CN102517687A

CN102517687A - Elastic fiber with multi-level micro-nano structure and bionic preparation method thereof

Info

Publication number: CN102517687A
Application number: CN2011103650756A
Authority: CN
Inventors: 刘全勇; 江雷
Original assignee: Beihang University
Current assignee: Beihang University
Priority date: 2011-11-17
Filing date: 2011-11-17
Publication date: 2012-06-27

Abstract

The invention relates to elastic fiber with a multi-level micro-nano structure. The elastic fiber has 8 structures: (1) the fiber surface is provided with grooves of 1-10 microns; (2) the fiber surface is provided with grooves of 1-10 microns, and nano particles are contained in the fiber; (3) the fiber surface is provided with grooves of 1-10 microns and nano microspheres, and nano particles are contained in the fiber; (4) the fiber surface is provided with grooves of 1-10 microns and nano particle aggregate of 20 nanometers to 8 microns, and nano particles are contained in the fiber; (5) the fiber surface is provided with grooves of 1-10 microns and nano particle aggregates of 20 nanometers to 8 microns, and nano particles and spheres of 400 nanometers to 1.2 microns induced by the nano particles are contained in the fiber; (6) the elastic fiber is spiral elastic fiber, and the fiber surface is provided with a concave-convex structure; (7) the elastic fiber is spiral elastic fiber, the fiber surface is provided with a concave-convex structure, and nano particles are contained in the fiber; and (8) the elastic fiber is spiral elastic fiber, the fiber surface is provided with a concave-convex structure and nano microspheres, and nano particles are contained in the fiber.

Description

Elastomer and bionics method for preparation thereof with multistage micro nano structure

Technical field

The invention belongs to the polymer fiber material technical field, relate to a kind of elastomer and bionics method for preparation thereof specifically with multistage micro nano structure, relevant with bionical science, micro-nano technology, material science with the fibrous woven technology.

Background technology

Occurring in nature, many natural biomaterials like lotus leaf, butterfly's wing, water skipper leg, mosquito compound eye, fish scale, gecko pin etc., have been evolved more than one hundred million year and have been had perfect multistage micro nano structure.Also just because of this multistage micro nano structure, these natural biomaterials have the function of many uniquenesses, like ultraphobic water-based, automatically cleaning, structural color, antireflection, antifog, antipollution, drag reduction, reversible adhesive etc.Based on bionics principle, the multistage micro nano structure of imitation natural biologic material, design, the novel 26S Proteasome Structure and Function material of preparation have become an important development direction in the material science.

Spider silk is a kind of famous, natural elastomer; It has many outstanding character and function, like outstanding mechanical property, fabulous SME, high damping capacity, directive water collection property, certain biological adsorption capacity, outstanding biocompatibility etc.Just because of these outstanding character, spider silk has been used in fields such as Aero-Space, military affairs, building, agricultural, water collection, biomedicine by exploitation.Further investigation is found, spider silk these outstanding character and functions mainly give the credit to the reason of two aspects: the unique natural spinning process of (1) spider silk; (2) the multistage micro nano structure of spider silk.

According to bibliographical information; Multistage micro nano structure through the imitation spider silk; As the unformed phase structure of the brilliant enhancing of the protein nano that imitates the spider traction fiber, perhaps imitating the periodicity joint structure that spider captures silk, people have developed several kinds of distinctive 26S Proteasome Structure and Function fibrous materials.Through improved coagulating bath based on fiber spinning technology, prepared a kind of SWCN/polyvinyl alcohol composite fiber, this fiber has high intensity and toughness; Through multi-pulse gas-phase permeation technology, produced the spider silk that a kind of metallic zinc, titanium or aluminium inject, the spider silk of this modification has the strength and stiffness of raising; Nylon fiber is immersed in the polymer solution; Flatly fiber is pulled out from solution then and drying; Through this process; Made a series of artificial spider silk, this manual work spider silk has periodic joint structure, and this periodic joint structure can be ordered about little water droplet and directionality is arranged on fiber moved; Spin the method that combines with EFI through coaxial electricity, designed a kind of polyvinyl alcohol/polystyrene composite fibre, this fiber has the heterojunction structure that the pearl line links to each other.Have the report of multistage micro nano structure fiber from these, can find, on the one hand, fiber preparation method is extremely important, on the other hand, does not also have the report of multistage micro nano structure elastomer.

Polyurethane elastomer has characteristics such as sound insulation, thermal insulation, wear-resisting, oil resistant, fast light, anti-aging, shape memory, is widely used in fields such as aviation, electromechanics, boats and ships, vehicle, civil construction, light industry, weaving.Polyurethane elastomer has been used as raw material and has removed to prepare well-known elastomer-spandex, and this elastomer has advantages such as percentage elongation is big, elastic recovery rate is high, fatigue durability is superior, dyeability is good.In addition, polyurethane elastomer has many similar architectural features with spider silk fibroin, like block type strand, stable amido link, abundant hydrogen bond etc.Therefore, select for use polyurethane elastomer to remove to prepare elastomer, with significant with multistage micro nano structure as material of main part.

Micro-nano technology; Be meant and adopt certain method and technological means; Like template, laser ablation technology, phase separation method, electrostatic spinning technique, self-assembly method, spray drying technology, chemical synthesis, plasma technique, in-situ compositing, physical blending technology etc.; Make material have similar perfect micro nano structure with receiving to see on the yardstick, and then give the material optimum properties with natural biologic material at microcosmic.With the polyurethane elastomer is matrix material, introduces nano particle simultaneously, and adopts micro-nano technology, and preparation has the elastomer of multistage micro nano structure, will be a kind of new challenge.

It is reported, in the natural spinning process of spider silk, at first, formed the protein solution of high concentration, and be stored in the inner chamber of sericterium body.Then, protein solution flows in the tapered gradually spinning conduit, is accompanied by the extraction of aqueous solvent, the exchange of ion and the change of pH value, and silk-fibroin begins self assembly in the spinning conduit, forms the initial silk with multistage micro nano structure.At last, formed initial silk is extruded from the spinning conduit, in air, is stretched, and in air, is dried, removes simultaneously remaining aqueous solvent, obtains final spider silk.In this natural spinning process; The program of a key is: in tapered gradually spinning conduit; Silk-fibroin at first is self-assembled into the β sheet under the driving of hydrogen bond and hydrophobic effect; And further be assembled into soft protomere (diameter 10～100nm), and then protomere is transformed into metastable liquid crystal structure again; Under the triggering that the extraction of aqueous solvent, ion-exchange and pH value change, metastable liquid crystal structure further is transformed into more β chip architecture, and is last, and the initial silk with multistage micro nano structure has just formed in the spinning conduit.In the spinning process of traditional artificial fibre, this program normally is difficult to occur.

In view of above background introduction; The present invention attempts, and directly imitates the natural spinning process of spider silk, is material of main part with the polyurethane elastomer; Introduce nano particle simultaneously; And adopt micro-nano technology, bionical preparation has the elastomer of multistage micro nano structure, and proposes its unique bionics method for preparation and spinning technique.

Summary of the invention

The object of the present invention is to provide a kind of elastomer and bionics method for preparation thereof with multistage micro nano structure; Promptly through directly imitating the natural spinning process of spider silk; Preparation has the elastomer of multistage micro nano structure, and proposes its unique bionics method for preparation and spinning technique.

Among the present invention, the prepared elastomer with multistage micro nano structure has following 8 kinds:

1. wherein a kind of elastomer with multistage micro nano structure, its fiber surface only has the groove of 1～10 micron-scale;

2. wherein a kind of elastomer with multistage micro nano structure, its fiber surface only has the groove of 1～10 micron-scale, its fibrous inside also contains nano particle, the size of fibrous inside nano particle depend primarily on add the particle diameter of nano particle;

3. wherein a kind of elastomer (like Fig. 1 a, 1b, 1c and 1d) with multistage micro nano structure; Its fiber surface has the groove of 1～10 micron-scale and the microballoon of nano-scale simultaneously; Its fibrous inside also contains nano particle, the size of fiber surface microballoon and fibrous inside nano particle depend primarily on add the particle diameter of nano particle;

4. wherein a kind of elastomer (like Fig. 2 a, 2b, 2c and 2d) with multistage micro nano structure; Its fiber surface has the groove of 1～10 micron-scale and the nanometer particle congery of 20 nanometers～8 micron-scales simultaneously; Its fibrous inside also contains nano particle, the size of fibrous inside nano particle depend primarily on add the particle diameter of nano particle;

5. wherein a kind of elastomer (like Fig. 3 a, 3b, 3c and 3d) with multistage micro nano structure; Its fiber surface has the groove of 1～10 micron-scale and the nanometer particle congery of 20 nanometers～8 micron-scales simultaneously; Its fibrous inside also contains the spheroid that nano particle and nano particle are induced 400 nanometers of generation～1.2 micron-scales simultaneously, the size of fibrous inside nano particle depend primarily on add the particle diameter of nano particle;

6. wherein a kind of elastomer with multistage micro nano structure is the screw type elastomer, and its fiber surface only has concaveconvex structure;

7. wherein a kind of elastomer with multistage micro nano structure; It is the screw type elastomer; Its fiber surface only has concaveconvex structure, and its fibrous inside also contains nano particle, the size of fibrous inside nano particle depend primarily on add the particle diameter of nano particle;

8. wherein a kind of elastomer (like Fig. 4 a, 4b, 4c and 4d) with multistage micro nano structure; It is the screw type elastomer; Its fiber surface has the microballoon of concaveconvex structure and nano-scale simultaneously; Its fibrous inside also contains nano particle, the size of fiber surface microballoon and fibrous inside nano particle depend primarily on add the particle diameter of nano particle.

Among the present invention, its bionics method for preparation 1 is mainly used in preparation the in above 8 kinds of fibers and 1. plants fiber, mainly may further comprise the steps:

(1) preparation of composite spinning solution: earlier with N, dinethylformamide is that the solvent compound concentration ratio of polyurethane quality and solvent for use volume (add) is the polyurethane solutions of 0.1～0.4 grams per milliliter; Then, add isopyknic N respectively, dinethylformamide and alcohol solvent make the concentration ratio of solvent for use cumulative volume (the polyurethane quality with) of polyurethane solutions reduce to the half the of initial concentration, are 0.05～0.2 grams per milliliter; Last dispersed with stirring to solution is even, gets composite spinning solution.

(2) storage of composite spinning solution and extruding: composite spinning solution is placed the reservoir vessel that has piston and conduit, utilize pressure control device and spinning solution is compressed into conduit, and spinning solution is extruded from conduit through piston; The speed that from reservoir vessel, gets into conduit through pressure control device adjusting spinning solution is 0.2～5 milliliter/hour, and the internal diameter of conduit is 0.2～0.7 millimeter.

(3) moulding of elastomer: at room temperature, composite spinning solution is clamp-oned in conduit the one-tenth silk tank that running water is housed, composite spinning solution solidifies in water, and solvent spreads in water, and polyurethane elastomer carries out self assembly, forms initial elastomer.

(4) stretch processing of elastomer: at room temperature, place running water or air to carry out vertical stretch processing initial elastomer; Initial elastomer is stretched to 2～10 times of former length, and the extended state of elastomer is kept being not less than 10 minutes.

(5) drying of elastomer: the elastomer after the stretched processing is carried out drying, removing remaining solvent, thereby make final elastomer.

Among the present invention, its bionics method for preparation 2 is mainly used in preparation the in above 8 kinds of fibers and 2., 3., 4., 5. plants fiber, mainly may further comprise the steps:

(1) preparation of composite spinning solution: earlier with N, dinethylformamide is that the solvent compound concentration ratio of solvent for use volume (the polyurethane quality with) is the polyurethane solutions of 0.1～0.4 grams per milliliter; Then; Took by weighing the nano particle of certain mass in 1: 20～5: 20 by the mass ratio ratio of polyurethane quality (the used nano particle quality with); And the ethanol of getting certain volume carries out wetting and ultrasonic dispersion treatment to nano particle; Treated nano particle and ethanol are poured in the polyurethane solutions of being prepared together, added the isopyknic N of used ethanol again, the dinethylformamide solvent is in polyurethane solutions; Make the concentration ratio of solvent for use cumulative volume (the polyurethane quality with) of polyurethane solutions reduce to the half the of initial concentration, be 0.05～0.2 grams per milliliter; At last, dispersed with stirring be not less than 1 hour even to solution, composite spinning solution.

(3) moulding of elastomer: at room temperature; Composite spinning solution is clamp-oned in conduit the one-tenth silk tank that running water is housed, and composite spinning solution solidifies in water, and solvent spreads in water; Polyurethane elastomer and nano particle carry out self assembly, form initial elastomer.

Among the present invention, its bionics method for preparation 3 is mainly used in preparation the in above 8 kinds of fibers and 6. plants fiber, mainly may further comprise the steps:

(3) moulding of elastomer: at room temperature; Composite spinning solution is clamp-oned in conduit the one-tenth silk tank that running water is housed, become the silk bottom of gullet to stir running water through a magneton and form a small rotation fluctuation, composite spinning solution solidifies in water; Solvent spreads in water; Polyurethane elastomer carries out self assembly, and from spiral rising under water, forms initial screw type elastomer.

(4) stretch processing of elastomer: at room temperature, place air to carry out vertical stretch processing initial elastomer; Initial elastomer is stretched to 0～6 times of former length, and the extended state of elastomer is kept being not less than 10 minutes.

(5) drying of elastomer: the screw type elastomer after the stretched processing is carried out drying, removing remaining solvent, thereby make final elastomer.

Among the present invention, its bionics method for preparation 4 is mainly used in preparation the in above 8 kinds of fibers and 7., 8. plants fiber, mainly may further comprise the steps:

(3) moulding of elastomer: at room temperature; Composite spinning solution is clamp-oned in conduit the one-tenth silk tank that running water is housed, become the silk bottom of gullet to stir running water through a magneton and form a small rotation fluctuation, composite spinning solution solidifies in water; Solvent spreads in water; Polyurethane elastomer and nano particle carry out self assembly, and from spiral rising under water, form initial screw type elastomer.

Among the present invention; Spinning technique installation drawing in its bionics method for preparation 1 and 2 (seeing Fig. 5 a and 5b), mainly comprise pressure control device 1, at least have moveable piston 21 and conduit 22 reservoir vessel 2, become silk a tank 3, transfer device 4, stretching device 5, drying device 6 and gathering-device 7; Pressure control device 1 links to each other with piston 21, regulates the speed that piston mobile 21 is advanced through pressure control device 1, thus the speed that spinning solution gets into conduit 22 in the control reservoir vessel 2; Piston on the reservoir vessel 2 and conduit can load and unload flexibly, clean and change with convenient; Become the bottom and the top of silk tank 3 that a water inlet 32 and delivery port 31 are arranged respectively, so that add at any time, change and the recycle running water; The conduit 22 of reservoir vessel 2 gets into the running water from the bottom that becomes silk tank 3, and spinning solution pushes in the running water that gets into a tank and is solidified into silk via conduit; Transfer device 4 is arranged in the running water of a tank (sees Fig. 5 a; Be applicable to that mainly fiber F carries out stretch processing in water W); Perhaps be arranged on the running water of a tank (to see Fig. 5 b outward; Be applicable to that mainly fiber F carries out stretch processing in air), the effect of transfer device mainly is through its rotating shaft rotation, and the fiber that forms is shifted to target direction; Stretching device 5 through the rotating speed of rotating shaft on the control stretching device 5, carries out stretch processing to shifting the fiber of coming through transfer device 4 directly over transfer device 4; Stretched fibre treated is carried out drying via drying device 6, to remove remaining solvent; At last, the fiber that is dried moves into the row collection via the commentaries on classics of guidewire shaft on the gathering-device 7.

Among the present invention; Spinning technique installation drawing (see figure 6) in its bionics method for preparation 3 and 4, mainly comprise pressure control device 1, at least have moveable piston 21 and conduit 22 reservoir vessel 2, magnetic stirring apparatus 8, become silk a tank 3, transfer device 4, stretching device 5, drying device 6 and gathering-device 7; Pressure control device 1 links to each other with piston 21, regulates the speed that piston mobile 21 is advanced through pressure control device 1, thus the speed that spinning solution gets into conduit 21 in the control reservoir vessel 2; Piston 21 on the reservoir vessel can load and unload with conduit 22 flexibly, cleans and changes with convenient; Magnetic stirring apparatus 8 places below the tank 3, becomes the bottom in the silk tank 3 to place a magneton 81, through the rotation of magnetic stirring apparatus 8 control magnetons 81, so that in running water, form small rotation fluctuation; Become the bottom and the top of silk tank 3 that a water inlet 32 and delivery port 31 are arranged respectively, so that add at any time, change and the recycle running water; The conduit 21 of reservoir vessel 2 gets into the running water from the bottom that becomes silk tank 3, and spinning solution pushes in the running water that gets into a tank and is solidified into silk via conduit; Transfer device 4 is outside the running water that becomes the silk tank (being applicable to that mainly fiber F carries out stretch processing in air), and the effect of transfer device 4 mainly is through its rotating shaft rotation, and the fiber that forms is shifted to target direction; Stretching device 5 through the rotating speed of rotating shaft on the control stretching device 5, carries out stretch processing to shifting the fiber of coming through transfer device 4 directly over transfer device; Stretched fibre treated is carried out drying via drying device 6, to remove remaining solvent; At last, the fiber that is dried moves into the row collection via the commentaries on classics of guidewire shaft on the gathering-device 7.

Among the present invention; Select a kind of material of main part for use, like thermoplastic polyurethane

1180A, 1185A and the 1190A etc. of BASF Aktiengesellschaft with the water-disintegrable TPUE of good resistance as the preparation elastomer.

Among the present invention, employed nano particle comprises various polymer microballoons, like polystyrene microsphere, ultra-fine form of finely divided powder, mehtod acrylonitrile-butadiene rubber, polyacrylic acid ester microsphere etc.; Also comprise various inorganic matter microballoons, nanocrystalline etc. like silicon dioxide microsphere, Fe 3 O 4 magnetic microballoon, cadmium telluride; With formed protomere in the natural spinning process of these nano particle imitation spider silks, they will carry out self assembly in the process of fiberizing.

Advantage of the present invention is; Through the natural spinning process of direct imitation spider silk; With the polyurethane elastomer is material of main part, introduces nano particle simultaneously, and adopts micro-nano technology; Prepared to novelty elastomer, and proposed the bionics method for preparation and the spinning technique of a series of uniquenesses with multistage micro nano structure.Prepared elastomer; Owing to have and many natural biomaterials; Like similar multistage micro nano structures such as lotus leaf, butterfly's wing, water skipper leg, mosquito compound eye, fish scale, gecko pin, spider silks; Therefore will show many character similar and function, like ultraphobic water-based, automatically cleaning, structural color, antireflection, antifog, antipollution, self-reinforcing etc. with natural biologic material.Bionics method for preparation that is proposed and spinning technique, novelty, simple, easy-to-understand, easy operating helps realizing suitability for industrialized production.

Description of drawings

Fig. 1 a scanning electron microscope diagram with elastomer surface of multistage micro nano structure;

Fig. 1 b scanning electron microscope diagram with elastomer surface of multistage micro nano structure;

Fig. 1 c scanning electron microscope diagram with elastomer surface of multistage micro nano structure;

Fig. 1 d scanning electron microscope diagram with elastomer surface of multistage micro nano structure;

Fig. 1 a, Fig. 1 b, Fig. 1 c and Fig. 1 d observe same fiber surface position; Multiplication factor progressively improves; Figure shows that its fiber surface has the groove of 1～10 micron-scale and the microballoon of nano-scale simultaneously, the size of fiber surface microballoon depend primarily on add the particle diameter of nano particle.

Fig. 2 a scanning electron microscope diagram with elastomer surface of multistage micro nano structure;

Fig. 2 b scanning electron microscope diagram with elastomer surface of multistage micro nano structure;

Fig. 2 c scanning electron microscope diagram with elastomer section of multistage micro nano structure;

Fig. 2 d scanning electron microscope diagram with elastomer section of multistage micro nano structure;

Fig. 2 a, 2b, 2c and 2d observe same fiber surface or cross section place, and multiplication factor progressively improves, and Fig. 2 a and 2b show that its fiber surface has the groove of 1～10 micron-scale and the nanometer particle congery of 20 nanometer to 8 micron-scales simultaneously; Fig. 2 c and 2d show that its fibrous inside also contains nano particle, the size of fibrous inside nano particle depend primarily on add the particle diameter of nano particle.

Fig. 3 a scanning electron microscope diagram with elastomer surface of multistage micro nano structure;

Fig. 3 b scanning electron microscope diagram with elastomer surface of multistage micro nano structure;

Fig. 3 c scanning electron microscope diagram with elastomer section of multistage micro nano structure;

Fig. 3 d scanning electron microscope diagram with elastomer section of multistage micro nano structure;

Fig. 3 a, 3b, 3c and 3d are that institute is observed same fiber surface or cross section place, and multiplication factor progressively improves, and Fig. 3 a and 3b show that its fiber surface has the groove of 1～10 micron-scale and the nanometer particle congery of 20 nanometer to 8 micron-scales simultaneously; Fig. 3 c and 3d show that its fibrous inside also contains the spheroid that nano particle and nano particle are induced 400 nanometer to 1.2 micron-scales of generation simultaneously, the size of fibrous inside nano particle depend primarily on add the particle diameter of nano particle.

Fig. 4 a scanning electron microscope diagram with screw type elastomer surface of multistage micro nano structure;

Fig. 4 b scanning electron microscope diagram with screw type elastomer surface of multistage micro nano structure;

Fig. 4 c scanning electron microscope diagram with screw type elastomer surface of multistage micro nano structure;

Fig. 4 d scanning electron microscope diagram with screw type elastomer surface of multistage micro nano structure;

Fig. 4 a, 4b, 4c and 4d; Be that same fiber surface position is observed; Multiplication factor progressively improves, and figure shows that its fiber surface has the microballoon of concaveconvex structure and nano-scale simultaneously, the size of fiber surface microballoon depend primarily on add the particle diameter of nano particle.

Fig. 5 a is the spinning technique installation drawing () in bionics method for

preparation

1 and 2;

Fig. 5 b is the spinning technique installation drawing (two) in bionics method for

preparation

1 and 2;

Fig. 6 is the spinning technique installation drawing in bionics method for preparation 3 and 4.

Concrete label is following among the figure:

1, pressure control device 2, storage device 21, piston 22, conduit

3, become silk tank 31, delivery port 32, water inlet 4, transfer device

5, stretching device 6, drying device 7, gathering-device 8, magnetic stirring apparatus

81, magneton W, water F, fiber

The specific embodiment

Below in conjunction with embodiment the present invention is done further detailed description.

Embodiment 1:

(1) preparation of composite spinning solution: earlier with N, dinethylformamide is that the solvent compound concentration ratio of polyurethane quality and solvent for use volume (add) is the polyurethane solutions of 0.2 grams per milliliter; Then, add isopyknic N respectively, dinethylformamide and alcohol solvent make the concentration ratio of solvent for use cumulative volume (the polyurethane quality with) of polyurethane solutions reduce to the half the of initial concentration, are 0.1 grams per milliliter; Last dispersed with stirring to solution is even, gets composite spinning solution.

(2) storage of composite spinning solution and extruding: composite spinning solution is placed the reservoir vessel that has piston and conduit, utilize pressure control device and spinning solution is compressed into conduit, and spinning solution is extruded from conduit through piston; The speed that from reservoir vessel, gets into conduit through pressure control device adjusting spinning solution is 0.5 milliliter/hour, and the internal diameter of conduit is 0.5 millimeter.

(4) stretch processing of elastomer: at room temperature, place running water or air to carry out vertical stretch processing initial elastomer; Initial elastomer is stretched to 6 times of former length, and the extended state of elastomer is kept being not less than 10 minutes.

(5) drying of elastomer: the elastomer after the stretched processing is carried out drying, removing remaining solvent, thereby make the final elastomer with multistage micro nano structure, its fiber surface only has the groove of 1～10 micron-scale.

Embodiment 2:

(1) preparation of composite spinning solution: earlier with N, dinethylformamide is that the solvent compound concentration ratio of polyurethane quality and solvent for use volume (add) is the polyurethane solutions of 0.4 grams per milliliter; Then, add isopyknic N respectively, dinethylformamide and alcohol solvent make the concentration ratio of solvent for use cumulative volume (the polyurethane quality with) of polyurethane solutions reduce to the half the of initial concentration, are 0.2 grams per milliliter; Last dispersed with stirring to solution is even, gets composite spinning solution.

(2) storage of composite spinning solution and extruding: composite spinning solution is placed the reservoir vessel that has piston and conduit, utilize pressure control device and spinning solution is compressed into conduit, and spinning solution is extruded from conduit through piston; The speed that from reservoir vessel, gets into conduit through pressure control device adjusting spinning solution is 0.5 milliliter/hour, and the internal diameter of conduit is 0.3 millimeter.

(4) stretch processing of elastomer: at room temperature, place running water or air to carry out vertical stretch processing initial elastomer; Initial elastomer is stretched to 8 times of former length, and the extended state of elastomer is kept being not less than 10 minutes.

Embodiment 3:

(2) storage of composite spinning solution and extruding: composite spinning solution is placed the reservoir vessel that has piston and conduit, utilize pressure control device and spinning solution is compressed into conduit, and spinning solution is extruded from conduit through piston; The speed that from reservoir vessel, gets into conduit through pressure control device adjusting spinning solution is 1 milliliter/hour, and the internal diameter of conduit is 0.5 millimeter.

(4) stretch processing of elastomer: at room temperature, place running water or air to carry out vertical stretch processing initial elastomer; Initial elastomer is stretched to 5 times of former length, and the extended state of elastomer is kept being not less than 10 minutes.

Embodiment 4:

(1) preparation of composite spinning solution: earlier with N, dinethylformamide is that the solvent compound concentration ratio of solvent for use volume (the polyurethane quality with) is the polyurethane solutions of 0.2 grams per milliliter; Then; Take by weighing the ultra-fine form of finely divided powder, mehtod acrylonitrile-butadiene rubber (about 100 nanometers of particle diameter) of certain mass at 1: 20 by the mass ratio ratio of polyurethane quality (the used nano particle quality with); And the ethanol of getting certain volume carries out wetting and ultrasonic dispersion treatment to nano particle; Treated nano particle and ethanol are poured in the polyurethane solutions of being prepared together, added the isopyknic N of used ethanol again, the dinethylformamide solvent is in polyurethane solutions; Make the concentration ratio of solvent for use cumulative volume (the polyurethane quality with) of polyurethane solutions reduce to the half the of initial concentration, be 0.1 grams per milliliter; At last, dispersed with stirring be not less than 1 hour even to solution, composite spinning solution.

(4) stretch processing of elastomer: at room temperature, place running water to carry out vertical stretch processing initial elastomer; Initial elastomer is stretched to 5 times of former length, and the extended state of elastomer is kept being not less than 10 minutes.

(5) drying of elastomer: the elastomer after the stretched processing is carried out drying; To remove remaining solvent; Thereby make final elastomer with multistage micro nano structure; Its fiber surface only has the groove of 1～10 micron-scale, and its fibrous inside also contains the nano particle of 100 nano-scales.

Embodiment 5:

(1) preparation of composite spinning solution: earlier with N, dinethylformamide is that the solvent compound concentration ratio of solvent for use volume (the polyurethane quality with) is the polyurethane solutions of 0.2 grams per milliliter; Then; Take by weighing the ultra-fine form of finely divided powder, mehtod acrylonitrile-butadiene rubber (about 100 nanometers of particle diameter) of certain mass at 3: 20 by the mass ratio ratio of polyurethane quality (the used nano particle quality with); And the ethanol of getting certain volume carries out wetting and ultrasonic dispersion treatment to nano particle; Treated nano particle and ethanol are poured in the polyurethane solutions of being prepared together, added the isopyknic N of used ethanol again, the dinethylformamide solvent is in polyurethane solutions; Make the concentration ratio of solvent for use cumulative volume (the polyurethane quality with) of polyurethane solutions reduce to the half the of initial concentration, be 0.1 grams per milliliter; At last, dispersed with stirring be not less than 1 hour even to solution, composite spinning solution.

(4) stretch processing of elastomer: at room temperature, place running water to carry out vertical stretch processing initial elastomer; Initial elastomer is stretched to 6 times of former length, and the extended state of elastomer is kept being not less than 10 minutes.

(5) drying of elastomer: the elastomer after the stretched processing is carried out drying; To remove remaining solvent; Thereby make final elastomer with multistage micro nano structure; Its fiber surface has the groove of 1～10 micron-scale and the microballoon of 100 nano-scales simultaneously, and its fibrous inside also contains the nano particle of 100 nano-scales.

Embodiment 6:

(1) preparation of composite spinning solution: earlier with N, dinethylformamide is that the solvent compound concentration ratio of solvent for use volume (the polyurethane quality with) is the polyurethane solutions of 0.4 grams per milliliter; Then; Take by weighing the ultra-fine form of finely divided powder, mehtod acrylonitrile-butadiene rubber (about 100 nanometers of particle diameter) of certain mass at 4: 20 by the mass ratio ratio of polyurethane quality (the used nano particle quality with); And the ethanol of getting certain volume carries out wetting and ultrasonic dispersion treatment to nano particle; Treated nano particle and ethanol are poured in the polyurethane solutions of being prepared together, added the isopyknic N of used ethanol again, the dinethylformamide solvent is in polyurethane solutions; Make the concentration ratio of solvent for use cumulative volume (the polyurethane quality with) of polyurethane solutions reduce to the half the of initial concentration, be 0.2 grams per milliliter; At last, dispersed with stirring be not less than 1 hour even to solution, composite spinning solution.

(2) storage of composite spinning solution and extruding: composite spinning solution is placed the reservoir vessel that has piston and conduit, utilize pressure control device and spinning solution is compressed into conduit, and spinning solution is extruded from conduit through piston; The speed that from reservoir vessel, gets into conduit through pressure control device adjusting spinning solution is 1 milliliter/hour, and the internal diameter of conduit is 0.3 millimeter.

(4) stretch processing of elastomer: at room temperature, place running water to carry out vertical stretch processing initial elastomer; Initial elastomer is stretched to 7 times of former length, and the extended state of elastomer is kept being not less than 10 minutes.

Embodiment 7:

(4) stretch processing of elastomer: at room temperature, place air to carry out vertical stretch processing initial elastomer; Initial elastomer is stretched to 5 times of former length, and the extended state of elastomer is kept being not less than 10 minutes.

Embodiment 8:

(1) preparation of composite spinning solution: earlier with N, dinethylformamide is that the solvent compound concentration ratio of solvent for use volume (the polyurethane quality with) is the polyurethane solutions of 0.2 grams per milliliter; Then; Take by weighing the ultra-fine form of finely divided powder, mehtod acrylonitrile-butadiene rubber (about 100 nanometers of particle diameter) of certain mass at 5: 20 by the mass ratio ratio of polyurethane quality (the used nano particle quality with); And the ethanol of getting certain volume carries out wetting and ultrasonic dispersion treatment to nano particle; Treated nano particle and ethanol are poured in the polyurethane solutions of being prepared together, added the isopyknic N of used ethanol again, the dinethylformamide solvent is in polyurethane solutions; Make the concentration ratio of solvent for use cumulative volume (the polyurethane quality with) of polyurethane solutions reduce to the half the of initial concentration, be 0.1 grams per milliliter; At last, dispersed with stirring be not less than 1 hour even to solution, composite spinning solution.

(4) stretch processing of elastomer: at room temperature, place air to carry out vertical stretch processing initial elastomer; Initial elastomer is stretched to 6 times of former length, and the extended state of elastomer is kept being not less than 10 minutes.

Embodiment 9:

(1) preparation of composite spinning solution: earlier with N, dinethylformamide is that the solvent compound concentration ratio of solvent for use volume (the polyurethane quality with) is the polyurethane solutions of 0.2 grams per milliliter; Then; Take by weighing the crosslinked polystyrene microsphere (about 500 nanometers of particle diameter) of diethylbenzene of certain mass at 1: 20 by the mass ratio ratio of polyurethane quality (the used nano particle quality with); And the ethanol of getting certain volume carries out wetting and ultrasonic dispersion treatment to nano particle; Treated nano particle and ethanol are poured in the polyurethane solutions of being prepared together, added the isopyknic N of used ethanol again, the dinethylformamide solvent is in polyurethane solutions; Make the concentration ratio of solvent for use cumulative volume (the polyurethane quality with) of polyurethane solutions reduce to the half the of initial concentration, be 0.1 grams per milliliter; At last, dispersed with stirring be not less than 1 hour even to solution, composite spinning solution.

(5) drying of elastomer: the elastomer after the stretched processing is carried out drying; To remove remaining solvent; Thereby make final elastomer with multistage micro nano structure; Its fiber surface only has the groove of 1～10 micron-scale, and its fibrous inside also contains the nano particle of 500 nano-scales.

Embodiment 10:

(1) preparation of composite spinning solution: earlier with N, dinethylformamide is that the solvent compound concentration ratio of solvent for use volume (the polyurethane quality with) is the polyurethane solutions of 0.2 grams per milliliter; Then; Take by weighing the crosslinked polystyrene microsphere (about 500 nanometers of particle diameter) of diethylbenzene of certain mass at 5: 20 by the mass ratio ratio of polyurethane quality (the used nano particle quality with); And the ethanol of getting certain volume carries out wetting and ultrasonic dispersion treatment to nano particle; Treated nano particle and ethanol are poured in the polyurethane solutions of being prepared together, added the isopyknic N of used ethanol again, the dinethylformamide solvent is in polyurethane solutions; Make the concentration ratio of solvent for use cumulative volume (the polyurethane quality with) of polyurethane solutions reduce to the half the of initial concentration, be 0.1 grams per milliliter; At last, dispersed with stirring be not less than 1 hour even to solution, composite spinning solution.

(5) drying of elastomer: the elastomer after the stretched processing is carried out drying; To remove remaining solvent; Thereby make final elastomer with multistage micro nano structure; Its fiber surface has the groove of 1～10 micron-scale and the microballoon of 500 nano-scales simultaneously, and its fibrous inside also contains the nano particle of 500 nano-scales.

Embodiment 11:

(1) preparation of composite spinning solution: earlier with N, dinethylformamide is that the solvent compound concentration ratio of solvent for use volume (the polyurethane quality with) is the polyurethane solutions of 0.2 grams per milliliter; Then; Take by weighing the crosslinked polystyrene microsphere (about 500 nanometers of particle diameter) of diethylbenzene of certain mass at 3: 20 by the mass ratio ratio of polyurethane quality (the used nano particle quality with); And the ethanol of getting certain volume carries out wetting and ultrasonic dispersion treatment to nano particle; Treated nano particle and ethanol are poured in the polyurethane solutions of being prepared together, added the isopyknic N of used ethanol again, the dinethylformamide solvent is in polyurethane solutions; Make the concentration ratio of solvent for use cumulative volume (the polyurethane quality with) of polyurethane solutions reduce to the half the of initial concentration, be 0.1 grams per milliliter; At last, dispersed with stirring be not less than 1 hour even to solution, composite spinning solution.

(4) stretch processing of elastomer: at room temperature, place air to carry out vertical stretch processing initial elastomer; Initial elastomer is stretched to 7 times of former length, and the extended state of elastomer is kept being not less than 10 minutes.

Embodiment 12:

(1) preparation of composite spinning solution: earlier with N, dinethylformamide is that the solvent compound concentration ratio of solvent for use volume (the polyurethane quality with) is the polyurethane solutions of 0.2 grams per milliliter; Then; Take by weighing the silicon dioxide microsphere (about 10 nanometers of particle diameter) of certain mass at 5: 20 by the mass ratio ratio of polyurethane quality (the used nano particle quality with); And the ethanol of getting certain volume carries out wetting and ultrasonic dispersion treatment to nano particle; Treated nano particle and ethanol are poured in the polyurethane solutions of being prepared together, added the isopyknic N of used ethanol again, the dinethylformamide solvent is in polyurethane solutions; Make the concentration ratio of solvent for use cumulative volume (the polyurethane quality with) of polyurethane solutions reduce to the half the of initial concentration, be 0.1 grams per milliliter; At last, dispersed with stirring be not less than 1 hour even to solution, composite spinning solution.

(5) drying of elastomer: the elastomer after the stretched processing is carried out drying; To remove remaining solvent; Thereby make final elastomer with multistage micro nano structure; Its fiber surface has the groove of 1～10 micron-scale and the nanometer particle congery of 20 nanometer to 8 micron-scales simultaneously, and its fibrous inside also contains the nano particle of 10 nano-scales.

Embodiment 13:

(1) preparation of composite spinning solution: earlier with N, dinethylformamide is that the solvent compound concentration ratio of solvent for use volume (the polyurethane quality with) is the polyurethane solutions of 0.2 grams per milliliter; Then; Take by weighing the silicon dioxide microsphere (about 10 nanometers of particle diameter) of certain mass at 3: 20 by the mass ratio ratio of polyurethane quality (the used nano particle quality with); And the ethanol of getting certain volume carries out wetting and ultrasonic dispersion treatment to nano particle; Treated nano particle and ethanol are poured in the polyurethane solutions of being prepared together, added the isopyknic N of used ethanol again, the dinethylformamide solvent is in polyurethane solutions; Make the concentration ratio of solvent for use cumulative volume (the polyurethane quality with) of polyurethane solutions reduce to the half the of initial concentration, be 0.1 grams per milliliter; At last, dispersed with stirring be not less than 1 hour even to solution, composite spinning solution.

(4) stretch processing of elastomer: at room temperature, place running water to carry out vertical stretch processing initial elastomer; Initial elastomer is stretched to 2.5 times of former length, and the extended state of elastomer is kept being not less than 10 minutes.

(5) drying of elastomer: the elastomer after the stretched processing is carried out drying; To remove remaining solvent; Thereby make final elastomer with multistage micro nano structure; Its fiber surface has the groove of 1～10 micron-scale and the nanometer particle congery of 20 nanometer to 8 micron-scales simultaneously, and its fibrous inside also contains the nano particle of 10 nano-scales and the spheroid of 400 nanometer to 1.2 micron-scales that nano particle is induced generation simultaneously.

Embodiment 14:

(1) preparation of composite spinning solution: earlier with N, dinethylformamide is that the solvent compound concentration ratio of solvent for use volume (the polyurethane quality with) is the polyurethane solutions of 0.4 grams per milliliter; Then; Take by weighing the silicon dioxide microsphere (about 10 nanometers of particle diameter) of certain mass at 2: 20 by the mass ratio ratio of polyurethane quality (the used nano particle quality with); And the ethanol of getting certain volume carries out wetting and ultrasonic dispersion treatment to nano particle; Treated nano particle and ethanol are poured in the polyurethane solutions of being prepared together, added the isopyknic N of used ethanol again, the dinethylformamide solvent is in polyurethane solutions; Make the concentration ratio of solvent for use cumulative volume (the polyurethane quality with) of polyurethane solutions reduce to the half the of initial concentration, be 0.2 grams per milliliter; At last, dispersed with stirring be not less than 1 hour even to solution, composite spinning solution.

(4) stretch processing of elastomer: at room temperature, place running water to carry out vertical stretch processing initial elastomer; Initial elastomer is stretched to 3 times of former length, and the extended state of elastomer is kept being not less than 10 minutes.

Embodiment 15:

(4) stretch processing of elastomer: at room temperature, place air to carry out vertical stretch processing initial elastomer; Initial elastomer is stretched to 2.5 times of former length, and the extended state of elastomer is kept being not less than 10 minutes.

Embodiment 16:

(1) preparation of composite spinning solution: earlier with N, dinethylformamide is that the solvent compound concentration ratio of solvent for use volume (the polyurethane quality with) is the polyurethane solutions of 0.2 grams per milliliter; Then; Take by weighing the silicon dioxide microsphere (about 100 nanometers of particle diameter) of certain mass at 2: 20 by the mass ratio ratio of polyurethane quality (the used nano particle quality with); And the ethanol of getting certain volume carries out wetting and ultrasonic dispersion treatment to nano particle; Treated nano particle and ethanol are poured in the polyurethane solutions of being prepared together, added the isopyknic N of used ethanol again, the dinethylformamide solvent is in polyurethane solutions; Make the concentration ratio of solvent for use cumulative volume (the polyurethane quality with) of polyurethane solutions reduce to the half the of initial concentration, be 0.1 grams per milliliter; At last, dispersed with stirring be not less than 1 hour even to solution, composite spinning solution.

Embodiment 17:

(1) preparation of composite spinning solution: earlier with N, dinethylformamide is that the solvent compound concentration ratio of solvent for use volume (the polyurethane quality with) is the polyurethane solutions of 0.2 grams per milliliter; Then; Take by weighing the silicon dioxide microsphere (about 100 nanometers of particle diameter) of certain mass at 4: 20 by the mass ratio ratio of polyurethane quality (the used nano particle quality with); And the ethanol of getting certain volume carries out wetting and ultrasonic dispersion treatment to nano particle; Treated nano particle and ethanol are poured in the polyurethane solutions of being prepared together, added the isopyknic N of used ethanol again, the dinethylformamide solvent is in polyurethane solutions; Make the concentration ratio of solvent for use cumulative volume (the polyurethane quality with) of polyurethane solutions reduce to the half the of initial concentration, be 0.1 grams per milliliter; At last, dispersed with stirring be not less than 1 hour even to solution, composite spinning solution.

Embodiment 18:

(1) preparation of composite spinning solution: earlier with N, dinethylformamide is that the solvent compound concentration ratio of solvent for use volume (the polyurethane quality with) is the polyurethane solutions of 0.2 grams per milliliter; Then; Take by weighing the silicon dioxide microsphere (about 100 nanometers of particle diameter) of certain mass at 3: 20 by the mass ratio ratio of polyurethane quality (the used nano particle quality with); And the ethanol of getting certain volume carries out wetting and ultrasonic dispersion treatment to nano particle; Treated nano particle and ethanol are poured in the polyurethane solutions of being prepared together, added the isopyknic N of used ethanol again, the dinethylformamide solvent is in polyurethane solutions; Make the concentration ratio of solvent for use cumulative volume (the polyurethane quality with) of polyurethane solutions reduce to the half the of initial concentration, be 0.1 grams per milliliter; At last, dispersed with stirring be not less than 1 hour even to solution, composite spinning solution.

Embodiment 19:

(1) preparation of composite spinning solution: earlier with N, dinethylformamide is that the solvent compound concentration ratio of solvent for use volume (the polyurethane quality with) is the polyurethane solutions of 0.2 grams per milliliter; Then; Take by weighing the Fe 3 O 4 magnetic microballoon (about 200 nanometers of particle diameter) of certain mass at 3: 20 by the mass ratio ratio of polyurethane quality (the used nano particle quality with); And the ethanol of getting certain volume carries out wetting and ultrasonic dispersion treatment to nano particle; Treated nano particle and ethanol are poured in the polyurethane solutions of being prepared together, added the isopyknic N of used ethanol again, the dinethylformamide solvent is in polyurethane solutions; Make the concentration ratio of solvent for use cumulative volume (the polyurethane quality with) of polyurethane solutions reduce to the half the of initial concentration, be 0.1 grams per milliliter; At last, dispersed with stirring be not less than 1 hour even to solution, composite spinning solution.

(5) drying of elastomer: the elastomer after the stretched processing is carried out drying; To remove remaining solvent; Thereby make final elastomer with multistage micro nano structure; Its fiber surface has the groove of 1～10 micron-scale and the microballoon of 200 nano-scales simultaneously, and its fibrous inside also contains the nano particle of 200 nano-scales.

Embodiment 20:

(1) preparation of composite spinning solution: earlier with N, dinethylformamide is that the solvent compound concentration ratio of solvent for use volume (the polyurethane quality with) is the polyurethane solutions of 0.2 grams per milliliter; Then; Take by weighing the Fe 3 O 4 magnetic microballoon (about 200 nanometers of particle diameter) of certain mass at 4: 20 by the mass ratio ratio of polyurethane quality (the used nano particle quality with); And the ethanol of getting certain volume carries out wetting and ultrasonic dispersion treatment to nano particle; Treated nano particle and ethanol are poured in the polyurethane solutions of being prepared together, added the isopyknic N of used ethanol again, the dinethylformamide solvent is in polyurethane solutions; Make the concentration ratio of solvent for use cumulative volume (the polyurethane quality with) of polyurethane solutions reduce to the half the of initial concentration, be 0.1 grams per milliliter; At last, dispersed with stirring be not less than 1 hour even to solution, composite spinning solution.

Embodiment 21:

(4) stretch processing of elastomer: at room temperature, place air to carry out vertical stretch processing initial elastomer; Initial elastomer is stretched to 0 times of former length, and the extended state of elastomer is kept being not less than 10 minutes.

(5) drying of elastomer: the screw type elastomer after the stretched processing is carried out drying, removing remaining solvent, thereby make the final screw type elastomer with multistage micro nano structure, its fiber surface only has concaveconvex structure.

Embodiment 22:

Embodiment 23:

(4) stretch processing of elastomer: at room temperature, place air to carry out vertical stretch processing initial elastomer; Initial elastomer is stretched to 3 times of former length, and the extended state of elastomer is kept being not less than 10 minutes.

Embodiment 24:

(4) stretch processing of elastomer: at room temperature, place air to carry out vertical stretch processing initial elastomer; Initial elastomer is stretched to 1 times of former length, and the extended state of elastomer is kept being not less than 10 minutes.

(5) drying of elastomer: the screw type elastomer after the stretched processing is carried out drying; To remove remaining solvent; Thereby make final screw type elastomer with multistage micro nano structure; Its fiber surface only has concaveconvex structure, and its fibrous inside also contains the nano particle of 100 nano-scales.

Embodiment 25:

(5) drying of elastomer: the screw type elastomer after the stretched processing is carried out drying; To remove remaining solvent; Thereby make final screw type elastomer with multistage micro nano structure; Its fiber surface has the microballoon of concaveconvex structure and 100 nano-scales simultaneously, and its fibrous inside also contains the nano particle of 100 nano-scales.

Embodiment 26:

(1) preparation of composite spinning solution: earlier with N, dinethylformamide is that the solvent compound concentration ratio of solvent for use volume (the polyurethane quality with) is the polyurethane solutions of 0.2 grams per milliliter; Then; Take by weighing the ultra-fine form of finely divided powder, mehtod acrylonitrile-butadiene rubber (about 100 nanometers of particle diameter) of certain mass at 2: 20 by the mass ratio ratio of polyurethane quality (the used nano particle quality with); And the ethanol of getting certain volume carries out wetting and ultrasonic dispersion treatment to nano particle; Treated nano particle and ethanol are poured in the polyurethane solutions of being prepared together, added the isopyknic N of used ethanol again, the dinethylformamide solvent is in polyurethane solutions; Make the concentration ratio of solvent for use cumulative volume (the polyurethane quality with) of polyurethane solutions reduce to the half the of initial concentration, be 0.1 grams per milliliter; At last, dispersed with stirring be not less than 1 hour even to solution, composite spinning solution.

(4) stretch processing of elastomer: at room temperature, place air to carry out vertical stretch processing initial elastomer; Initial elastomer is stretched to 4 times of former length, and the extended state of elastomer is kept being not less than 10 minutes.

Embodiment 27:

(1) preparation of composite spinning solution: earlier with N, dinethylformamide is that the solvent compound concentration ratio of solvent for use volume (the polyurethane quality with) is the polyurethane solutions of 0.4 grams per milliliter; Then; Take by weighing the ultra-fine form of finely divided powder, mehtod acrylonitrile-butadiene rubber (about 100 nanometers of particle diameter) of certain mass at 3: 20 by the mass ratio ratio of polyurethane quality (the used nano particle quality with); And the ethanol of getting certain volume carries out wetting and ultrasonic dispersion treatment to nano particle; Treated nano particle and ethanol are poured in the polyurethane solutions of being prepared together, added the isopyknic N of used ethanol again, the dinethylformamide solvent is in polyurethane solutions; Make the concentration ratio of solvent for use cumulative volume (the polyurethane quality with) of polyurethane solutions reduce to the half the of initial concentration, be 0.2 grams per milliliter; At last, dispersed with stirring be not less than 1 hour even to solution, composite spinning solution.

Embodiment 28:

(1) preparation of composite spinning solution: earlier with N, dinethylformamide is that the solvent compound concentration ratio of solvent for use volume (the polyurethane quality with) is the polyurethane solutions of 0.2 grams per milliliter; Then; Take by weighing the crosslinked polystyrene microsphere (about 500 nanometers of particle diameter) of diethylbenzene of certain mass at 2: 20 by the mass ratio ratio of polyurethane quality (the used nano particle quality with); And the ethanol of getting certain volume carries out wetting and ultrasonic dispersion treatment to nano particle; Treated nano particle and ethanol are poured in the polyurethane solutions of being prepared together, added the isopyknic N of used ethanol again, the dinethylformamide solvent is in polyurethane solutions; Make the concentration ratio of solvent for use cumulative volume (the polyurethane quality with) of polyurethane solutions reduce to the half the of initial concentration, be 0.1 grams per milliliter; At last, dispersed with stirring be not less than 1 hour even to solution, composite spinning solution.

(4) stretch processing of elastomer: at room temperature, place air to carry out vertical stretch processing initial elastomer; Initial elastomer is stretched to 2 times of former length, and the extended state of elastomer is kept being not less than 10 minutes.

(5) drying of elastomer: the screw type elastomer after the stretched processing is carried out drying; To remove remaining solvent; Thereby make final screw type elastomer with multistage micro nano structure; Its fiber surface has the microballoon of concaveconvex structure and 500 nano-scales simultaneously, and its fibrous inside also contains the nano particle of 500 nano-scales.

Embodiment 29:

Embodiment 30:

(5) drying of elastomer: the screw type elastomer after the stretched processing is carried out drying; To remove remaining solvent; Thereby make final screw type elastomer with multistage micro nano structure; Its fiber surface has the microballoon of concaveconvex structure and 200 nano-scales simultaneously, and its fibrous inside also contains the nano particle of 200 nano-scales.

Claims

1. elastomer with multistage micro nano structure, it is characterized in that: this elastomer surface has the groove of 1～10 micron-scale.

2. elastomer with multistage micro nano structure, it is characterized in that: this elastomer surface has the groove of 1～10 micron-scale, and its fibrous inside also contains nano particle.

3. elastomer with multistage micro nano structure, it is characterized in that: this elastomer surface has the groove of 1～10 micron-scale and the microballoon of nano-scale simultaneously, and its fibrous inside also contains nano particle.

4. elastomer with multistage micro nano structure, it is characterized in that: this elastomer surface has the groove of 1～10 micron-scale and the nanometer particle congery of 20 nanometers～8 micron-scales simultaneously, and its fibrous inside also contains nano particle.

5. elastomer with multistage micro nano structure; It is characterized in that: this elastomer surface has the groove of 1～10 micron-scale and the nanometer particle congery of 20 nanometers～8 micron-scales simultaneously, and its fibrous inside also contains the spheroid that nano particle and nano particle are induced 400 nanometers of generation～1.2 micron-scales simultaneously.

6. elastomer with multistage micro nano structure, it is characterized in that: this elastomer is the screw type elastomer, and its fiber surface has concaveconvex structure.

7. elastomer with multistage micro nano structure, it is characterized in that: this elastomer is the screw type elastomer, and its fiber surface has concaveconvex structure, and its fibrous inside also contains nano particle.

8. elastomer with multistage micro nano structure, it is characterized in that: this elastomer is the screw type elastomer, and its fiber surface has the microballoon of concaveconvex structure and nano-scale simultaneously, and its fibrous inside also contains nano particle.

9. one kind prepares aforesaid right requirement 1 described bionics method for preparation with elastomer of multistage micro nano structure, mainly may further comprise the steps:

(1) preparation of composite spinning solution: earlier with N, dinethylformamide is the polyurethane solutions of 0.1～0.4 grams per milliliter for the solvent compound concentration; Then, add isopyknic N respectively, dinethylformamide and alcohol solvent make the concentration of polyurethane solutions reduce to the half the of initial concentration, are 0.05～0.2 grams per milliliter; Last dispersed with stirring to solution is even, gets composite spinning solution; Described concentration is meant that institute adds the ratio of polyurethane quality and solvent for use volume;

(2) storage of composite spinning solution and extruding: composite spinning solution is placed the reservoir vessel that has piston and conduit, utilize pressure control device and spinning solution is compressed into conduit, and spinning solution is extruded from conduit through piston; The speed that from reservoir vessel, gets into conduit through pressure control device adjusting spinning solution is 0.2～5 milliliter/hour, and the internal diameter of conduit is 0.2～0.7 millimeter;

(3) moulding of elastomer: at room temperature, composite spinning solution is clamp-oned in conduit the one-tenth silk tank that running water is housed, composite spinning solution solidifies in water, and solvent spreads in water, and polyurethane elastomer carries out self assembly, forms initial elastomer;

(4) stretch processing of elastomer: at room temperature, place running water or air to carry out vertical stretch processing initial elastomer; Initial elastomer is stretched to 2～10 times of former length, and the extended state of elastomer is kept being not less than 10 minutes;

10. one kind prepares aforesaid right requirement 2 or 3 or 4 or 5 described bionics method for preparation with elastomer of multistage micro nano structure, mainly may further comprise the steps:

(1) preparation of composite spinning solution: earlier with N, dinethylformamide is the polyurethane solutions of 0.1～0.4 grams per milliliter for the solvent compound concentration; Then; Took by weighing the nano particle of certain mass in 1: 20～5: 20 by mass ratio, and the ethanol of getting certain volume carries out wetting and ultrasonic dispersion treatment to nano particle, pour into treated nano particle and ethanol in the polyurethane solutions of being prepared together; Add the isopyknic N of used ethanol again; The dinethylformamide solvent makes the concentration of polyurethane solutions reduce to the half the of initial concentration in polyurethane solutions, is 0.05～0.2 grams per milliliter; At last, dispersed with stirring be not less than 1 hour even to solution, composite spinning solution; Described concentration is meant the ratio of polyurethane quality and solvent for use volume, and described mass ratio is meant the ratio of used nano particle quality and polyurethane quality;

(3) moulding of elastomer: at room temperature; Composite spinning solution is clamp-oned in conduit the one-tenth silk tank that running water is housed, and composite spinning solution solidifies in water, and solvent spreads in water; Polyurethane elastomer and nano particle carry out self assembly, form initial elastomer;

11. one kind prepares aforesaid right requirement 6 described bionics method for preparation with elastomer of multistage micro nano structure, mainly may further comprise the steps:

(3) moulding of elastomer: at room temperature; Composite spinning solution is clamp-oned in conduit the one-tenth silk tank that running water is housed, become the silk bottom of gullet to stir running water through a magneton and form a small rotation fluctuation, composite spinning solution solidifies in water; Solvent spreads in water; Polyurethane elastomer carries out self assembly, and from spiral rising under water, forms initial screw type elastomer;

(4) stretch processing of elastomer: at room temperature, place air to carry out vertical stretch processing initial elastomer; Initial elastomer is stretched to 0～6 times of former length, and the extended state of elastomer is kept being not less than 10 minutes;

12. one kind prepares aforesaid right requirement 7 or 8 described bionics method for preparation with elastomer of multistage micro nano structure, mainly may further comprise the steps:

(3) moulding of elastomer: at room temperature; Composite spinning solution is clamp-oned in conduit the one-tenth silk tank that running water is housed, become the silk bottom of gullet to stir running water through a magneton and form a small rotation fluctuation, composite spinning solution solidifies in water; Solvent spreads in water; Polyurethane elastomer and nano particle carry out self assembly, and from spiral rising under water, form initial screw type elastomer;

13., it is characterized in that: select a kind of material of main part for use with the water-disintegrable TPUE of good resistance as the preparation elastomer according to claim 9 or 10 or 11 or 12 described bionical compound methods with elastomer of multistage micro nano structure.

14. according to claim 9 or 10 or 11 or 12 described bionical compound methods with elastomer of multistage micro nano structure, it is characterized in that: employed nano particle comprises polymer microballoon or inorganic matter microballoon.

15. one kind prepares aforesaid right requirement 1 or 2 or 3 or 4 or 5 described devices with multistage micro nano structure elastomer, it is characterized in that: this device mainly comprise pressure control device (1), at least have moveable piston (21) and conduit (22) reservoir vessel (2), become silk a tank (3), transfer device (4), stretching device (5), drying device (6) and gathering-device (7); Pressure control device (1) links to each other with piston (21), regulates the speed that piston mobile (21) is advanced through pressure control device (1), thus the speed that spinning solution gets into conduit (22) in the control reservoir vessel (2); Piston and conduit on the reservoir vessel (2) can load and unload flexibly, clean and change with convenient; Become the bottom and the top of silk tank (3) that a water inlet (32) and delivery port (31) are arranged respectively; The conduit (22) of reservoir vessel (2) gets into the running water from the bottom that becomes silk tank (3); Transfer device (4) is arranged in the running water of a tank or is arranged on outside the running water of a tank; Stretching device (5) is gone up the rotating speed of rotating shaft through control stretching device (5) directly over transfer device (4), come to carry out stretch processing to shifting the fiber of coming through transfer device (4); Stretched fibre treated is carried out drying via drying device (6); At last, the commentaries on classics that the fiber that is dried is gone up guidewire shaft via gathering-device (7) moves into the row collection.

16. one kind prepares aforesaid right requirement 6 or 7 or 8 described devices with multistage micro nano structure elastomer, it is characterized in that: this device mainly comprise pressure control device (1), at least have moveable piston (21) and conduit (22) reservoir vessel (2), magnetic stirring apparatus (8), become silk a tank (3), transfer device (4), stretching device (5), drying device (6) and gathering-device (7); Pressure control device (1) links to each other with piston (21), regulates the speed that piston mobile (21) is advanced through pressure control device (1), thus the speed that spinning solution gets into conduit (22) in the control reservoir vessel (2); Piston on the reservoir vessel (21) and conduit (22) can load and unload flexibly, clean and change with convenient; Magnetic stirring apparatus (8) places below the tank (3), becomes the bottom in the silk tank (3) to place a magneton (81), through the rotation of magnetic stirring apparatus (8) control magneton (81), so that in running water, form small rotation fluctuation; Become the bottom and the top of silk tank (3) that a water inlet (32) and delivery port (31) are arranged respectively; The conduit (21) of reservoir vessel (2) gets into the running water from the bottom that becomes silk tank (3); Transfer device (4) is outside the running water that becomes the silk tank; Stretching device (5) is gone up the rotating speed of rotating shaft through control stretching device (5) directly over transfer device, come to carry out stretch processing to shifting the fiber of coming through transfer device (4); Stretched fibre treated is carried out drying via drying device (6); At last, the commentaries on classics that the fiber that is dried is gone up guidewire shaft via gathering-device (7) moves into the row collection.