopt the index of powder resistance rate to distinguish non-conducting filler and conductive filler in general prior art, 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.Melting is there is not in non-conducting filler of the present invention under described polymer process temperature.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 to 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 μm, is preferably less than the filler of 300 μm; More preferably nano level non-conducting filler in prior art.Namely 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 the 0 dimension nanoscale non-conducting filler diameter that preferably 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 thickness is nano level sheet non-conducting filler.So-called nano-grade size, generally refers to the size being less than 100nm, but some known nano-sized filler in prior art, and such as nanometer calcium sulfate whisker average diameter in hundreds of nanometer, but also usually can be called nanoscale.So the non-conducting filler of the present invention's nano-scale herein refers to the nanoscale non-conducting filler usually thought 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; Be 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, is 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, namely fusing point is at 20 ~ 480 ° of C, be preferably 100 ~ 250 ° of C, be more preferably at least one in the single component metal of 120 ~ 230 ° of C and metal alloy, and its fusing point is simultaneously lower than described polymer process temperature.
Preferably, the single component 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 the metal alloy of at least one in gallium, caesium, rubidium, indium, tin, bismuth, cadmium, lead element and at least one in copper, silver, gold, iron or Zn-ef ficiency, or be the alloy that at least one in gallium, caesium, rubidium, indium, tin, bismuth, cadmium, lead element and at least one in copper, silver, gold, iron or Zn-ef ficiency and element silicon and/or carbon are formed.
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, is 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 broken-staple metal fibre in polymer fiber, its preferred diameter is less than or equal to 12 μm, is more preferably and is less than or equal to 8 μm, most preferably is and is less than or equal to 3 μm.
The preparation method of polymer/non-conducting filler/metal composite fiber of the present invention comprises the following steps:
Step one, by described amount, the component comprising described thermoplastic resin, described non-conducting filler and described metal is carried out melt blending, obtain polymer/non-conducting filler/metal blends.
Wherein said melt blending is the processing conditions of usual thermoplastic resin melt blending.
The microscopic pattern of the polymer/non-conducting filler/metal blends 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 there is 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, thus makes low-melting-point metal in polymeric matrix, disperse particle diameter to diminish, on the other hand, also reduce the probability that metallic particles collision rift occurs to merge again, make the particle diameter of metallic particles become less, metallic particles is more, and the spacing of metallic particles is less.
Step 2, by resulting polymers in step one/non-conducting filler/metal blends spinning on spinning equipment, obtain polymer/non-conducting filler/metal composite precursor.
Wherein said spinning equipment is spinning equipment general in prior art, under the usual spinning condition of adopted thermoplastic resin spinning, adopts common spray silk and rolling speed to carry out spinning.Usually, rolling speed is faster, and the fibre diameter obtained is thinner, and wherein broken-staple metal fibre diameter is less, causes the electrical property of the composite fibre finally obtained better.
Step 3, the polymer/non-conducting filler/metal composite precursor of gained in step 2 is added hot-stretch in the temperature lower than adopted thermoplastic resin fusing point 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 wherein adding hot-stretch adopts usual stretching ratio, preferably greater than or equal to 2 times, is more preferably and is more than or equal to 5 times, most preferably be and be 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, simultaneously due to the existence of non-conducting filler in system, in step one, the particle diameter of the decentralized photo metallic particles of resulting polymers/non-conducting filler/metal blends becomes less, metallic particles is more, the spacing of metallic particles is less, so broken-staple metal fibre diameter is less in composite fibre prepared after step 2 and step 3, the spacing of broken-staple metal fibre is shorter, makes the electrical property of composite fibre better.
Be exactly common melt-blending process during rubber and plastic is processed by blended to described polymer, non-conducting filler and metal melting adopted method in the step one of the preparation method of polymer/non-conducting filler/metal composite fiber of the present invention, the usual processing temperature of blending temperature and thermoplastic resin, shortly should not only ensureing to select in adopted thermoplastic resin and the complete melting of metal but also the scope that adopted thermoplastic resin can not be made to decompose.In addition, according to processing needs, in blended material, the conven-tional adjuvants of thermoplastic resin processing can be added in right amount.Each components such as described thermoplastic resin, non-conducting filler and metal can be added in melt blending equipment by modes such as metered charge in Blending Processes simultaneously and carry out melt blending; Also first by general mixing device, in advance each component described can be mixed, and then through rubber plastic blend equipment melt blending.
The rubber plastic blend equipment used in the step one of preparation method 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.
Also can containing auxiliary agent conventional in field of plastics processing in the raw material of the step one of preparation method.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 ensureing 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 there is co-mixing system due to non-conducting filler in system in step one improves very large, under the condition of identical shear rate, system is subject to larger shear action, thus make low-melting-point metal in polymeric matrix, disperse particle diameter to diminish, on the other hand, also reduce the probability that metallic particles collision rift occurs to merge again, the particle diameter of metallic particles is made to become less, metallic particles is more, the spacing of metallic particles is less, this is the guarantee obtaining polymer/non-conducting filler/metal composite fiber of the present invention.The microscopic pattern of polymer/non-conducting filler/metal composite fiber prepared is like this: 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 the existence due to non-conducting filler makes staple fibre diameter less, and the spacing of staple fibre is shorter, and the antistatic property of obtained fiber is improved, and the feel keeping fiber good; Simultaneously, because broken-staple metal fibre is arranged in polymer fiber inside, protection broken-staple metal fibre not by bending, stretch, folding, wearing and tearing and washing time infringement, solve layer on surface of metal oxidizable, easily to come off or metal dust is easily reunited, thus the problem causing antistatic effect to decline; And due to adding of metal, solve 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.Low-melting-point metal selected by polymer/non-conducting filler/metal composite fiber of the present invention can improve the spinning properties of the fiber in the processability of granulation process and spinning process, enhances productivity, saves production cost; And by selecting the large thermoplastic resin of fusing point difference scope and metal to arrange in pairs or groups to widen working condition, be easy to produce.
Detailed description of the invention
The present invention is further described below in conjunction with embodiment.Scope of the present invention is not by the restriction of these embodiments, and scope of the present invention proposes in the dependent claims.
in embodiment, experimental data following instrument and equipment and assay method measures:
(1) method of testing of the diameter of broken-staple metal fibre utilizes 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-volume resistivity is: the composite fibre 1, choosing about 2cm length, at two ends with conductive tape adhesiving metal aluminium foil as test electrode, the length t of the composite fibre between measurement electrode the inner; 2, the diameter d of composite fibre is measured with optics fibrescope; 3, the PC-68 high resistant instrument of Shanghai precision instrumentation company is used to measure fiber volume resistance R
v; 4, according to the specific insulation ρ of following formulae discovery fiber sample
v,
average after measuring 10 fibers.
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., Ltd, fusing point 138 DEG C), 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); Be wherein 100 weight parts with polypropylene, 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 German HAAKE company PolymLab double screw extruder extruding pelletization afterwards, extruder each section of temperature is: 190 DEG C, 200 DEG C, 210 DEG C, 210 DEG C, 210 DEG C, 200 DEG C (head temperature).Pellet to be added in capillary rheometer spinning at 200 DEG C and obtain compound precursor, velocity of plunger is 5mm/min, and rolling speed is 60m/min.Obtain polymer-montmorillonoid/metal composite fiber after compound precursor being stretched under 150 DEG C of conditions 15 times of former length, carry out every test, test result lists in table 1.
With flying-spot microscope observation, in composite fibre, the diameter of broken-staple metal fibre is less than 1.06 μm.Length is for being more than or equal to 7.5 μm.Seldom occur fracture of wire phenomenon in spinning process, the fiber surface obtained is smooth.
Embodiment 2
Except the volume ratio of metal alloy and polymer is pressed except 1:100, all the other are all identical with embodiment 1, and resulting polymers/imvite/metal composite fiber, carry out every test, test result lists in table 1.
With flying-spot microscope observation, in composite fibre, the diameter of broken-staple metal fibre is less than 2.15 μm.Length is for being more than or equal to 7.5 μm.Seldom occur fracture of wire phenomenon in spinning process, the fiber surface obtained is smooth.
Embodiment 3
Except the volume ratio of metal alloy and polymer is pressed except 2:100, all the other are all identical with embodiment 1, and resulting polymers/imvite/metal composite fiber, carry out every test, test result lists in table 1.
With flying-spot microscope observation, in composite fibre, the diameter of broken-staple metal fibre is less than 2.46 μm.Length is for being more than or equal to 7.5 μm.Seldom occur fracture of wire phenomenon in spinning process, the fiber surface obtained is smooth.
Comparative example 1
Except not adding except metal alloy, all the other are all identical with embodiment 1, and gained level polypropylene/montmorillonoid fiber, carry out every test, test result lists in table 1.Occur fracture of wire phenomenon in a large number in spinning process, and the fiber surface obtained is coarse.
Embodiment 4
Be stretched at 150 DEG C except 5 times of former length except by compound precursor, all the other are all identical with embodiment 3, and resulting polymers/imvite/metal composite fiber, carry out every test, test result lists in table 1.
With flying-spot microscope observation, in composite fibre, the diameter of broken-staple metal fibre is less than 3.01 μm.Length is for being more than or equal to 6.5 μm.Seldom occur fracture of wire phenomenon in spinning process, the fiber surface obtained is smooth.
Comparative example 2
Except not adding except metal alloy, all the other are all identical with embodiment 4, and gained level polypropylene/montmorillonoid fiber, carry out every test, test result lists in table 1.Occur fracture of wire phenomenon in a large number in spinning process, and the fiber surface obtained is coarse.
Embodiment 5
Be stretched at 150 DEG C except 10 times of former length except by compound precursor, all the other are all identical with embodiment 3, and resulting polymers/imvite/metal composite fiber, carry out every test, test result lists in table 1.
With flying-spot microscope observation, in composite fibre, the diameter of broken-staple metal fibre is less than 2.05 μm.Length is for being more than or equal to 8.5 μm.Seldom occur fracture of wire phenomenon in spinning process, the fiber surface obtained is smooth.
Comparative example 3
Except not adding except metal alloy, all the other are all identical with embodiment 5, and gained level polypropylene/montmorillonoid fiber, carry out every test, test result lists in table 1.Occur fracture of wire phenomenon in a large number in spinning process, and the fiber surface obtained 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 (fusing point 138 DEG C), 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); Be wherein 100 weight parts with polypropylene, 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 German HAAKE company PolymLab double screw extruder extruding pelletization afterwards, extruder each section of temperature is: 190 DEG C, 200 DEG C, 210 DEG C, 210 DEG C, 210 DEG C, 200 DEG C (head temperature).Pellet to be added in capillary rheometer spinning at 200 DEG C and obtain compound precursor, velocity of plunger is 5mm/min, and rolling speed is 60m/min.Obtain polymer/calcium carbonate/metal composite fiber after compound precursor being stretched under 150 DEG C of conditions 15 times of former length, carry out every test, test result lists in table 1.
With flying-spot microscope observation, in composite fibre, the diameter of broken-staple metal fibre is less than 2.06 μm.Length is for being more than or equal to 7.8 μm.Seldom occur fracture of wire phenomenon in spinning process, the fiber surface obtained is smooth.
Comparative example 4
Except not adding except metal alloy, all the other are all identical with embodiment 6, and gained polypropylene/calcium carbonate fiber, carry out every test, test result lists in table 1.Occur fracture of wire phenomenon in a large number in spinning process, and the fiber surface obtained is coarse.
Embodiment 7
Except being except 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, carry out every test, test result lists in table 1.
With flying-spot microscope observation, in composite fibre, the diameter of broken-staple metal fibre is less than 2.09 μm.Length is for being more than or equal to 7.5 μm.Seldom occur fracture of wire phenomenon in spinning process, the fiber surface obtained is smooth.
Comparative example 5
Except not adding except metal alloy, all the other are all identical with embodiment 7, and gained polypropylene/calcium carbonate fiber, carry out every test, test result lists in table 1.Occur fracture of wire phenomenon in a large number in spinning process, and the fiber surface obtained 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 (fusing point 138 DEG C), 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); Be wherein 100 weight parts with polypropylene, 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 German HAAKE company PolymLab double screw extruder extruding pelletization afterwards, extruder each section of temperature is: 190 DEG C, 200 DEG C, 210 DEG C, 210 DEG C, 210 DEG C, 200 DEG C (head temperature).Pellet to be added in capillary rheometer spinning at 200 DEG C and obtain compound precursor, velocity of plunger is 5mm/min, and rolling speed is 60m/min.Obtain polymer/calcium sulfate crystal whiskers/metal composite fiber after compound precursor being stretched under 150 DEG C of conditions 15 times of former length, carry out every test, test result lists in table 1.
With flying-spot microscope observation, in composite fibre, the diameter of broken-staple metal fibre is less than 3.06 μm.Length is for being more than or equal to 8 μm.Seldom occur fracture of wire phenomenon in spinning process, the fiber surface obtained is smooth.
Comparative example 6
Except not adding except metal alloy, all the other are all identical with embodiment 8, and gained polypropylene/calcium sulfate crystal whiskers fiber, carry out every test, test result lists in table 1.Occur fracture of wire phenomenon in a large number in spinning process, and the fiber surface obtained is coarse.
Embodiment 9
Polymer adopts polyamide 11(France A Kema, trade mark NaturalD40, and fusing point is 179 DEG C), metal alloy is sn-bi alloy (fusing point 138 DEG C), 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); Be wherein 100 weight parts with polyamide 11, 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 German HAAKE company PolymLab double screw extruder extruding pelletization afterwards, extruder each section of temperature is: 200 DEG C, 210 DEG C, 220 DEG C, 220 DEG C, 220 DEG C, 210 DEG C (head temperature).Pellet to be added in capillary rheometer spinning at 200 DEG C and obtain compound precursor, velocity of plunger is 5mm/min, and rolling speed is 60m/min.Compound precursor is stretched under 170 DEG C of conditions genuine 15 times after obtain polymer/calcium carbonate/metal composite fiber, carry out every test, test result lists in table 1.
With flying-spot microscope observation, in composite fibre, the diameter of broken-staple metal fibre is less than 1.50 μm.Length is for being more than or equal to 7.1 μm.Seldom occur fracture of wire phenomenon in spinning process, the fiber surface obtained is smooth.
Comparative example 7
Except not adding except metal alloy, all the other are all identical with embodiment 9, and polyamide/calcium carbonate fiber test result lists in table 1.Occur fracture of wire phenomenon in a large number in spinning process, and the fiber surface obtained is coarse.
Table 1
Claims (27)
1. polymer/non-conducting filler/metal composite fiber, it comprises the polymer fiber containing 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; Melting is there is not in described non-conducting filler under described polymer process temperature; Described metal is low-melting-point metal, is selected from least one in single component metal and metal alloy, and its fusing point is at 20 ~ 480 DEG C, and its fusing point is simultaneously lower than described polymer process temperature.
2. polymer/non-conducting 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 0.01:100 ~ 20:100.
3. polymer/non-conducting filler/metal composite fiber according to claim 2, is characterized in that, described broken-staple metal fibre and the volume ratio of polymer fiber are 0.1:100 ~ 4:100.
4. polymer/non-conducting filler/metal composite fiber according to claim 2, is characterized in that, described broken-staple metal fibre and the volume ratio of polymer fiber are 0.5:100 ~ 2:100.
5. polymer/non-conducting filler/metal composite fiber according to claim 1, it is characterized in that, described melting point metal is at 100 ~ 250 DEG C.
6. polymer/non-conducting filler/metal composite fiber according to claim 5, it is characterized in that, described melting point metal is at 120 ~ 230 DEG C.
7. polymer/non-conducting filler/metal composite fiber according to claim 1, is characterized in that, the single component 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 the metal alloy of at least one in gallium, caesium, rubidium, indium, tin, bismuth, cadmium, lead element and at least one in copper, silver, gold, iron or Zn-ef ficiency, or be the alloy that at least one in gallium, caesium, rubidium, indium, tin, bismuth, cadmium, lead element and at least one in copper, silver, gold, iron or Zn-ef ficiency and element silicon and/or carbon are formed.
8. 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 μm.
9. polymer/non-conducting filler/metal composite fiber according to claim 8, is characterized in that described broken-staple metal fibre diameter is less than or equal to 8 μm.
10. polymer/non-conducting filler/metal composite fiber according to claim 8, is characterized in that described broken-staple metal fibre diameter is less than or equal to 3 μm.
11. polymer/non-conducting filler/metal composite fibers according to claim 1, is characterized in that, described polymer is fusing point at the thermoplastic resin of 90 ~ 450 DEG C.
12. polymer/non-conducting filler/metal composite fibers according to claim 11, is characterized in that, described polymer is fusing point at the thermoplastic resin of 100 ~ 290 DEG C.
13. polymer/non-conducting filler/metal composite fibers according to claim 11, it is characterized in that, described polymer is selected from the one in polyethylene, polypropylene, polyamide, polyester.
14. polymer/non-conducting filler/metal composite fibers according to claim 1, it is characterized in that, described non-conducting filler and the weight ratio of polymer are 0.1:100 ~ 30:100.
15. polymer/non-conducting filler/metal composite fibers according to claim 14, it is characterized in that, described non-conducting filler and the weight ratio of polymer are 0.5:100 ~ 10:100.
16. polymer/non-conducting filler/metal composite fibers according to claim 14, it is characterized in that, described non-conducting filler and the weight ratio of polymer are 1:100 ~ 2:100.
17. polymer/non-conducting filler/metal composite fibers according to claim 1, it is characterized in that, described non-conducting filler is at least less than 500 μm in one dimension size on its three-dimensional dimension.
18. polymer/non-conducting filler/metal composite fibers according to claim 17, it is characterized in that, described non-conducting filler is at least less than 300 μm in one dimension size on its three-dimensional dimension.
19. 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 non-conductive slaine, metal nitride, non-metal nitride, non-metallic carbide, metal hydroxides, metal oxide, nonmetal oxide, natural crystal.
20. 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.
21., according to the polymer/non-conducting filler/metal composite fiber one of claim 17 ~ 20 Suo Shu, is characterized in that, described non-conducting filler is nanoscale non-conducting filler.
22. polymer/non-conducting filler/metal composite fibers according to claim 21, it is characterized in that, described nanoscale non-conducting filler has at least one dimension to be less than 100nm on its three-dimensional dimension.
23. polymer/non-conducting filler/metal composite fibers according to claim 22, it is characterized in that, described nanoscale non-conducting filler has at least one dimension to be less than 50nm on its three-dimensional dimension.
The preparation method of 24. 1 kinds of polymer/non-conducting filler/metal composite fibers according to any one of claim 1 ~ 23, comprises the steps:
Step one, the described component comprising thermoplastic resin, non-conducting filler and metal is carried out melt blending, obtain polymer/non-conducting filler/metal blends;
Step 2, by above resulting polymers/non-conducting filler/metal blends spinning on spinning equipment, obtain polymer/non-conducting filler/metal composite precursor;
Step 3, by above resulting polymers/non-conducting filler/metal composite precursor in the temperature lower than adopted thermoplastic resin fusing point, and add hot-stretch in temperature range greater than or equal to adopted low-melting-point metal fusing point and obtain polymer/non-conducting filler/metal composite fiber.
The preparation method of 25. polymer/non-conducting filler/metal composite fibers according to claim 24, is characterized in that the stretching ratio adding hot-stretch described in step 3 is more than or equal to 2 times.
The preparation method of 26. polymer/non-conducting filler/metal composite fibers according to claim 25, is characterized in that the stretching ratio adding hot-stretch described in step 3 is more than or equal to 5 times.
The preparation method of 27. polymer/non-conducting filler/metal composite fibers according to claim 25, is characterized in that the stretching ratio adding hot-stretch described in step 3 is 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 |
| KR1020157031983A KR101917257B1 (en) | 2013-04-12 | 2014-04-11 | Polymer/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 |
| 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 |
| US14/783,813 US10787754B2 (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 |
| TW103113454A TWI647263B (en) | 2013-04-12 | 2014-04-11 | Polymer/filler/metal composite fiber and preparation method thereof |
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