CN103556451A - Method for compounding functional nanoparticles on surfaces of polymer filaments - Google Patents
Method for compounding functional nanoparticles on surfaces of polymer filaments Download PDFInfo
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Abstract
The invention relates to a method for compounding functional nanoparticles on surfaces of polymer filaments, belonging to the technical field of new fiber materials. The method comprises the steps of protein-based modification on surfaces of functional nanoparticles, preparation of a blended solution, formation of polymer filaments with surfaces compounded with the blended solution and control of thickness, phase inversion primary formation of the polymer filaments with surfaces compounded with the blended solution and thermosetting formation of the polymer filaments with surfaces compounded with the blended solution, thus obtaining the polymer filaments with surfaces compounded with the functional nanoparticles. In the preparation method, carbon nano tubes, graphene, carbon black, titanium dioxide, zinc dioxide, iron particles, iron oxide, aluminium oxide, silver particles and other nanoparticles can be compounded on the surfaces of the polymer filaments. The polymer filaments after compounding have good mechanical properties and functionality. The preparation method is simple to operate, dispenses with special equipment and achieves industrial production easily.
Description
Technical field
A kind of method that the present invention relates to polymer filaments surface recombination function nano particle, belongs to new fiber materials technical field.
Background technology
Functional filament is high, functional outstanding, the broad-spectrum new material of a kind of added value.Yet the technology of preparing of functional filament is comparatively complicated, equipment requirement is high, and operation is numerous and diverse, needs the technical staff of higher level.China lags behind developed country in functional filament field, is not only embodied on engineering and equipment, is more embodied in functional filament preparation method's innovation, causes being limited by abroad in some high-tech sophisticated technology fields.Therefore, novel preparation method and the technological means of development functional filament have important strategic importance and economic worth.
Function nano particle refers to the nano particle with single or several functions, comprises CNT, Graphene, carbon black, titanium dioxide, zinc oxide, iron particle, tri-iron tetroxide, alundum (Al2O3), silver particles etc.These function nano particles have conduction, magnetic conduction, antibiotic, uvioresistant, self-catalysis, the several functions such as heat insulation.At present, function nano particle and polymer are carried out to co-blended spinning, and to prepare functional filament be the most common method and technology, and co-blended spinning comprises wet method co-blended spinning and melt blending spinning.Wet method co-blended spinning is mainly for polyvinyl alcohol base product, but due to the problems such as environmental protection, degraded and hydrothermal stability of polyvinyl alcohol itself, its scale application is subject to great restriction.Melt blending spinning is mainly for terylene, polyamide fibre, polypropylene fibre or polyethylene base product, because melt blending spinning technique is simple, it is little to take up an area, the functional filament that adopts the method to prepare has had commodity to sell on market, but adopt the method to prepare functional filament and also run into following several problem: one, the dispersion problem of function nano particle, function nano particle is due to its nanometer size effect, cause it in melt blending spinning process, to be difficult for disperseing, not only affect the performance of product, also increased the loss of process equipment; Two, the covering property problem of function nano particle, in melt blending spinning process, it is coated that function nano particle is easily aggregated thing matrix, causes blend filament cannot embody the functional of function nano particle, as: antibiotic property, electric conductivity etc.; Three, the loading of function nano particle is lower, the maximization that lower loading cannot practical function long filament functional performance, and higher loading certainly will affect the mechanical property of polymer filaments, causes it not possess use value.These problems cause functional filament prepared by melt blending spinning process cannot on it is functional, realize further lifting, need new technology and method improve the functional of functional filament.For a difficult problem as above, we adopt a kind of method of polymer filaments surface recombination in polymer filaments surface recombination function nano particle/thermoplastic polyurethane modified layer, realize the functionalization on polymer filaments surface.
Summary of the invention
Problem for above-mentioned existence, the object of the invention is to overcome above-mentioned defect, provide a kind of and can effectively solve the dispersion problem of function nano particle, the method for the polymer filaments surface recombination function nano particle of the problem such as the loading of the covering property problem of function nano particle, function nano particle is lower for meeting the solution of the object of the invention is:
A kind of method of polymer filaments surface recombination function nano particle adopts following steps:
The albumen modification of A function nano particle surface
Adopt ultrasonic wave that function nano particle is dispersed in the water soluble protein aqueous solution that mass fraction is 0.5-2%, the mass ratio of function nano particle and the water soluble protein aqueous solution is 1:10-1:20, dispersion temperature is 50-60 ° of C, disperse, after 1-3h, the temperature of dispersion soln is reduced to 1-5 ° of C, after static placement 24-72h through centrifuge the centrifugal and dry function nano particle that obtains surface protein, the centrifugation rate of centrifuge is 5000 revs/min, and baking temperature is 80 ° of C;
The preparation of B blend solution
Press following mass percent:
The function nano particle 1-16% of surface protein
Thermoplastic polyurethane 1-12%
Dimethyl formamide 72-98%
The function nano particle of the surface protein of preparing through steps A is put into dimethyl formamide, adopt ultrasonic wave to disperse after 1-3h, add thermoplastic polyurethane, in temperature, be under the condition of 25-35 ° of C, adopt mechanical agitation that thermoplastic polyurethane is dissolved, after dissolving 3-5h, through static vacuumizing and defoaming, obtain blend solution, the viscosity of blend solution is 500-2000mPas, and static vacuumizing and defoaming temperature is 25-35 ° of C;
The formation of C polymer filaments surface recombination blend solution and the control of thickness
The blend solution of preparing through step B is warming up under ultrasonic oscillation state to 35-45 ° of C, polymer filaments is passed through to the thread eye on blend solution and THICKNESS CONTROL mould with the speed of 50-400m/min, obtaining surface recombination blend solution thickness is the polymer filaments of 10-200 μ m, and polymer filaments is 2-15cm through the distance of blend solution;
The inversion of phases of D polymer filaments surface recombination blend solution is one-step forming just
By the polymer filaments of the surface recombination blend solution of preparing through step C take the speed of 50-400m/min through excess temperature after the deionized water of 60-85 ° of C, obtain the just polymer filaments of one-step forming of surface recombination blend solution, the polymer filaments of surface recombination blend solution is 1-5cm through the distance of deionized water;
The heat cure moulding of E polymer filaments surface recombination blend solution
In speed process heated drying case by the polymer filaments of the first one-step forming of the surface recombination blend solution of preparing through step D with 50-400m/min, heat-treat, heat treatment temperature is 90-150 ° of C, after heat treatment 10-40s, formation thickness in polymer filaments surface is function nano particle/thermoplastic polyurethane blended layer of 0.2-56 μ m, obtains the polymer filaments of surface recombination function nano particle.
Described function nano particle is a kind of in CNT or Graphene or carbon black or titanium dioxide or zinc oxide or iron particle or tri-iron tetroxide or alundum (Al2O3) or silver particles, the average grain diameter≤300nm of function nano particle.
Described water soluble protein is a kind of in keratin or fibroin or gelatin, and number-average molecular weight is 1000-10000.
The number-average molecular weight of described thermoplastic polyurethane is 20000-180000, and fusing point is 160-190 ° of C.
Described polymer filaments is a kind of in terylene or polyamide fibre or polyvinyl or acrylic fibers or viscose or polypropylene fibre or polyethylene, and the dawn number of polymer filaments is the 1-200 dawn, and radical is 1-160 root.
The aperture of the thread eye on described THICKNESS CONTROL mould is 25-380 μ m, and the length of thread eye is 5-20mm.
Owing to having adopted above technical scheme, the present invention has the following advantages:
The first, according to long-term verification experimental verification, the functional characteristic of polymer filaments all depends on its surface characteristic, and mechanics isostructuralism can depend on its this structure characteristic, namely its matrix material characteristic.Therefore, patent of the present invention forms one deck function nano particle/thermoplastic polyurethane blended layer on polymer filaments surface.Owing to belonging to the surface recombination of polymer filaments, do not affect the mechanical property of polymer filaments itself, realized the functional modification of polymer filaments, retained again the mechanical property of polymer filaments itself.Meanwhile, the method for surface recombination has also been avoided matrix material in melt blending spinning and has easily been coated a difficult problem for function nano particle.
The second, through long-term verification experimental verification, thermoplastic polyurethane material has good compatibility, flexibility and pardon, select thermoplastic polyurethane can realize simultaneously with the interface adhesion of polymer, with the plyability of function nano particle and the retentivity of polymer filaments mechanical property.Simultaneously, thermoplastic polyurethane possesses the thermal property of thermoplastic, in the process of the heat cure moulding of polymer filaments surface recombination blend solution, heat treatment temperature can effectively plastify thermoplastic polyurethane, can optimize the structure of self, on polymer filaments surface, form function nano particle/thermoplastic polyurethane blended layer of compact structure, good mechanical performance.
Three, adopt the modifying surface of water-solubility protein confrontation function nano particle, mainly solve compatibility, dispersiveness and the high problem of filling of function nano particle.According to verification experimental verification repeatedly, in melt spinning, function nano particle content cannot spinning over 20%.Meanwhile, the content of function nano particle cannot maximize its advantage lower than 40%.Gelatin is artificial bioprotein, and keratin and fibroin are native protein, all has the same amido link structure with the large molecule of thermoplastic polyurethane.Therefore, the albumen of function nano particle surface increased and thermoplastic polyurethane between compatibility, and then short can being dispersed in uniformly in thermoplastic polyurethane solution.Surface proteinization can also be increased to the content of function nano particle more than 90%, at the functional function nano particle/thermoplastic polyurethane blend solution of surface protein that makes of maximum functionality nano particle simultaneously, there is certain viscosity and mobility, the lack of homogeneity of having avoided function nano particle and high cannot the becoming silk or reconstituting the problem of fiber of causing of filling.
Four, polymer filaments surface recombination blend solution thickness can regulate according to the pore size of thread eye on THICKNESS CONTROL mould.THICKNESS CONTROL mould contains 100-2000 thread eye, and the length of thread eye is 5-20mm, and aperture is 25-380 μ m and the diameter that is greater than polymer filaments.Utilize function nano particle/thermoplastic polyurethane blend solution of surface protein to there is certain viscosity, when immersing the polymer filaments of blend solution, enter after the thread eye on THICKNESS CONTROL mould, according to fluid mechanics principle blend solution, can enter thread eye along with polymer filaments, then utilize the pore size of thread eye to control out the thickness of polymer filaments surface recombination blend solution after thread eye.Therefore, utilize thread eye on THICKNESS CONTROL mould and the dawn number of polymer filaments, can accurately control the thickness of polymer filaments surface recombination blend solution, the dawn number of polymer filaments and the reduction formula of its diameter are as follows:
, wherein:
dfor diameter,
dfor dawn number,
ρfor density.In addition, in blend solution, the distance of polymer filaments process is 2-15cm, if lower than this distance, blend solution and polymer filaments Surface Contact time are shorter, cannot effectively be compounded in polymer filaments surface; If be greater than this distance, blend solution easily enters in polymer filaments, is present in the gap between monofilament in polymer filaments, just can affect greatly the feel of polymer filaments after these blend solutions solidify, causes polymer filaments to use.
The 5th, for polymer filaments surface recombination blend solution, the method that the present invention has adopted the first one-step forming of inversion of phases and heat cure moulding to combine, as: by the polymer filaments of surface recombination blend solution take the speed of 50-400m/min through excess temperature after the coagulating bath of 60-85 ° of C, obtain the just polymer filaments of one-step forming of surface recombination blend solution, and then it is still heat-treated in the speed process heated drying case with 50-400m/min, heat treatment temperature is 90-150 ° of C, after heat treatment 10-40s, formation thickness in polymer filaments surface is function nano particle/thermoplastic polyurethane blended layer of 0.2-56 μ m, obtain the polymer filaments of surface recombination function nano particle.If only adopt coagulating bath to carry out inversion of phases moulding, will there is the skin-core structure of multiple hole in polymer filaments surface recombination blend solution, and such blended layer will lose mechanical property and adhesiveness, easily separated with polymer filaments; If only adopt heat cure moulding, the high surface tension on polymer filaments surface easily causes function nano particle/thermoplastic polyurethane blend solution to infiltrate for negative, and then the formation droplet-like that swells, cause polymer filaments surface to occur discontinuous form and comparatively coarse function nano particle blended layer, lose the accurate control ability of thickness simultaneously.Therefore, through long-term test and exploration, the present invention combines the method for inversion of phases moulding and heat cure forming method, and is shaped to master with heat cure, and inversion of phases is shaped to auxiliary process conditions.Utilize the preliminary method of forming of inversion of phases to carry out inversion of phases moulding to polymer filaments surface recombination blend solution tentatively fixing, the surface of blend solution layer is first solidified, present continuous shape.Then adopt heat cure forming method, under Thermodynamic effect, make the heat cure of blend solution layer and shrink gradually the surface that is compounded in polymer filaments.In addition, it is 1-5cm that the method requires the distance of polymer filaments process in coagulating bath, is less than the distance of conventional spinning technique requirement.If be less than this distance, the surface of polymer filaments surface recombination blend solution can not be solidified, and cannot effectively carry out next step technique; If be greater than this distance, the inversion of phases moulding of polymer filaments surface recombination blend solution is comparatively serious, causes its surperficial blended layer can not meet mechanical property requirements.Therefore, by heat cure, be shaped to master, inversion of phases is shaped to auxiliary technology and method, the blended layer compact structure after polymer filaments surface cure, good mechanical properties.
Six, in the method, as long as polymer filaments does not have the physical property that is dissolved in water or dimethyl formamide or dimethylacetylamide in 1s, all can use the method at polymer filaments surface recombination function nano particle, realize the functionalization of polymer filaments, the polymer filaments kind that can select is more.Meanwhile, in the method, the technique of polymer filaments surface recombination function nano particle is continuous, and the constant and scope of processing speed is 50-400m/min, can meet the requirement of continuous industrial production.
The method of a kind of polymer filaments surface recombination function nano particle of the present invention, after modification, polymer filaments is simple in structure, and product is various, be widely used, preparation method's technique is simple, and equipment requirement is low, convenient operation and control, is easy to realize suitability for industrialized production, without special installation.
The specific embodiment
A kind of method of polymer filaments surface recombination function nano particle adopts following steps:
The albumen modification of A function nano particle surface
Adopt ultrasonic wave by a kind of being dispersed in the keratin or a kind of aqueous solution in fibroin or gelatin that mass fraction is 0.5-2% in the CNT of average grain diameter≤300nm or Graphene or carbon black or titanium dioxide or zinc oxide or iron particle or tri-iron tetroxide or alundum (Al2O3) or silver particles, its number-average molecular weight is 1000-10000, the mass ratio of function nano particle and the water soluble protein aqueous solution is 1:10-1:20, dispersion temperature is 50-60 ° of C, disperse, after 1-3h, the temperature of dispersion soln is reduced to 1-5 ° of C, after static placement 24-72h through centrifuge the centrifugal and dry function nano particle that obtains surface protein, the centrifugation rate of centrifuge is 5000 revs/min, baking temperature is 80 ° of C,
The preparation of B blend solution
Press following mass percent:
The function nano particle 1-16% of surface protein
Thermoplastic polyurethane 1-12%
Dimethyl formamide 72-98%
The function nano particle of the surface protein of preparing through steps A is put into dimethyl formamide, adopt ultrasonic wave to disperse after 1-3h, adding number-average molecular weight is 20000-180000, fusing point is the thermoplastic polyurethane of 160-190 ° of C, in temperature, be under the condition of 25-35 ° of C, adopt mechanical agitation that thermoplastic polyurethane is dissolved, after dissolving 3-5h, through static vacuumizing and defoaming, obtain blend solution, the viscosity of blend solution is 500-2000mPas, and static vacuumizing and defoaming temperature is 25-35 ° of C;
The formation of C polymer filaments surface recombination blend solution and the control of thickness
The blend solution of preparing through step B is warming up under ultrasonic oscillation state to 35-45 ° of C, by dawn number, it it is the 1-200 dawn, radical is the terylene of 1-160 root or a kind of process blend solution of the speed with 50-400m/min in polyamide fibre or polyvinyl or acrylic fibers or viscose or polypropylene fibre or polyethylene and the thread eye on THICKNESS CONTROL mould, obtaining surface recombination blend solution thickness is the polymer filaments of 10-200 μ m, polymer filaments is 2-15cm through the distance of blend solution, the aperture of thread eye is 25-380 μ m, and the length of thread eye is 5-20mm;
The inversion of phases of D polymer filaments surface recombination blend solution is one-step forming just
By the polymer filaments of the surface recombination blend solution of preparing through step C take the speed of 50-400m/min through excess temperature after the deionized water of 60-85 ° of C, obtain the just polymer filaments of one-step forming of surface recombination blend solution, the polymer filaments of surface recombination blend solution is 1-5cm through the distance of deionized water;
The heat cure moulding of E polymer filaments surface recombination blend solution
In speed process heated drying case by the polymer filaments of the first one-step forming of the surface recombination blend solution of preparing through step D with 50-400m/min, heat-treat, heat treatment temperature is 90-150 ° of C, after heat treatment 10-40s, formation thickness in polymer filaments surface is function nano particle/thermoplastic polyurethane blended layer of 0.2-56 μ m, obtains the polymer filaments of surface recombination function nano particle.
Below in conjunction with specific embodiment, the method for polymer filaments surface recombination function nano particle of the present invention is described in further detail:
Embodiment mono-
The albumen modification of A function nano particle surface
Adopting CNT 5g that ultrasonic wave is 20nm by average grain diameter to be dispersed in mass fraction is in 0.5% keratin aqueous solution 100g, keratic number-average molecular weight is 1000, dispersion temperature is 50 ° of C, disperse, after 1h, the temperature of dispersion soln is reduced to 1 ° of C, after static placement 24h through centrifuge the centrifugal and dry CNT that obtains surface protein, the centrifugation rate of centrifuge is 5000 revs/min, and baking temperature is 80 ° of C;
B puts into 98g dimethyl formamide by the CNT 1g of the surface protein of preparing through steps A, adopt ultrasonic wave to disperse after 1h, add that number-average molecular weight is 20000, fusing point is the thermoplastic polyurethane 1g of 160 ° of C, in temperature, be under the condition of 25 ° of C, adopt mechanical agitation that thermoplastic polyurethane is dissolved, after dissolving 3h, through static vacuumizing and defoaming, obtain blend solution, the viscosity of blend solution is 500 mPas, and static vacuumizing and defoaming temperature is 25 ° of C;
C is warming up to the blend solution of preparing through step B 35 ° of C under ultrasonic oscillation state, by dawn number, it it was 1 dawn, radical is that the terylene of 1 be take the thread eye that length that the speed of 50 m/min is 25 μ m, hole through aperture on blend solution and THICKNESS CONTROL mould is 5mm, obtaining surface recombination blend solution thickness is the terylene of 10 μ m, and terylene is 2 cm through the distance of blend solution;
D by the terylene of the surface recombination blend solution of preparing through step C take the speed of 50 m/min through excess temperature after the deionized water of 60 ° of C, obtain the terylene of the preliminary sizing of surface recombination blend solution, the terylene of surface recombination blend solution is 1 cm through the distance of deionized water;
E heat-treats the terylene of the preliminary sizing of the surface recombination blend solution of preparing through step D in the speed process heated drying case with 50 m/min, heat treatment temperature is 90 ° of C, after heat treatment 10s, formation thickness in terylene surface is CNT/thermoplastic polyurethane blended layer of 0.2 μ m, obtains the terylene of surface recombination CNT.
Embodiment bis-
The albumen modification of A function nano particle surface
Adopting Graphene 6g that ultrasonic wave is 50nm by average grain diameter to be dispersed in mass fraction is in 0.8% silk fibroin aqueous solution 100g, the number-average molecular weight of fibroin is 2000, dispersion temperature is 55 ° of C, disperse, after 2h, the temperature of dispersion soln is reduced to 2 ° of C, after static placement 36h through centrifuge the centrifugal and dry Graphene that obtains surface protein, the centrifugation rate of centrifuge is 5000 revs/min, and baking temperature is 80 ° of C;
B puts into 97g dimethyl formamide by the Graphene 2g of the surface protein of preparing through steps A, adopt ultrasonic wave to disperse after 2h, add that number-average molecular weight is 300000, fusing point is the thermoplastic polyurethane 1g of 170 ° of C, in temperature, be under the condition of 30 ° of C, adopt mechanical agitation that thermoplastic polyurethane is dissolved, after dissolving 4h, through static vacuumizing and defoaming, obtain blend solution, the viscosity of blend solution is 700 mPas, and static vacuumizing and defoaming temperature is 30 ° of C;
C is warming up to the blend solution of preparing through step B 40 ° of C under ultrasonic oscillation state, by dawn number, it was 10 dawn, radical is that the polyamide fibre of 4 be take the thread eye that length that the speed of 80 m/min is 50 μ m, hole through aperture on blend solution and THICKNESS CONTROL mould is 10mm, obtaining surface recombination blend solution thickness is the polyamide fibre of 12 μ m, and polyamide fibre is 4 cm through the distance of blend solution;
D by the polyamide fibre of the surface recombination blend solution of preparing through step C take the speed of 80 m/min through excess temperature after the deionized water of 65 ° of C, obtain the polyamide fibre of the preliminary sizing of surface recombination blend solution, the polyamide fibre of surface recombination blend solution is 2 cm through the distance of deionized water;
E heat-treats the polyamide fibre of the preliminary sizing of the surface recombination blend solution of preparing through step D in the speed process heated drying case with 80 m/min, heat treatment temperature is 100 ° of C, after heat treatment 20s, formation thickness in polyamide fibre surface is Graphene/thermoplastic polyurethane blended layer of 0.36 μ m, obtains the polyamide fibre of surface recombination Graphene.
Embodiment tri-
The albumen modification of A function nano particle surface
Adopting carbon black 7g that ultrasonic wave is 100nm by average grain diameter to be dispersed in mass fraction is in 1% aqueous gelatin solution 100g, the number-average molecular weight of gelatin is 3000, dispersion temperature is 60 ° of C, disperse, after 3h, the temperature of dispersion soln is reduced to 3 ° of C, after static placement 48h through centrifuge the centrifugal and dry carbon black that obtains surface protein, the centrifugation rate of centrifuge is 5000 revs/min, and baking temperature is 80 ° of C;
B puts into 93g dimethyl formamide by the carbon black 5g of the surface protein of preparing through steps A, adopt ultrasonic wave to disperse after 3h, add that number-average molecular weight is 500000, fusing point is the thermoplastic polyurethane 2g of 180 ° of C, in temperature, be under the condition of 35 ° of C, adopt mechanical agitation that thermoplastic polyurethane is dissolved, after dissolving 5h, through static vacuumizing and defoaming, obtain blend solution, the viscosity of blend solution is 900 mPas, and static vacuumizing and defoaming temperature is 35 ° of C;
C is warming up to the blend solution of preparing through step B 45 ° of C under ultrasonic oscillation state, by dawn number, it was 30 dawn, radical is that the polyvinyl of 12 be take the thread eye that length that the speed of 100 m/min is 100 μ m, hole through aperture on blend solution and THICKNESS CONTROL mould is 15mm, obtaining surface recombination blend solution thickness is the polyvinyl of 34 μ m, and polyvinyl is 6 cm through the distance of blend solution;
D by the polyvinyl of the surface recombination blend solution of preparing through step C take the speed of 100 m/min through excess temperature after the deionized water of 70 ° of C, obtain the polyvinyl of the preliminary sizing of surface recombination blend solution, the polyvinyl of surface recombination blend solution is 3 cm through the distance of deionized water;
E heat-treats the polyvinyl of the preliminary sizing of the surface recombination blend solution of preparing through step D in the speed process heated drying case with 100 m/min, heat treatment temperature is 110 ° of C, after heat treatment 30s, formation thickness in polyvinyl surface is carbon black/thermoplastic polyurethane blended layer of 2.38 μ m, obtains the polyvinyl of surface recombination carbon black.
Embodiment tetra-
The albumen modification of A function nano particle surface
Adopting titanium dioxide 8g that ultrasonic wave is 120nm by average grain diameter to be dispersed in mass fraction is in 1.2% keratin aqueous solution 100g, keratic number-average molecular weight is 4000, dispersion temperature is 50 ° of C, disperse, after 1h, the temperature of dispersion soln is reduced to 4 ° of C, after static placement 60h through centrifuge the centrifugal and dry titanium dioxide that obtains surface protein, the centrifugation rate of centrifuge is 5000 revs/min, and baking temperature is 80 ° of C;
B puts into 90g dimethyl formamide by the titanium dioxide 7g of the surface protein of preparing through steps A, adopt ultrasonic wave to disperse after 1h, add that number-average molecular weight is 700000, fusing point is the thermoplastic polyurethane 3g of 190 ° of C, in temperature, be under the condition of 25 ° of C, adopt mechanical agitation that thermoplastic polyurethane is dissolved, after dissolving 3h, through static vacuumizing and defoaming, obtain blend solution, the viscosity of blend solution is 1000 mPas, and static vacuumizing and defoaming temperature is 25 ° of C;
C is warming up to the blend solution of preparing through step B 35 ° of C under ultrasonic oscillation state, by dawn number, it was 60 dawn, radical is that the acrylic fibers of 24 be take the thread eye that length that the speed of 150 m/min is 150 μ m, hole through aperture on blend solution and THICKNESS CONTROL mould is 20mm, obtaining surface recombination blend solution thickness is the acrylic fibers of 57 μ m, and acrylic fibers are 8 cm through the distance of blend solution;
D by the acrylic fibers of the surface recombination blend solution of preparing through step C take the speed of 150 m/min through excess temperature after the deionized water of 75 ° of C, obtain the acrylic fibers of the preliminary sizing of surface recombination blend solution, the acrylic fibers of surface recombination blend solution are 4 cm through the distance of deionized water;
E heat-treats the acrylic fibers of the preliminary sizing of the surface recombination blend solution of preparing through step D in the speed process heated drying case with 150 m/min, heat treatment temperature is 120 ° of C, after heat treatment 40s, formation thickness in acrylic fibers surface is titanium dioxide/thermoplastic polyurethane blended layer of 5.7 μ m, obtains the acrylic fibers of surface recombination titanium dioxide.
Embodiment five
The albumen modification of A function nano particle surface
Adopting zinc oxide 9g that ultrasonic wave is 150nm by average grain diameter to be dispersed in mass fraction is in 1.4% silk fibroin aqueous solution 100g, the number-average molecular weight of fibroin is 5000, dispersion temperature is 55 ° of C, disperse, after 2h, the temperature of dispersion soln is reduced to 5 ° of C, after static placement 72h through centrifuge the centrifugal and dry zinc oxide that obtains surface protein, the centrifugation rate of centrifuge is 5000 revs/min, and baking temperature is 80 ° of C;
B puts into 87g dimethyl formamide by the zinc oxide 8g of the surface protein of preparing through steps A, adopt ultrasonic wave to disperse after 2h, add that number-average molecular weight is 1000000, fusing point is the thermoplastic polyurethane 5g of 160 ° of C, in temperature, be under the condition of 30 ° of C, adopt mechanical agitation that thermoplastic polyurethane is dissolved, after dissolving 4h, through static vacuumizing and defoaming, obtain blend solution, the viscosity of blend solution is 1200 mPas, and static vacuumizing and defoaming temperature is 30 ° of C;
C is warming up to the blend solution of preparing through step B 40 ° of C under ultrasonic oscillation state, by dawn number, it was 100 dawn, radical is that the viscose of 35 be take the thread eye that length that the speed of 200 m/min is 200 μ m, hole through aperture on blend solution and THICKNESS CONTROL mould is 5mm, obtaining surface recombination blend solution thickness is the viscose of 80 μ m, and viscose is 10 cm through the distance of blend solution;
D by the viscose of the surface recombination blend solution of preparing through step C take the speed of 200 m/min through excess temperature after the deionized water of 80 ° of C, obtain the viscose of the preliminary sizing of surface recombination blend solution, the viscose of surface recombination blend solution is 5cm through the distance of deionized water;
E heat-treats the viscose of the preliminary sizing of the surface recombination blend solution of preparing through step D in the speed process heated drying case with 200 m/min, heat treatment temperature is 130 ° of C, after heat treatment 10s, formation thickness in viscose surface is zinc oxide/thermoplastic polyurethane blended layer of 10.4 μ m, obtains the viscose of surface recombination zinc oxide.
Embodiment six
The albumen modification of A function nano particle surface
Adopting iron particle 10g that ultrasonic wave is 180nm by average grain diameter to be dispersed in mass fraction is in 1.6% aqueous gelatin solution 100g, the number-average molecular weight of gelatin is 6000, dispersion temperature is 60 ° of C, disperse, after 3h, the temperature of dispersion soln is reduced to 1 ° of C, after static placement 24h through centrifuge the centrifugal and dry iron particle that obtains surface protein, the centrifugation rate of centrifuge is 5000 revs/min, and baking temperature is 80 ° of C;
B puts into 89g dimethyl formamide by the iron particle 10g of the surface protein of preparing through steps A, adopt ultrasonic wave to disperse after 3h, add that number-average molecular weight is 1200000, fusing point is the thermoplastic polyurethane 1g of 170 ° of C, in temperature, be under the condition of 35 ° of C, adopt mechanical agitation that thermoplastic polyurethane is dissolved, after dissolving 5h, through static vacuumizing and defoaming, obtain blend solution, the viscosity of blend solution is 1400 mPas, and static vacuumizing and defoaming temperature is 35 ° of C;
C is warming up to the blend solution of preparing through step B 45 ° of C under ultrasonic oscillation state, by dawn number, it was 120 dawn, radical is that the polypropylene fibre of 50 be take the thread eye that length that the speed of 250 m/min is 250 μ m, hole through aperture on blend solution and THICKNESS CONTROL mould is 10mm, obtaining surface recombination blend solution thickness is the polypropylene fibre of 120 μ m, and polypropylene fibre is 12 cm through the distance of blend solution;
D by the polypropylene fibre of the surface recombination blend solution of preparing through step C take the speed of 250 m/min through excess temperature after the deionized water of 85 ° of C, obtain the polypropylene fibre of the preliminary sizing of surface recombination blend solution, the polypropylene fibre of surface recombination blend solution is 1 cm through the distance of deionized water;
E heat-treats the polypropylene fibre of the preliminary sizing of the surface recombination blend solution of preparing through step D in the speed process heated drying case with 250 m/min, heat treatment temperature is 140 ° of C, after heat treatment 20s, formation thickness in polypropylene fibre surface is iron particle/thermoplastic polyurethane blended layer of 13.2 μ m, obtains the polypropylene fibre of surface recombination iron particle.
Embodiment seven
The albumen modification of A function nano particle surface
Adopting tri-iron tetroxide 5g that ultrasonic wave is 200nm by average grain diameter to be dispersed in mass fraction is in 1.8% keratin aqueous solution 100g, keratic number-average molecular weight is 7000, dispersion temperature is 50 ° of C, disperse, after 1h, the temperature of dispersion soln is reduced to 2 ° of C, after static placement 36h through centrifuge the centrifugal and dry tri-iron tetroxide that obtains surface protein, the centrifugation rate of centrifuge is 5000 revs/min, and baking temperature is 80 ° of C;
B puts into 84g dimethyl formamide by the tri-iron tetroxide 11g of the surface protein of preparing through steps A, adopt ultrasonic wave to disperse after 1h, add that number-average molecular weight is 1400000, fusing point is the thermoplastic polyurethane 5g of 180 ° of C, in temperature, be under the condition of 25 ° of C, adopt mechanical agitation that thermoplastic polyurethane is dissolved, after dissolving 3h, through static vacuumizing and defoaming, obtain blend solution, the viscosity of blend solution is 1600 mPas, and static vacuumizing and defoaming temperature is 25 ° of C;
C is warming up to the blend solution of preparing through step B 35 ° of C under ultrasonic oscillation state, by dawn number, it was 160 dawn, radical is that the polyethylene of 80 be take the thread eye that length that the speed of 300 m/min is 310 μ m, hole through aperture on blend solution and THICKNESS CONTROL mould is 15mm, obtaining surface recombination blend solution thickness is the polyethylene of 160 μ m, and polyethylene is 14 cm through the distance of blend solution;
D by the polyethylene of the surface recombination blend solution of preparing through step C take the speed of 300 m/min through excess temperature after the deionized water of 60 ° of C, obtain the polyethylene of the preliminary sizing of surface recombination blend solution, the polyethylene of surface recombination blend solution is 2 cm through the distance of deionized water;
E heat-treats the polyethylene of the preliminary sizing of the surface recombination blend solution of preparing through step D in the speed process heated drying case with 300 m/min, heat treatment temperature is 150 ° of C, after heat treatment 30s, formation thickness in polyethylene surface is tri-iron tetroxide/thermoplastic polyurethane blended layer of 25.6 μ m, obtains the polyethylene of surface recombination tri-iron tetroxide.
Embodiment eight
The albumen modification of A function nano particle surface
Adopting alundum (Al2O3) 6g that ultrasonic wave is 250nm by average grain diameter to be dispersed in mass fraction is in 1.9% silk fibroin aqueous solution 100g, the number-average molecular weight of fibroin is 8000, dispersion temperature is 55 ° of C, disperse, after 2h, the temperature of dispersion soln is reduced to 3 ° of C, after static placement 48h through centrifuge the centrifugal and dry alundum (Al2O3) that obtains surface protein, the centrifugation rate of centrifuge is 5000 revs/min, and baking temperature is 80 ° of C;
B puts into 77g dimethyl formamide by the alundum (Al2O3) 13g of the surface protein of preparing through steps A, adopt ultrasonic wave to disperse after 2h, add that number-average molecular weight is 1600000, fusing point is the thermoplastic polyurethane 10g of 190 ° of C, in temperature, be under the condition of 30 ° of C, adopt mechanical agitation that thermoplastic polyurethane is dissolved, after dissolving 4h, through static vacuumizing and defoaming, obtain blend solution, the viscosity of blend solution is 1800 mPas, and static vacuumizing and defoaming temperature is 30 ° of C;
C is warming up to the blend solution of preparing through step B 40 ° of C under ultrasonic oscillation state, by dawn number, it was 180 dawn, radical is that the terylene of 100 be take the thread eye that length that the speed of 350 m/min is 340 μ m, hole through aperture on blend solution and THICKNESS CONTROL mould is 20mm, obtaining surface recombination blend solution thickness is the terylene of 180 μ m, and terylene is 15 through the distance of blend solution;
D by the terylene of the surface recombination blend solution of preparing through step C take the speed of 350 m/min through excess temperature after the deionized water of 65 ° of C, obtain the terylene of the preliminary sizing of surface recombination blend solution, the terylene of surface recombination blend solution is 3 cm through the distance of deionized water;
E heat-treats the terylene of the preliminary sizing of the surface recombination blend solution of preparing through step D in the speed process heated drying case with 350 m/min, heat treatment temperature is 115 ° of C, after heat treatment 40s, formation thickness in terylene surface is alundum (Al2O3)/thermoplastic polyurethane blended layer of 41.4 μ m, obtains the terylene of surface recombination alundum (Al2O3).
Embodiment nine
The albumen modification of A function nano particle surface
Adopting silver particles 7g that ultrasonic wave is 300nm by average grain diameter to be dispersed in mass fraction is in 2% aqueous gelatin solution 100g, the number-average molecular weight of gelatin is 10000, dispersion temperature is 60 ° of C, disperse, after 3h, the temperature of dispersion soln is reduced to 4 ° of C, after static placement 60h through centrifuge the centrifugal and dry silver particles that obtains surface protein, the centrifugation rate of centrifuge is 5000 revs/min, and baking temperature is 80 ° of C;
B puts into 72g dimethyl formamide by the silver particles 16g of the surface protein of preparing through steps A, adopt ultrasonic wave to disperse after 3h, add that number-average molecular weight is 1800000, fusing point is the thermoplastic polyurethane 12g of 175 ° of C, in temperature, be under the condition of 35 ° of C, adopt mechanical agitation that thermoplastic polyurethane is dissolved, after dissolving 5h, through static vacuumizing and defoaming, obtain blend solution, the viscosity of blend solution is 2000 mPas, and static vacuumizing and defoaming temperature is 35 ° of C;
C is warming up to the blend solution of preparing through step B 45 ° of C under ultrasonic oscillation state, by dawn number, it was 200 dawn, radical is that the polyamide fibre of 160 be take the thread eye that length that the speed of 400m/min is 380 μ m, hole through aperture on blend solution and THICKNESS CONTROL mould is 12mm, obtaining surface recombination blend solution thickness is the polyamide fibre of 200 μ m, and polyamide fibre is 5 cm through the distance of blend solution;
D by the polyamide fibre of the surface recombination blend solution of preparing through step C take the speed of 400m/min through excess temperature after the deionized water of 70 ° of C, obtain the polyamide fibre of the preliminary sizing of surface recombination blend solution, the polyamide fibre of surface recombination blend solution is 4 cm through the distance of deionized water;
E heat-treats the polyamide fibre of the preliminary sizing of the surface recombination blend solution of preparing through step D in the speed process heated drying case with 400m/min, heat treatment temperature is 135 ° of C, after heat treatment 25s, formation thickness in polyamide fibre surface is silver particles/thermoplastic polyurethane blended layer of 56 μ m, obtains the polyamide fibre of surface recombination silver particles.
Claims (6)
1. a method for polymer filaments surface recombination function nano particle, is characterized in that: described method adopts following steps:
The albumen modification of A function nano particle surface
Adopt ultrasonic wave that function nano particle is dispersed in the water soluble protein aqueous solution that mass fraction is 0.5-2%, the mass ratio of function nano particle and the water soluble protein aqueous solution is 1:10-1:20, dispersion temperature is 50-60 ° of C, disperse, after 1-3h, the temperature of dispersion soln is reduced to 1-5 ° of C, after static placement 24-72h through centrifuge the centrifugal and dry function nano particle that obtains surface protein, the centrifugation rate of centrifuge is 5000 revs/min, and baking temperature is 80 ° of C;
The preparation of B blend solution
Press following mass percent:
The function nano particle 1-16% of surface protein
Thermoplastic polyurethane 1-12%
Dimethyl formamide 72-98%
First the function nano particle of the surface protein of preparing through steps A is put into dimethyl formamide, ultrasonic wave disperses after 1-3h, add again thermoplastic polyurethane, in temperature, be under the condition of 25-35 ° of C, adopt mechanical agitation that thermoplastic polyurethane is dissolved, after dissolving 3-5h, through static vacuumizing and defoaming, obtain blend solution, the viscosity of blend solution is 500-2000mPas, and static vacuumizing and defoaming temperature is 25-35 ° of C;
The formation of C polymer filaments surface recombination blend solution and the control of thickness
The blend solution of preparing through step B is warming up under ultrasonic oscillation state to 35-45 ° of C, polymer filaments is passed through to the thread eye on blend solution and THICKNESS CONTROL mould with the speed of 50-400m/min, obtaining surface recombination blend solution thickness is the polymer filaments of 10-200 μ m, and polymer filaments is 2-15cm through the distance of blend solution;
The inversion of phases of D polymer filaments surface recombination blend solution is one-step forming just
By the polymer filaments of the surface recombination blend solution of preparing through step C take the speed of 50-400m/min through excess temperature after the deionized water of 60-85 ° of C, obtain the just polymer filaments of one-step forming of surface recombination blend solution, the polymer filaments of surface recombination blend solution is 1-5cm through the distance of deionized water;
The heat cure moulding of E polymer filaments surface recombination blend solution
In speed process heated drying case by the polymer filaments of the first one-step forming of the surface recombination blend solution of preparing through step D with 50-400m/min, heat-treat, heat treatment temperature is 90-150 ° of C, after heat treatment 10-40s, formation thickness in polymer filaments surface is function nano particle/thermoplastic polyurethane blended layer of 0.2-56 μ m, obtains the polymer filaments of surface recombination function nano particle.
2. the method for a kind of polymer filaments surface recombination function nano particle according to claim 1, it is characterized in that: described function nano particle is a kind of in CNT or Graphene or carbon black or titanium dioxide or zinc oxide or iron particle or tri-iron tetroxide or alundum (Al2O3) or silver particles, the average grain diameter≤300nm of function nano particle.
3. the method for a kind of polymer filaments surface recombination function nano particle according to claim 1, is characterized in that: described water soluble protein is a kind of in keratin or fibroin or gelatin, and number-average molecular weight is 1000-10000.
4. the method for a kind of polymer filaments surface recombination function nano particle according to claim 1, is characterized in that: the number-average molecular weight of described thermoplastic polyurethane is 20000-180000, and fusing point is 160-190 ° of C.
5. the method for a kind of polymer filaments surface recombination function nano particle according to claim 1, it is characterized in that: described polymer filaments is a kind of in terylene or polyamide fibre or polyvinyl or acrylic fibers or viscose or polypropylene fibre or polyethylene, the dawn number of polymer filaments is the 1-200 dawn, and radical is 1-160 root.
6. the method for a kind of polymer filaments surface recombination function nano particle according to claim 1, is characterized in that: the aperture of the thread eye on described THICKNESS CONTROL mould is 25-380 μ m, and the length of thread eye is 5-20mm.
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