CN103556451B - A kind of method of polymer filaments surface recombination function nano particle - Google Patents

Abstract

The invention relates to a method for compounding functional nanoparticles on the surface of polymer filaments, belonging to the technical field of new fiber materials. A method for compounding functional nanoparticles on the surface of polymer filaments according to the present invention is to process polymer filaments through protein modification on the surface of functional nanoparticles, preparation of a blend solution, and formation of a composite blend solution on the surface of polymer filaments The polymer filaments with composite functional nanoparticles on the surface are obtained through the control of the thickness, the phase inversion preliminary molding of the composite blend solution on the surface of the polymer filament, and the thermosetting molding of the composite blend solution on the surface of the polymer filament. The preparation method of the present invention can compound nanoparticles such as carbon nanotubes, graphene, carbon black, titanium dioxide, zinc dioxide, iron particles, ferric oxide, aluminum oxide, silver particles, etc. on the surface of polymer filaments, The composite polymer filaments have good mechanical properties and functionality. The preparation method of the invention is simple to operate, does not require special equipment, and is easy to realize industrial production.

Description

A method for compounding functional nanoparticles on the surface of polymer filaments

technical field

The invention relates to a method for compounding functional nanoparticles on the surface of polymer filaments, belonging to the technical field of new fiber materials.

Background technique

Functional filament is a new type of material with high added value, outstanding functionality and wide application. However, the preparation technology of functional filaments is relatively complicated, the equipment requirements are high, the process is complicated, and a high level of technical personnel is required. my country lags behind developed countries in the field of functional filaments, which is not only reflected in engineering technology and equipment, but also in the innovation of functional filament preparation methods, resulting in some high-tech cutting-edge technology fields being controlled by foreign countries. Therefore, the development of new preparation methods and technical means of functional filaments has important strategic significance and economic value.

Functional nanoparticles refer to nanoparticles with single or multiple functions, including carbon nanotubes, graphene, carbon black, titanium dioxide, zinc dioxide, iron particles, ferric oxide, aluminum oxide, silver particles, etc. . These functional nanoparticles have many functions such as electric conduction, magnetic conduction, antibacterial, anti-ultraviolet, self-catalysis, and heat insulation. At present, blending and spinning functional nanoparticles and polymers to prepare functional filaments is the most common method and technology, and blend spinning includes wet blend spinning and melt blend spinning. Wet blend spinning is mainly aimed at polyvinyl alcohol-based products, but its large-scale application is greatly limited due to the environmental protection, degradation and moisture-heat stability of polyvinyl alcohol itself. Melt blend spinning is mainly aimed at polyester, nylon, polypropylene or ethylene-based products. Due to the simple process of melt blend spinning and small footprint, the functional filaments prepared by this method have been sold in the market, but the method used to prepare Functional filaments also encountered the following problems: 1. The dispersibility of functional nanoparticles. Due to their nano-size effect, functional nanoparticles are not easy to disperse in the process of melt blending and spinning, which not only affects the performance of the product, but also Increased the loss of processing equipment; 2. The coating problem of functional nanoparticles. In the process of melt blending and spinning, functional nanoparticles are easily covered by polymer matrix, resulting in the failure of blended filaments to reflect the function of functional nanoparticles. properties, such as: antibacterial, electrical conductivity, etc.; 3. The filling amount of functional nanoparticles is low, and the lower filling amount cannot maximize the functional performance of functional filaments, while the higher filling amount will inevitably affect the performance of polymer filaments. The mechanical properties make it useless. These problems lead to the inability to further improve the functionality of the functional filaments prepared by the melt blending spinning method, and new technologies and methods are needed to improve the functionality of the functional filaments. To solve the problems mentioned above, we adopt a method of polymer filament surface compounding to compound functional nanoparticles/thermoplastic polyurethane modified layer on the surface of polymer filament to realize the functionalization of the surface of polymer filament.

Contents of the invention

In view of the above-mentioned existing problems, the purpose of the present invention is to overcome the above-mentioned defects, and provide a kind of polymerization system that can effectively solve the problems of dispersion of functional nanoparticles, encapsulation of functional nanoparticles, and low filling amount of functional nanoparticles. The method for compounding functional nanoparticles on the surface of the long filament, the solution for meeting the purpose of the present invention is:

A method for compounding functional nanoparticles on the surface of polymer filaments adopts the following steps:

A Protein modification on the surface of functional nanoparticles

Ultrasound is used to disperse functional nanoparticles in a water-soluble protein aqueous solution with a mass fraction of 0.5-2%, the mass ratio of functional nanoparticles to water-soluble protein aqueous solution is 1:10-1:20, and the dispersion temperature is 50-60°C After dispersing for 1-3h, reduce the temperature of the dispersion solution to 1-5°C, and after standing still for 24-72h, centrifuge and dry to obtain surface proteinized functional nanoparticles. The centrifugal speed of the centrifuge is 5000 rpm , the drying temperature is 80°C;

Preparation of B blend solution

According to the following mass percentage:

Surface proteinized functional nanoparticles 1-16%

Thermoplastic Polyurethane 1-12%

Dimethylformamide 72-98%

Put the surface proteinified functional nanoparticles prepared in step A into dimethylformamide, disperse by ultrasonic waves for 1-3h, add thermoplastic polyurethane, and use mechanical stirring under the condition of temperature 25-35°C The thermoplastic polyurethane is dissolved, and after dissolving for 3-5 hours, a blended solution is obtained through static vacuum degassing, the viscosity of the blended solution is 500-2000mPa s, and the static vacuum degassing temperature is 25-35°C;

C Formation and Thickness Control of Composite Blend Solution on the Surface of Polymer Filament

Warming up the blend solution prepared in step B to 35-45°C under ultrasonic vibration, passing the polymer filament through the guide wire hole on the blend solution and the thickness control mold at a speed of 50-400m/min, to obtain Polymer filaments with a surface composite blending solution thickness of 10-200 μm, and the distance of the polymer filaments passing through the blending solution is 2-15 cm;

D Preliminary formation of phase inversion of composite blend solution on the surface of polymer filaments

After the polymer filaments of the surface composite blend solution prepared in step C pass through deionized water at a temperature of 60-85° C. at a rate of 50-400 m/min, the polymer filaments initially formed by the surface composite blend solution are obtained. Silk, the distance of the polymer filament of the surface composite blend solution passing through the deionized water is 1-5cm;

E Thermosetting molding of composite blend solution on the surface of polymer filaments

The polymer filaments initially formed by the surface composite blending solution prepared in step D are heat-treated in a heat drying oven at a rate of 50-400m/min, and the heat treatment temperature is 90-150°C. After heat treatment for 10-40s, the polymer A blended layer of functional nanoparticles/thermoplastic polyurethane with a thickness of 0.2-56 μm is formed on the surface of the filaments to obtain polymer filaments with composite functional nanoparticles on the surface.

The functional nanoparticles are one of carbon nanotubes or graphene or carbon black or titanium dioxide or zinc dioxide or iron particles or ferric oxide or aluminum oxide or silver particles, and the average particle diameter of the functional nanoparticles is ≤300nm.

The water-soluble protein is one of keratin, silk fibroin or gelatin, and the number average molecular weight is 1000-10000.

The number average molecular weight of the thermoplastic polyurethane is 20000-180000, and the melting point is 160-190°C.

The polymer filament is one of polyester, nylon, vinylon, acrylic, viscose, polypropylene or polyethylene, and the denier of the polymer filament is 1-200 denier, and the number of filaments is 1-160.

The hole diameter of the guide wire hole on the thickness control mold is 25-380 μm, and the length of the guide wire hole is 5-20 mm.

Owing to adopting above technical scheme, the present invention has the following advantages:

First, according to long-term experimental verification, the functional properties of polymer filaments depend on their surface properties, while the mechanical and other structural properties depend on their constitutive properties, that is, the properties of their matrix materials. Therefore, the patent of the present invention forms a functional nanoparticle/thermoplastic polyurethane blend layer on the surface of the polymer filament. Due to the surface compounding of the polymer filaments, the mechanical properties of the polymer filaments are not affected, that is, the functional modification of the polymer filaments is realized, and the mechanical properties of the polymer filaments are retained. At the same time, the method of surface compounding also avoids the problem that the matrix material is easy to coat functional nanoparticles in melt blending spinning.

Second, after long-term experiments, thermoplastic polyurethane materials have good compatibility, softness and inclusiveness. Selecting thermoplastic polyurethane can simultaneously achieve interface adhesion with polymers, composite properties with functional nanoparticles, and polymer Retention of filament mechanical properties. At the same time, thermoplastic polyurethane has the thermal properties of thermoplastic materials. During the thermosetting molding process of the composite blend solution on the surface of polymer filaments, the heat treatment temperature can effectively plasticize thermoplastic polyurethane so that it can optimize its own structure. A functional nanoparticle/thermoplastic polyurethane blend layer with dense structure and excellent mechanical properties is formed on the surface of the filament.

Third, use water-soluble proteins to modify the surface of functional nanoparticles, mainly to solve the problems of compatibility, dispersibility and high filling of functional nanoparticles. According to many tests and verifications, if the content of functional nanoparticles in melt spinning exceeds 20%, it cannot be spun. Meanwhile, the content of functional nanoparticles below 40% cannot maximize its advantages. Gelatin is an artificial biological protein, and keratin and silk fibroin are natural proteins, both of which have the same amide bond structure as thermoplastic polyurethane macromolecules. Therefore, the proteinization of the surface of functional nanoparticles increases the compatibility with thermoplastic polyurethane, and then promotes their uniform dispersion in thermoplastic polyurethane solution. Surface proteinization can also increase the content of functional nanoparticles to more than 90%. While maximizing the functionality of functional nanoparticles, the surface proteinized functional nanoparticles/thermoplastic polyurethane blend solution has a certain viscosity and fluidity, avoiding The poor uniformity and high filling of functional nanoparticles lead to the inability to form filaments or restructure into fibers.

Fourth, the thickness of the composite blend solution on the surface of the polymer filament can be adjusted according to the diameter of the guide wire hole on the thickness control mold. The thickness control mold contains 100-2000 guidewire holes, the length of the guidewire holes is 5-20mm, the hole diameter is 25-380μm and is larger than the diameter of the polymer filament. The functional nanoparticle/thermoplastic polyurethane blend solution that uses surface proteinization has a certain viscosity. When the polymer filament immersed in the blend solution enters the guide wire hole on the thickness control mold, the blend solution will follow the principle of fluid mechanics. The polymer filament enters the guide wire hole, and then the thickness of the composite blending solution on the surface of the polymer filament after exiting the guide wire hole is controlled by the diameter of the guide wire hole. Therefore, the thickness of the composite blend solution on the surface of the polymer filament can be precisely controlled by using the guide wire hole on the thickness control mold and the denier of the polymer filament. The conversion formula between the denier of the polymer filament and its diameter is as follows: , where: d is the diameter, D is the denier, and ρ is the density. In addition, the distance traveled by the polymer filament in the blend solution is 2-15cm. If it is lower than this distance, the contact time between the blend solution and the surface of the polymer filament is short, and it cannot be effectively compounded on the surface of the polymer filament; If it is greater than this distance, the blending solution will easily enter the polymer filaments, and exist in the gaps between the monofilaments in the polymer filaments. When these blending solutions solidify, it will greatly affect the feel of the polymer filaments. Rendering the polymer filament unusable.

Fifth, for the composite blending solution on the surface of polymer filaments, the present invention adopts the method of combining phase inversion preliminary molding and thermosetting molding, such as: the polymer filaments of the surface composite blending solution are mixed at a rate of 50-400m/min After passing through the coagulation bath with a temperature of 60-85°C at a rate of 60-85°C, the polymer filaments formed by the surface composite blend solution are obtained, and then they are still heat-treated at a rate of 50-400m/min in a heat drying oven. The heat treatment temperature is 90-150°C. After heat treatment for 10-40s, a functional nanoparticle/thermoplastic polyurethane blend layer with a thickness of 0.2-56 μm is formed on the surface of the polymer filament to obtain a polymer filament with surface composite functional nanoparticles. If only a coagulation bath is used for phase inversion molding, the composite blend solution on the surface of the polymer filament will have a porous sheath-core structure, and such a blend layer will lose its mechanical properties and adhesion, and will be easily separated from the polymer filament; If only thermosetting molding is used, the high surface tension on the surface of the polymer filament will easily lead to negative infiltration of the functional nanoparticle/thermoplastic polyurethane blend solution, and then expand to form a droplet, resulting in a discontinuous shape on the surface of the polymer filament. The coarser functional nanoparticle blend layer loses the ability to precisely control the thickness at the same time. Therefore, after long-term experiments and explorations, the present invention combines the methods of phase inversion molding and thermosetting molding, and uses thermosetting molding as the main process condition, and phase inversion molding as the auxiliary process condition. The composite blending solution on the surface of the polymer filament is preliminarily fixed by phase inversion molding using a phase inversion preliminary forming method, so that the surface of the blending solution layer is solidified first and presents a continuous shape. Then, a thermosetting molding method is adopted to heat-cure the blended solution layer under the action of thermodynamics and gradually shrink and compound on the surface of the polymer filament. In addition, the method requires that the polymer filaments travel a distance of 1-5 cm in the coagulation bath, which is smaller than that required by conventional spinning processes. If it is less than this distance, the surface of the composite blend solution on the surface of the polymer filament cannot be solidified, and the next step process cannot be effectively carried out; if it is greater than this distance, the phase inversion molding of the composite blend solution on the surface of the polymer filament is relatively serious, resulting in its The surface blended layer cannot meet the requirements of mechanical properties. Therefore, through the technology and method of thermosetting molding as the main part and phase inversion molding as the auxiliary part, the blended layer after the surface curing of the polymer filament has a compact structure and good mechanical properties.

Sixth, in this method, as long as the polymer filament does not have the physical property of dissolving in water or dimethylformamide or dimethylacetamide within 1s, this method can be used to compound functional nanometers on the surface of the polymer filament. Particles realize the functionalization of polymer filaments, and there are many types of polymer filaments that can be selected. At the same time, the process of compounding functional nanoparticles on the surface of polymer filaments in the method is continuous, and the processing rate is constant and the range is 50-400m/min, which can meet the requirements of continuous industrial production.

The method for compounding functional nanoparticles on the surface of a polymer filament according to the present invention has the advantages of simple structure of the modified polymer filament, various products, wide application, simple preparation method, low equipment requirements, convenient operation and control, and easy Realize industrial production without special equipment.

Detailed ways

A method for compounding functional nanoparticles on the surface of polymer filaments adopts the following steps:

A Protein modification on the surface of functional nanoparticles

Use ultrasonic waves to disperse one of carbon nanotubes or graphene or carbon black or titanium dioxide or zinc dioxide or iron particles or ferric oxide or aluminum oxide or silver particles with an average particle size of ≤300nm in a mass fraction of 0.5 -In an aqueous solution of 2% keratin or silk fibroin or gelatin, its number average molecular weight is 1000-10000, the mass ratio of functional nanoparticles to water-soluble protein aqueous solution is 1:10-1:20, and the dispersion temperature is 50-60°C, after dispersing for 1-3h, reduce the temperature of the dispersion solution to 1-5°C, after standing still for 24-72h, centrifuge and dry in a centrifuge to obtain functional nanoparticles with surface proteinization, the centrifuge speed 5000 rpm, drying temperature is 80°C;

Preparation of B blend solution

According to the following mass percentage:

Surface proteinized functional nanoparticles 1-16%

Thermoplastic Polyurethane 1-12%

Dimethylformamide 72-98%

Put the surface proteinized functional nanoparticles prepared by step A into dimethylformamide, and after ultrasonic dispersion for 1-3h, add thermoplastic polyurethane with a number average molecular weight of 20000-180000 and a melting point of 160-190°C, Under the condition that the temperature is 25-35°C, mechanical stirring is used to dissolve the thermoplastic polyurethane. After dissolving for 3-5 hours, a blended solution is obtained through static vacuum degassing. The viscosity of the blended solution is 500-2000mPa·s. The vacuum defoaming temperature is 25-35°C;

C Formation and Thickness Control of Composite Blend Solution on the Surface of Polymer Filament

Warm up the blended solution prepared in step B to 35-45°C under ultrasonic vibration, and make polyester or nylon or vinylon or acrylic fiber or viscose or One of polypropylene or polyethylene passes through the blending solution and the guide wire hole on the thickness control mold at a rate of 50-400m/min to obtain polymer filaments with a surface composite blending solution thickness of 10-200μm, and the length of the polymer is The distance of the wire passing through the blending solution is 2-15cm, the diameter of the guide wire hole is 25-380μm, and the length of the guide wire hole is 5-20mm;

D Preliminary formation of phase inversion of composite blend solution on the surface of polymer filaments

After the polymer filaments of the surface composite blend solution prepared in step C pass through deionized water at a temperature of 60-85° C. at a rate of 50-400 m/min, the polymer filaments initially formed by the surface composite blend solution are obtained. Silk, the distance of the polymer filament of the surface composite blend solution passing through the deionized water is 1-5cm;

E Thermosetting molding of composite blend solution on the surface of polymer filaments

The polymer filaments initially formed by the surface composite blending solution prepared in step D are heat-treated in a heat drying oven at a rate of 50-400m/min, and the heat treatment temperature is 90-150°C. After heat treatment for 10-40s, the polymer A blended layer of functional nanoparticles/thermoplastic polyurethane with a thickness of 0.2-56 μm is formed on the surface of the filaments to obtain polymer filaments with composite functional nanoparticles on the surface.

The method for compounding functional nanoparticles on the surface of polymer filaments of the present invention is described in further detail below in conjunction with specific examples:

Embodiment one

A Protein modification on the surface of functional nanoparticles

Adopt ultrasonic wave to be that the carbon nanotube 5g that average particle diameter is 20nm is dispersed in the keratin aqueous solution 100g that mass fraction is 0.5%, the number-average molecular weight of keratin is 1000, and dispersion temperature is 50 ℃, after dispersing 1h, will disperse solution The temperature was lowered to 1 ° C, and after standing still for 24 hours, centrifuged and dried to obtain surface proteinized carbon nanotubes, the centrifugal speed of the centrifuge was 5000 rpm, and the drying temperature was 80 ° C;

B Put 1 g of surface proteinized carbon nanotubes prepared in step A into 98 g of dimethylformamide, and after ultrasonic dispersion for 1 h, add 1 g of thermoplastic polyurethane with a number average molecular weight of 20,000 and a melting point of 160° C. Under the condition of 25°C, mechanical stirring was used to dissolve the thermoplastic polyurethane. After dissolving for 3 hours, a blend solution was obtained through static vacuum degassing. The viscosity of the blend solution was 500 mPa s, and the static vacuum degassing temperature was 25 °C. C;

C. Warm up the blended solution prepared in step B to 35°C under ultrasonic vibration, pass the polyester with a denier of 1 denier and 1 thread through the blended solution and the thickness control mold at a speed of 50 m/min The upper aperture is 25 μ m, the length of the hole is a guide wire hole of 5 mm, and the polyester with a surface composite blend solution thickness of 10 μ m is obtained, and the distance of the polyester through the blend solution is 2 cm;

D After the polyester of the surface composite blend solution prepared by step C is passed through deionized water at a temperature of 60° C. at a rate of 50 m/min, the polyester of the surface composite blend solution is initially finalized, and the surface composite blend solution is obtained. The distance of polyester through deionized water is 1 cm;

E. Heat-treat the polyester initially shaped by the surface composite blending solution prepared in step D in a heat drying oven at a rate of 50 m/min. The heat treatment temperature is 90° C. After 10 seconds of heat treatment, carbon with a thickness of 0.2 μm is formed on the surface of the polyester. A nanotube/thermoplastic polyurethane blend layer is used to obtain a polyester surface compounded with carbon nanotubes.

Embodiment two

A Protein modification on the surface of functional nanoparticles

Adopt ultrasonic wave to be that the graphene 6g that average particle diameter is 50nm is dispersed in the silk fibroin aqueous solution 100g that mass fraction is 0.8%, the number-average molecular weight of silk fibroin is 2000, and dispersion temperature is 55 DEG C, disperse 2h after the temperature of dispersion solution Be reduced to 2 DEG C, after standing still for 36h, obtain surface proteinized graphene through centrifuge centrifugation and drying, the centrifugal speed of centrifuge is 5000 rev/min, and drying temperature is 80 DEG C;

B Put the surface proteinized graphene 2g prepared by step A into 97g dimethylformamide, after adopting ultrasonic dispersion for 2h, adding number average molecular weight is 300000, melting point is 170 DEG C of thermoplastic polyurethane 1g, at a temperature of Under the condition of 30°C, the thermoplastic polyurethane was dissolved by mechanical stirring, and after dissolving for 4 hours, the blend solution was obtained through static vacuum degassing. The viscosity of the blended solution was 700 mPa s, and the static vacuum degassing temperature was 30 °C ;

C. Warm up the blended solution prepared in step B to 40°C under ultrasonic vibration, and pass through the blended solution and the thickness control mold at a speed of 80 m/min with a denier of 10 denier and 4 nylon fibers The upper hole diameter is 50 μm, the length of the hole is 10mm guide wire hole, obtains the polyamide fiber that the thickness of surface composite blending solution is 12 μm, and the distance of nylon fiber passing through the blending solution is 4 cm;

D After the nylon of the surface composite blending solution prepared by step C is passed through deionized water at a temperature of 65° C. at a rate of 80 m/min, the nylon that the surface composite blending solution is initially finalized is obtained, and the surface composite blending solution is obtained. The distance of nylon passing through deionized water is 2 cm;

E. Heat-treat the nylon that has been preliminarily shaped by the surface composite blending solution prepared in step D in a heat drying oven at a rate of 80 m/min. The heat treatment temperature is 100° C. After 20 seconds of heat treatment, the surface of the nylon forms graphite with a thickness of 0.36 μm. Graphene/thermoplastic polyurethane blended layer to obtain nylon with graphene on the surface.

Embodiment three

A Protein modification of the surface of functional nanoparticles

Adopt ultrasonic wave to be that the carbon black 7g that average particle diameter is 100nm is dispersed in the gelatin aqueous solution 100g that mass fraction is 1%, the number-average molecular weight of gelatin is 3000, and dispersion temperature is 60 DEG C, after dispersing 3h, the temperature of dispersion solution is reduced to 3 DEG C, stand still for 48h and obtain surface proteinized carbon black through centrifuge centrifugation and drying, the centrifugal speed of centrifuge is 5000 rev/min, and drying temperature is 80 DEG C;

B put into 93g dimethylformamide the carbon black 5g of the surface proteinization prepared by step A, after adopting ultrasonic dispersion 3h, add the thermoplastic polyurethane 2g that number average molecular weight is 500000, fusing point is 180 ℃, at temperature Under the condition of 35°C, the thermoplastic polyurethane was dissolved by mechanical stirring, and after dissolving for 5 hours, the blend solution was obtained through static vacuum degassing. The viscosity of the blended solution was 900 mPa s, and the static vacuum degassing temperature was 35 °C ;

C. Warm up the blended solution prepared in step B to 45°C under ultrasonic vibration, pass the vinylon with a denier of 30 deniers and 12 roots through the blended solution and the thickness control mold at a rate of 100 m/min The upper hole diameter is 100 μm, the length of the hole is 15mm guide wire hole, obtains the vinylon whose surface composite blending solution thickness is 34 μm, and the distance of vinylon passing through the blending solution is 6 cm;

D After the vinylon of the surface composite blending solution prepared by step C is passed through deionized water at a temperature of 70° C. at a rate of 100 m/min, the vinylon of the surface composite blending solution is initially finalized, and the surface composite blending solution is obtained. The distance of vinylon passing through deionized water is 3 cm;

E. Preliminarily finalize the surface composite blending solution prepared by step D. Heat treatment in a heat drying oven at a rate of 100 m/min. The heat treatment temperature is 110 ° C. After 30 seconds of heat treatment, a charcoal with a thickness of 2.38 μm is formed on the surface of the vinylon. Black/thermoplastic polyurethane blend layer to obtain vinylon with carbon black on the surface.

Embodiment four

A Protein modification of the surface of functional nanoparticles

Adopt ultrasonic wave to be that the titanium dioxide 8g that average particle diameter is 120nm is dispersed in the keratin aqueous solution 100g that mass fraction is 1.2%, the number-average molecular weight of keratin is 4000, and dispersion temperature is 50 ℃, and the temperature of dispersion solution is lowered after dispersion 1h To 4 DEG C, stand still for 60h and obtain surface proteinized titanium dioxide through centrifuge centrifugation and drying, the centrifugal speed of centrifuge is 5000 rev/min, and drying temperature is 80 DEG C;

B Put 7 g of surface proteinized titanium dioxide prepared in step A into 90 g of dimethylformamide, and after ultrasonic dispersion for 1 h, add 3 g of thermoplastic polyurethane with a number average molecular weight of 700,000 and a melting point of 190° C., at a temperature of 25 Under the condition of ℃, adopt mechanical stirring to make thermoplastic polyurethane dissolve, after dissolving 3h, obtain blend solution through static vacuum degassing, the viscosity of blend solution is 1000 mPa s, static vacuum degassing temperature is 25 DEG C;

C The blending solution prepared through step B is heated up to 35° C. under the state of ultrasonic vibration, and the denier is 60 denier, and the acrylic fiber with the root number of 24 passes through the blending solution and the thickness control mold at a speed of 150 m/min. The upper aperture is 150 μ m, the length of the hole is a guide wire hole of 20 mm, and the acrylic fibers whose surface composite blending solution thickness is 57 μ m are obtained, and the distance of acrylic fibers passing through the blending solution is 8 cm;

D After the acrylic fiber of the surface composite blending solution prepared by step C is passed through the deionized water of 75° C. at a speed of 150 m/min, the acrylic fiber that the surface composite blending solution is initially finalized is obtained, and the surface composite blending solution is obtained. The distance of acrylic fiber passing through deionized water is 4 cm;

E The acrylic fiber that is initially finalized by the surface composite blending solution prepared in step D is heat-treated in a heat drying oven at a rate of 150 m/min. The heat treatment temperature is 120° C. After 40 seconds of heat treatment, the surface of the acrylic fiber forms a titanium dioxide with a thickness of 5.7 μm. /thermoplastic polyurethane blending layer to obtain acrylic fibers with titanium dioxide on the surface.

Embodiment five

A Protein modification of the surface of functional nanoparticles

Adopt ultrasonic wave to be that the zinc dioxide 9g that average particle diameter is 150nm is dispersed in the silk fibroin aqueous solution 100g that mass fraction is 1.4%, the number-average molecular weight of silk fibroin is 5000, and dispersion temperature is 55 ℃, after dispersing 2h, will disperse solution Temperature is reduced to 5 DEG C, and the zinc dioxide of surface proteinization is obtained through centrifuge centrifugation and drying after static placement 72h, and the centrifugal speed of centrifuge is 5000 rev/mins, and drying temperature is 80 DEG C;

B Put 8g of surface proteinized zinc dioxide prepared through step A into 87g dimethylformamide, after adopting ultrasonic dispersion for 2h, adding number average molecular weight is 1000000, fusing point is 160 DEG C of thermoplastic polyurethane 5g, at temperature Under the condition of 30°C, the thermoplastic polyurethane was dissolved by mechanical stirring, and after dissolving for 4 hours, a blended solution was obtained through static vacuum degassing. The viscosity of the blended solution was 1200 mPa s, and the static vacuum degassing temperature was 30 °C C;

C Warm up the blended solution prepared in step B to 40°C under ultrasonic vibration, and pass the viscose with a denier of 100 denier and 35 sticks through the blended solution and thickness control at a rate of 200 m/min. The diameter of the hole on the mold is 200 μm, and the length of the hole is 5 mm. The viscose with a thickness of 80 μm on the surface of the composite blend solution is obtained, and the distance of the viscose through the blend solution is 10 cm;

D After the viscose of the surface composite blending solution prepared in step C passes through the deionized water with a temperature of 80°C at a rate of 200 m/min, the viscose of the surface composite blending solution is initially finalized, and the surface composite blending The distance of the viscose of the solution passing through the deionized water is 5cm;

E. Heat the preliminarily shaped viscose prepared by the surface composite blending solution prepared in step D in a heat drying oven at a rate of 200 m/min. The heat treatment temperature is 130°C. After 10 seconds of heat treatment, the thickness of the viscose surface is 10.4 μm. The zinc dioxide/thermoplastic polyurethane blend layer was used to obtain the adhesive compounded with zinc dioxide on the surface.

Embodiment six

A Protein modification of the surface of functional nanoparticles

Ultrasonic wave is used to disperse 10g of iron particles with an average particle diameter of 180nm in 100g of gelatin aqueous solution with a mass fraction of 1.6%. The number average molecular weight of gelatin is 6000, and the dispersion temperature is 60°C. After dispersing for 3h, the temperature of the dispersion solution is reduced to 1 DEG C, stand still for 24 hours and obtain surface proteinized iron particles through centrifuge centrifugation and drying, the centrifugal speed of the centrifuge is 5000 rpm, and the drying temperature is 80 DEG C;

B Put 10 g of surface proteinized iron particles prepared in step A into 89 g of dimethylformamide, and after ultrasonic dispersion for 3 hours, add 1 g of thermoplastic polyurethane with a number average molecular weight of 1,200,000 and a melting point of 170° C. Under the condition of 35°C, the thermoplastic polyurethane was dissolved by mechanical stirring, and after dissolving for 5 hours, the blend solution was obtained through static vacuum degassing. The viscosity of the blended solution was 1400 mPa s, and the static vacuum degassing temperature was 35 °C ;

C Warm up the blended solution prepared in step B to 45°C under ultrasonic vibration, pass the polypropylene fiber with a denier of 120 denier and 50 fibers through the blended solution and the thickness control mold at a rate of 250 m/min The diameter of the upper hole is 250 μm, the length of the hole is 10 mm, and the polypropylene fiber with a surface composite blend solution thickness of 120 μm is obtained, and the distance of the polypropylene fiber through the blend solution is 12 cm;

D After the polypropylene fiber of the surface composite blend solution prepared by step C is passed through deionized water at a temperature of 85° C. at a rate of 250 m/min, the polypropylene fiber of the surface composite blend solution is initially finalized, and the surface composite blend solution is obtained. The distance of polypropylene passing through deionized water is 1 cm;

E The polypropylene fiber that is initially shaped by the surface composite blending solution prepared in step D is heat-treated in a heat drying oven at a rate of 250 m/min. The heat treatment temperature is 140 ° C. After 20 seconds of heat treatment, the surface of the polypropylene fiber is formed with a thickness of 13.2 μm. Particle/thermoplastic polyurethane blend layer to obtain polypropylene fiber with iron particles on the surface.

Embodiment seven

A Protein modification of the surface of functional nanoparticles

Ultrasonic wave is used to disperse 5g of ferric oxide with an average particle diameter of 200nm in 100g of keratin aqueous solution with a mass fraction of 1.8%. The number average molecular weight of keratin is 7000, and the dispersion temperature is 50°C. The temperature of the temperature is reduced to 2 DEG C, and the surface proteinized ferric iron tetroxide is obtained through centrifugation and drying after standing still for 36 hours. The centrifugal speed of the centrifuge is 5000 rev/min, and the drying temperature is 80 DEG C;

B put into 84g dimethylformamide 11g of surface proteinized iron ferric oxide prepared by step A, after adopting ultrasonic dispersion for 1h, adding number average molecular weight is 1400000, fusing point is 180 DEG C of thermoplastic polyurethane 5g, in Under the condition that the temperature is 25°C, mechanical stirring is used to dissolve the thermoplastic polyurethane. After dissolving for 3 hours, a blended solution is obtained through static vacuum degassing. The viscosity of the blended solution is 1600 mPa s, and the static vacuum degassing temperature is 25 °C;

C. Warm up the blended solution prepared in step B to 35°C under ultrasonic vibration, and pass through the blended solution and thickness control at a speed of 300 m/min with a denier of 160 denier and 80 polyethylene fibers. The hole diameter on the mold is 310 μ m, the length of the hole is a guide wire hole of 15 mm, and the thickness of the composite blend solution on the surface is 160 μ m, and the distance of the polyethylene fiber through the blend solution is 14 cm;

D After the polyethylene fiber of the surface composite blending solution prepared by step C is passed through deionized water at a temperature of 60° C. at a rate of 300 m/min, the polyethylene fiber of the surface composite blending solution is initially finalized, and the surface composite blending solution is obtained. The distance of the polyethylene fiber of the solution passing through the deionized water is 2 cm;

E The polyethylene fiber that has been initially shaped by the surface composite blending solution prepared in step D is heat-treated in a heat drying oven at a rate of 300 m/min. The heat treatment temperature is 150 ° C. After 30 seconds of heat treatment, the surface thickness of the polyethylene fiber is 25.6 μm. The ferroferric oxide/thermoplastic polyurethane blend layer is obtained to obtain the ethylene fiber compounded with ferric oxide on the surface.

Embodiment Eight

A Protein modification of the surface of functional nanoparticles

Ultrasound is used to disperse 6g of aluminum oxide with an average particle size of 250nm in 100g of silk fibroin aqueous solution with a mass fraction of 1.9%. The number average molecular weight of silk fibroin is 8000, and the dispersion temperature is 55°C. The temperature is reduced to 3°C, after 48 hours of standing still, the aluminum oxide on the surface is obtained through centrifugation and drying in a centrifuge, the centrifugal speed of the centrifuge is 5000 rpm, and the drying temperature is 80°C;

B Put 13g of the surface proteinified aluminum oxide prepared in step A into 77g of dimethylformamide, and after ultrasonic dispersion for 2h, add 10g of thermoplastic polyurethane with a number average molecular weight of 1,600,000 and a melting point of 190°C. Under the condition that the temperature is 30°C, the thermoplastic polyurethane is dissolved by mechanical stirring, and after dissolving for 4 hours, the blend solution is obtained through static vacuum degassing. The viscosity of the blend solution is 1800 mPa s, and the static vacuum degassing temperature is 30 °C;

C. Warm up the blended solution prepared in step B to 40°C under ultrasonic vibration, pass the polyester with a denier of 180 deniers and 100 strands through the blended solution and the thickness control mold at a rate of 350 m/min The upper hole diameter is 340 μ m, the length of the hole is 20 mm of the guide wire hole, and the polyester with a surface composite blend solution thickness of 180 μ m is obtained, and the distance of the polyester through the blend solution is 15;

D After the polyester of the surface composite blend solution prepared by step C is passed through deionized water at a temperature of 65°C at a rate of 350 m/min, the polyester obtained with the surface composite blend solution is initially finalized, and the surface composite blend solution is obtained. The distance of polyester through deionized water is 3 cm;

E The polyester that is preliminarily shaped by the surface composite blending solution prepared in step D is heat-treated in a heat drying oven at a rate of 350 m/min. The heat treatment temperature is 115° C. After 40 seconds of heat treatment, a three-dimensional layer with a thickness of 41.4 μm is formed on the surface of the polyester. Aluminum oxide/thermoplastic polyurethane blend layer is used to obtain the polyester surface compounded with aluminum oxide.

Embodiment nine

A Protein modification of the surface of functional nanoparticles

Adopt ultrasonic wave to be that the silver particle 7g that average particle diameter is 300nm is dispersed in the gelatin aqueous solution 100g that mass fraction is 2%, the number average molecular weight of gelatin is 10000, and dispersing temperature is 60 ℃, after dispersing 3h, the temperature of dispersing solution is reduced to 4 DEG C, stand still for 60h and obtain surface proteinized silver particles through centrifuge centrifugation and drying, the centrifugal speed of centrifuge is 5000 rev/min, and drying temperature is 80 DEG C;

B Put 16g of surface proteinized silver particles prepared through step A into 72g dimethylformamide, after adopting ultrasonic dispersion for 3h, adding number average molecular weight is 1800000, fusing point is 12g of thermoplastic polyurethane of 175 DEG C, at a temperature of Under the condition of 35°C, the thermoplastic polyurethane was dissolved by mechanical stirring, and after dissolving for 5 hours, the blend solution was obtained through static vacuum degassing. The viscosity of the blend solution was 2000 mPa s, and the static vacuum degassing temperature was 35 °C ;

C. Warm up the blended solution prepared in step B to 45°C under ultrasonic vibration, and pass the nylon with a denier of 200 denier and 160 roots through the blended solution and thickness control mold at a rate of 400m/min. Aperture is 380 μ m, the length of hole is the guide wire hole of 12 mm, obtains the polyamide fiber that the thickness of surface composite blending solution is 200 μ m, and the distance that nylon fiber passes through blending solution is 5 cm;

D After the nylon of the surface composite blending solution prepared by step C is passed through deionized water at a temperature of 70°C at a rate of 400m/min, the nylon of the surface composite blending solution is initially finalized, and the nylon of the surface composite blending solution is obtained. The distance through deionized water is 4 cm;

E The nylon fiber that the surface composite blending solution prepared by step D is initially finalized is heat-treated in a heat drying oven at a speed of 400m/min, and the heat treatment temperature is 135°C. After heat treatment for 25s, the surface of the nylon fiber forms a silver particle with a thickness of 56 μm/ A thermoplastic polyurethane blending layer is used to obtain nylon with silver particles on the surface.

Claims (2)

1. a method for polymer filaments surface recombination function nano particle, is characterized in that: described method adopts following steps:

The ubiquitinated modification of A function nano particle surface

Ultrasonic wave is adopted to be in the water soluble protein aqueous solution of 0.5-2% at mass fraction by function nano particle dispersion, the mass ratio of function nano particle and the water soluble protein aqueous solution is 1:10-1:20, dispersion temperature is 50-60 DEG C, after dispersion 1-3h, the temperature of dispersion soln is reduced to 1-5 DEG C, through centrifuge and the dry function nano particle obtaining surface protein after static placement 24-72h, the centrifugation rate of centrifuge is 5000 revs/min, baking temperature is 80 DEG C, wherein, described function nano particle is the one 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, average grain diameter≤the 300nm of function nano particle, described water soluble protein is the one in keratin or fibroin or gelatin, number-average molecular weight is 1000-10000,

The preparation of B blend solution

By 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 prepared through steps A is put into dimethyl formamide, after ultrasonic wave dispersion 1-3h, add thermoplastic polyurethane again, be under the condition of 25-35 DEG C in temperature, adopt mechanical agitation that thermoplastic polyurethane is dissolved, blend solution is obtained through static vacuumizing and defoaming after dissolving 3-5h, the viscosity of blend solution is 500-2000mPas, static vacuumizing and defoaming temperature is 25-35 DEG C, wherein, the number-average molecular weight of described thermoplastic polyurethane is 20000-180000, and fusing point is 160-190 DEG C;

The formation of C polymer filaments surface recombination blend solution and the control of thickness

The blend solution prepared through step B is warming up to 35-45 DEG C under ultrasonic oscillation state, by polymer filaments with the thread eye of the speed of 50-400m/min on blend solution and THICKNESS CONTROL mould, obtain the polymer filaments that surface recombination blend solution thickness is 10-200 μm, polymer filaments through the distance of blend solution be 2-15cm, wherein, described polymer filaments is the one 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;

The inversion of phases just one-step forming of D polymer filaments surface recombination blend solution

By the polymer filaments of surface recombination blend solution prepared through step C with the speed of 50-400m/min after the deionized water that excess temperature is 60-85 DEG C, obtain the polymer filaments of the first 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 of E polymer filaments surface recombination blend solution is shaping

The polymer filaments of first for the surface recombination blend solution prepared through step D one-step forming is heat-treated in heated drying case with the speed of 50-400m/min, heat treatment temperature is 90-150 DEG C, heat treatment 10-40s post-consumer polymer filament surface forms function nano particle/thermoplastic polyurethane blended layer that thickness is 0.2-56 μm, 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: the aperture of the thread eye on described THICKNESS CONTROL mould is 25-380 μm, the length of thread eye is 5-20mm.