CN108624978B - Polymer fiber of bionic spider silk with water collection characteristic and preparation method thereof - Google Patents

Abstract

The invention relates to a polymer fiber of bionic spider silk with water collection characteristic and a preparation method thereof, belonging to the technical field of chemical bionics. The polymer fiber of the bionic spider silk with the water-collecting property comprises the following components in parts by weight: 100 parts by weight of a fiber matrix polymer; b. 1-50 parts of spray-dried powder rubber. The monofilament of the polymer fiber is provided with a microstructure of spider silk-like fibers with protruding structural units and linking structural units distributed at intervals, the radial height of the protruding structural units is 10-300 micrometers, the axial length of the protruding structural units is 10-1000 micrometers, the diameter range of the linking structural units is 5-200 micrometers, and the length of the linking structural units is 10-5000 micrometers. The method can be realized by adopting the traditional spinning equipment without additionally adding additional equipment, is simple and stable, and can be used for continuous large-scale preparation; the spider silk structure-imitated fiber obtained by the invention has low cost and good stability.

Description

Polymer fiber of bionic spider silk with water collection characteristic and preparation method thereof

Technical Field

The invention relates to the technical field of chemical bionics, in particular to a polymer fiber of bionic spider silk with water collection characteristic and a preparation method thereof.

Background

In the modern society, the shortage of fresh water resources is gradually appearing. The 47 th united nations will determine 22 days in 3 months every year as "water days in the world", and call the world countries to cause high alertness to the problem of shortage of fresh water resources which is ubiquitous in the world. China is recognized by the United nations as one of the 13 most scarce fresh water countries in the world. The total amount of fresh water resources in China is listed in the sixth world, but the total amount of people is only 1/4 which is the average value of the world, and is located in the 109 th world. Shortage of fresh water resources has affected economic development to some extent. Therefore, the problem of fresh water resources is urgently solved to ensure the sustainable development of economy in China.

In nature, spiders collect water in the air through a spider web to guarantee the survival mode, and a new idea is provided for solving the freshwater crisis. It was observed that condensation of water vapor was mainly concentrated on the weft portion of the spider web, i.e. the Capture silk (Capture line) of the spider web. Through research on the structure of the capture filament, the capture filament is not a conventional cylindrical fiber, but a fiber body is distributed with a periodic protrusion structure (Spindle-knob) and a link structure (Joint). When the capture filament is placed in a humid environment, water vapor is condensed on the surface of the fiber due to the condensation effect to form small water drops at first; the existence of the protruding structure and the linking structure in the fiber causes the curvature radius of the capture silk to change periodically; this curvature change further causes the water drops on the surface of the fiber to be unevenly stressed in the radial direction of the fiber, i.e., a laplace pressure difference is generated, so as to push the water drops to move. This motion is directional: moving from the linking structure portion (high radius of curvature portion) to the protruding structure portion (low radius of curvature portion). The directional movement of the water drops is beneficial to the small liquid drops to be quickly gathered to form large water drops, reduces evaporation, is beneficial to the quick collection of moisture in the air, is expected to be applied to water collection engineering, is particularly expected to be applied to regions such as deserts with large day-night temperature difference and islands with high air humidity, and is also expected to be applied to the dispersion of water vapor around airports, street lamps and signal lamps.

The method for preparing the spider silk-like fiber in the prior art mainly comprises two methods, namely an impregnation method, wherein the existing fiber is put into a high molecular solution, the high molecular solution forms liquid drops on the surface of the fiber due to Rayleigh instability in the solvent volatilization process, and a raised structure of a high molecular substance is generated after the solvent is volatilized, so that the method belongs to the subsequent processing of the fiber; secondly, the electrostatic spinning method is utilized, so that the requirement on equipment is high.

A water-collecting polymer silk imitating spider silk structure and a preparation method thereof are disclosed in Chinese patent with publication number CN102776785A (application number 201110223679.7): the water-collecting polymer silk with a spider silk-like structure is obtained by immersing a common artificial silk into a polymer solution, then horizontally pulling the artificial silk out of the solution along the axial direction of the artificial silk, then enabling a liquid film of the polymer solution on the surface of the artificial silk to be evolved into a string of liquid drops to be hung on the artificial silk due to Rayleigh instability, and drying and solidifying the liquid drops to obtain the spindle knots which are axially arranged. On the basis of the above patent, chinese patent publication No. CN102587139A (application No. 201210004686.2) further realizes that the height of the protruding nodes on the surface of the prepared fiber is uniform and controllable from small to large, and the surface of the fiber has more microscopic protrusions or micropores, so that the collision probability and the spreading speed of air water drops are increased, the water collection efficiency is improved, and thus the collision probability and the spreading speed of the air water drops are increased, and the water collection efficiency is improved. Both of the above patents pertain to post-processing of existing fibers. Chinese patent with publication number CN103334244A (application number 201310227113.0) discloses a self-assembly preparation method of an electrospinning bead string fiber, which adopts an electrospinning technology to form a micron-sized bead string structure on the surface of artificial fiber by self-assembly to obtain an spider silk-like fiber. However, electrospinning equipment is expensive and fewer polymers can be used for electrospinning.

Disclosure of Invention

In order to solve the above problems in the prior art, the present invention proposes a polymer fiber of biomimetic spider silk having water-collecting characteristics. In particular to a polymer fiber of bionic spider silk with water collection characteristic and a preparation method thereof. The fiber can cause small water drops formed in the water vapor condensation process to directionally move to form large water drops, reduce the specific surface area of the water drops, and reduce the volatilization degree of the formed water drops, so that the water vapor collection is accelerated, and the water collection is facilitated. The method can obtain the protruding structure in the preparation process of the fiber, the existing spinning process is not required to be greatly changed, the equipment is not required to be changed, and the method is simpler in process and lower in cost.

The monofilament of the bionic spider silk-like polymer fiber with water collection property has a microstructure of spider silk-like with a protruding structure unit (Spindle-knob) and a linking structure unit (Joint) which are distributed at intervals, can realize the directional movement of water drops on the surface of the fiber, and has a water collection function. The radial height of the protruding structure units is 10-300 microns, preferably 20-200 microns, more preferably 30-150 microns, the axial length of the protruding structure units is 10-1000 microns, preferably 20-700 microns, more preferably 40-300 microns, the distance between the protruding structure units, namely the length of the link structure units is 10-5000 microns, preferably 50-3000 microns, more preferably 100-1000 microns. The diameter range of the linking structure unit is 5-200 microns, preferably 10-100 microns, and more preferably 20-50 microns.

The polymer fiber of the bionic spider silk with the water-collecting characteristic comprises the following components in parts by weight:

a. 100 parts by weight of a fiber matrix polymer;

b. 1 to 50 parts by weight of spray-dried powder rubber, preferably 10 to 40 parts by weight, more preferably 10 to 30 parts by weight, and still more preferably 20 to 30 parts by weight.

The component a fiber matrix polymer is used as a fiber matrix, and the component b spray-dried rubber is used as a protrusion structure.

The fiber matrix polymer is selected from at least one of polyacrylonitrile, polyurethane, polyvinyl alcohol, viscose fiber, nylon, cellulose sulfonate, cellulose acetate, polyvinyl chloride, polyisophthaloyl amide, polyisophthaloyl metaphenylene diamine and poly terephthaloyl p-phenylenediamine; preferably at least one of polyacrylonitrile, polyurethane, polyvinyl alcohol, viscose, poly (m-phenylene isophthalamide), poly (p-phenylene terephthalamide), and polyvinyl chloride, more preferably at least one of polyacrylonitrile, polyurethane, and polyvinyl alcohol, and more preferably polyvinyl alcohol.

When the fiber matrix polymer selects polyvinyl alcohol as a fiber main body, the polymerization degree of the polyvinyl alcohol is 400-2600, preferably 500-2000, and more preferably 1000-1700; the alcoholysis degree is 55-99%, preferably 88-99%.

The average particle size of the spray-dried powder rubber is 500 nanometers to 200 micrometers, preferably 10 micrometers to 100 micrometers, and more preferably 20 micrometers to 50 micrometers.

The spray-dried powder rubber used in the invention is prepared by irradiation crosslinking of rubber emulsion and drying by a spray drying method. In the preparation process of the spray-dried powder rubber, the high-energy radiation source used for irradiation crosslinking can be specifically selected from at least one of a cobalt source, ultraviolet and a high-energy electron accelerator, and preferably the wavelength of the high-energy radiation source is less than 0.1 μm, such as a cobalt source. In addition, the irradiation dose is generally such that the gel content of the rubber particles after irradiation-crosslinking of the rubber latex is 60% by weight or more, preferably 75% by weight or more, more preferably 80% by weight or more. Specifically, the irradiation dose can be 0.1-30 Mrad, preferably 0.5-20 Mrad.

The spray-dried powder rubber may be any of various spray-dried powder rubbers known in the art, and may be obtained commercially or prepared by any of various methods known in the art. For example, the spray-dried powder rubber may be a fully vulcanized powder rubber prepared according to international patent application WO01/40356 (priority date 1999, 12/3/10/priority patent is chinese patent C1152082C) filed by the applicant of the present invention on 9/18/2000 and international patent application WO01/98395 (priority date 2000, 6/15/2000, priority patent is chinese patent C1330097A) filed by the applicant of the present invention on 6/15/2001. Further, examples of the fully vulcanized powder rubber include, but are not limited to: fully vulcanized powder natural rubber, fully vulcanized powder styrene-butadiene rubber, fully vulcanized powder carboxylated styrene-butadiene rubber, fully vulcanized powder nitrile-butadiene rubber, fully vulcanized powder carboxylated nitrile-butadiene rubber, fully vulcanized powder polybutadiene rubber, fully vulcanized powder silicone rubber, fully vulcanized powder chloroprene rubber, fully vulcanized powder acrylate rubber, fully vulcanized powder vinylpyridine butadiene rubber, fully vulcanized powder isoprene rubber, fully vulcanized powder butyl rubber, fully vulcanized powder polysulfide rubber, fully vulcanized powder acrylate-butadiene rubber, fully vulcanized powder polyurethane rubber, fully vulcanized powder fluorine rubber, fully vulcanized powder ethylene-vinyl acetate rubber and the like, preferably at least one of fully vulcanized powder styrene-butadiene rubber, fully vulcanized powder carboxylated styrene-butadiene rubber, fully vulcanized powder nitrile-butadiene rubber, fully vulcanized powder carboxylated nitrile rubber, fully vulcanized powder acrylate rubber, Fully vulcanized powdered ethylene-vinyl acetate rubber. The gel content of the fully vulcanized powdery rubber is preferably 60% by weight or more, more preferably 75% by weight or more, and particularly preferably 80% by weight or more.

In addition, each particle in the fully vulcanized powder rubber is homogeneous, that is, no phenomenon of heterogeneous phase such as delamination and phase separation is observed in the particle under the observation of the prior art microscopy.

In addition, in the irradiation crosslinking preparation process of the spray-dried powder rubber, a crosslinking assistant may not be used, and may also be used. The crosslinking assistant may be any one selected from the group consisting of a monofunctional crosslinking assistant, a difunctional crosslinking assistant, a trifunctional crosslinking assistant, a tetrafunctional crosslinking assistant, and a pentafunctional or higher crosslinking assistant. Examples of monofunctional crosslinking coagents include, but are not limited to: at least one of octyl (meth) acrylate, isooctyl (meth) acrylate, and glycidyl (meth) acrylate; examples of the difunctional crosslinking coagent include, but are not limited to: at least one of 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and divinylbenzene; examples of the trifunctional crosslinking coagent include, but are not limited to: trimethylolpropane tri (meth) acrylate and/or pentaerythritol tri (meth) acrylate; examples of the tetrafunctional crosslinking coagent include, but are not limited to: pentaerythritol tetra (meth) acrylate and/or ethoxylated pentaerythritol tetra (meth) acrylate; examples of the above five-functional group crosslinking coagent include, but are not limited to: dipentaerythritol penta (meth) acrylate. Herein, the (meth) acrylate refers to an acrylate or a methacrylate. These crosslinking assistants may be used in any combination as long as they contribute to crosslinking under irradiation. In addition, the addition amount of the crosslinking assistant is generally 0.1 to 10 wt%, preferably 0.5 to 9 wt%, and more preferably 0.7 to 7 wt% of the weight of the dry rubber in the latex.

The second purpose of the application is to provide a preparation method of the polymer fiber of the bionic spider silk with the water collection characteristic. According to the method, a polymer and powder rubber are spun together by a traditional wet spinning method, spray-dried powder rubber is dispersed in a polymer solution, and in the process of forming fibers by a coagulating bath, as a solvent is continuously precipitated, the volume of a fiber main body is greatly shrunk, and the volume of the spray-dried powder rubber is not affected, so that the fibers are microscopically protruded to form a protruded structure in the existence position of the spray-dried powder rubber, and the fibers are naturally shrunk to form a linked structure, so that the bionic spider silk fiber with the water collection characteristic is obtained. The method has the advantages of one-step forming, simple and convenient process and easy industrial production.

The preparation method of the polymer fiber of the bionic spider silk with the water-collecting characteristic comprises the following steps:

(1) dispersing the fiber matrix polymer and the spray-dried powder rubber in a solvent, heating and stirring until the fiber matrix polymer is dissolved in the solvent, and uniformly dispersing the powder rubber in the solution to obtain a uniform spinning solution; wherein the heating temperature is 30-95 ℃, preferably 50-95 ℃, and more preferably 70-95 ℃;

(2) preparing corresponding coagulating baths corresponding to the adopted polymer main bodies;

(3) and extruding the spinning solution into a coagulating bath through a wet spinning machine or a peristaltic pump and the like, and coagulating, drying and collecting to obtain the bionic fiber.

Preferably after the above steps, comprising: (4) putting the bionic fiber in a cross-linking solution for a certain time; and (4) washing, drying and collecting to obtain the fiber. The cross-linking process can change the water resistance, strength and the like of the fiber, but does not affect the basic physical structure of the fiber, namely the protrusion structure and the link structure, and does not affect the directional movement of water drops on the surface of the fiber, so the cross-linking process is a selection process and does not affect the practical application of the fiber.

In particular, the amount of the solvent to be used,

in the step (1), the amount of the fiber matrix polymer is 5 to 50 parts by weight, preferably 10 to 40 parts by weight, and more preferably 10 to 25 parts by weight, based on 100 parts by weight of the solvent; the amount of the spray-dried powder rubber is 1 to 50 parts by weight, preferably 10 to 40 parts by weight, more preferably 10 to 30 parts by weight, and still more preferably 20 to 30 parts by weight, based on 100 parts by weight of the fiber matrix polymer. In the step (1), the solvent may be any common wet spinning solvent corresponding to the polymer used, and may be at least one selected from 1, 4-dioxane, N-dimethylformamide, tetrahydrofuran, water and sulfuric acid, and more preferably at least one selected from N, N-dimethylformamide and 1, 4-dioxane.

In the step (2), the coagulation bath can be any common wet spinning coagulation bath corresponding to the used fiber matrix polymer. The mixing process can adopt any existing liquid-liquid mixing equipment, such as mechanical stirring, ultrasonic dispersion and the like. The coagulating bath can be at least one or mixed solvent of sodium sulfate aqueous solution, methanol, ethyl acetate, water, 1, 4-dioxane and N, N-dimethylformamide, preferably at least one or mixed solvent of sodium sulfate aqueous solution, methanol, water, 1, 4-dioxane and N, N-dimethylformamide; the concentration of the sodium sulfate aqueous solution is 300-500 g/L, preferably 350-450 g/L.

If the aqueous solution of polyvinyl alcohol is selected as the spinning solution, at least one of aqueous solution of sodium sulfate, methanol and ethyl acetate can be selected as the coagulating bath, wherein the concentration of the aqueous solution of sodium sulfate is 300-500 g/L, preferably 350-450 g/L; preferably at least one of an aqueous sodium sulfate solution and methanol, more preferably an aqueous sodium sulfate solution; if a 1, 4-dioxane solution of polyvinyl alcohol is selected as a spinning solution, at least one of methanol, ethyl acetate and water or a binary solution selected from methanol and 1, 4-dioxane can be selected as a coagulating bath, preferably methanol or a binary solution of methanol and 1, 4-dioxane is selected, more preferably a binary solution of methanol and 1, 4-dioxane is selected, wherein in the binary solution of methanol and 1, 4-dioxane, the content of 1, 4-dioxane is 0.1-50 parts by weight, preferably 5-40 parts by weight, more preferably 10-30 parts by weight based on 100 parts by weight of methanol. Because the coagulation ability of pure methanol is stronger, the fiber coagulation is faster, which is not beneficial to the fine drawing of the fiber and the protrusion of the convex structure in the subsequent filament collecting process, a proper amount of 1, 4-dioxane can be added into the coagulation bath according to the requirement, the fiber forming speed can be reduced, and the formation of the convex structure is facilitated.

When the spinning solution is used for spinning, the spinneret orifices are all commonly used in the spinning process, preferably square, round, triangular or pentagonal, more preferably round, square or triangular, and even more preferably round; the inner diameter of the spinneret orifice can be 10-1000 microns, preferably 50-500 microns, and more preferably 50-300 microns; the filament receiving rate can be 0.1-100 meters per minute, preferably 0.1-10 meters per minute, and more preferably 0.2-1 meter per minute.

In the step (4), the crosslinking solution may be a common wet spinning crosslinking solution corresponding to the used fiber matrix polymer.

If polyvinyl alcohol is used as the fiber matrix polymer, the crosslinking solution can be composed of a solution of acids and aldehydes and/or sodium sulfate and water, i.e., the crosslinking solution is an aqueous solution of acids and aldehydes, optionally with the addition of sodium sulfate. The acid can be common inorganic acid, preferably at least one of hydrochloric acid and sulfuric acid, and more preferably sulfuric acid; the aldehyde is preferably at least one of formaldehyde and glutaraldehyde. Specifically, the cross-linking liquid is preferably an aqueous solution of sulfuric acid, glutaraldehyde, formaldehyde, sodium sulfate and water, wherein the concentration of the sulfuric acid can be 100-500 grams per liter, and preferably 200-350 grams per liter; the concentration of the glutaraldehyde can be 1-80 grams per liter, and preferably 30-60 grams per liter; the concentration of formaldehyde can be 1-50 grams per liter, and preferably 20-35 grams per liter; the concentration of sodium sulfate can be 0-350 g/L, preferably 50-200 g/L.

The artificial fiber obtained by the bionic spider silk with the water collection characteristic can collect water drops under high humidity, and water vapor is combined from a linking structure (high curvature radius) part to a protruding structure (low curvature radius) part in the condensation and growth processes, so that the water drops are accelerated to collect at the protruding part, and the collection is facilitated.

The invention has the advantages that:

(1) the method can be realized by adopting the traditional spinning equipment without additionally adding additional equipment, and is simple and stable;

(2) the water-collecting polymer silk imitating the spider silk structure can be continuously prepared in a large scale;

(3) the fiber with the spider silk-like structure obtained by the invention has low cost and good stability;

(4) the fiber with the spider silk-like structure obtained by the invention can be used for collecting water drops in the air and dispersing and dissipating dense fog around airports, expressways or lighthouses in regions such as temporary sea deserts, islands, foggy mountainous areas and the like.

Drawings

FIG. 1 is a scanning electron microscope photograph of the polymer fiber of biomimetic spider silk having water-collecting properties made in example 1;

FIG. 2 is a scanning electron microscope photograph of the polymer fibers of biomimetic spider silk having water-collecting properties made in example 2;

FIG. 3 is a scanning electron microscope photograph of the polymer fibers of biomimetic spider silk with water-collecting properties made in example 3;

FIG. 4 is a scanning electron micrograph of a pure polyethylene glycol fiber prepared in comparative example 1;

FIG. 5 is an optical photograph of the water-collecting polymer fibers of the biomimetic spider silk having water-collecting characteristics obtained in example 6 (order of pictures: from left to right, top to bottom).

FIGS. 1 to 3 show the microstructure of the obtained fiber, including the size and distribution of the convex structure, under different amounts of the powdered rubber. As the addition amount of the powdered rubber is increased, the size of the bulge structure is increased and the bulge structure is more dense. Therefore, fibers with different structures can be obtained by regulating and controlling the size and the adding amount of the powdered rubber. FIG. 4 shows, as a comparative example, that in the case of no addition of powdered rubber, no raised structures are present.

As can be seen from figure 5, in the process of water vapor condensation, small water drops are firstly formed on the surface of the fiber in a disordered manner, the curvature radius of the fiber around the fiber is changed due to the existence of the convex structure, the water drops receive Laplace pressure difference and move towards the convex structure, large water drops are formed in an accelerated manner, the specific surface area is reduced, and the volatilization degree is reduced. After the small water drops are formed again at other positions, the condition is repeated, the water drops are accelerated to be collected, and therefore the water drops can be used for collecting water vapor.

Detailed Description

The present invention will be further described with reference to the following examples. However, the present invention is not limited to these examples. The experimental data in the examples were measured using the following instruments and methods:

(1) experiment basic equipment: the extrusion apparatus was a peristaltic pump model SPLab01 manufactured by Baoding Pump industry, Inc.

(2) Experimental data determination apparatus: scanning electron micrographs were obtained from a Hitachi S-4800 scanning electron microscope and the process of directional movement of water droplets on the fiber surface was obtained from a contact angle measuring apparatus model SCA20 from Dataphysics, Germany.

Example 1

7g of polyvinyl alcohol (PVA 1799, Allantin, degree of polymerization 1700, degree of alcoholysis 99%) and 0.7 g of carboxylated styrene-butadiene spray-dried powder rubber were dispersed in 43 g of 1, 4-Dioxane (DMSO), and heated and stirred at 80 ℃ for 2 hours to obtain a uniform spinning dope. The spinning dope was extruded into a coagulation bath (a mixed solution of methanol and DMSO, based on 100 parts by weight of methanol, and DMSO20 parts by weight) by a peristaltic pump at room temperature to spin: the actual extrusion rate was 0.01 ml per minute, the spinneret size was 25G (round, 260 micron diameter), the take-up rate was 0.42 meters per minute, and the fibers were in the coagulation bath for at least 5 minutes. And (3) fully drying the obtained fibers in the air, collecting to obtain the polymer fibers of the bionic spider silk with the water-collecting property, and testing, wherein the test result is shown in figure 1. The diameter of a link structure unit of the obtained fiber is 30 micrometers, the radial height of a protrusion structure unit is 40-100 micrometers, the axial length of the protrusion structure unit is 50-200 micrometers, and the length of the link structure unit is 70-3000 micrometers.

The preparation method of the carboxylic styrene-butadiene spray-dried powder rubber comprises the following steps: 1kg of carboxylated styrene-butadiene latex with a solid content of 50 percent, manufactured by Yanshan petrochemical industry and under the brand name XSBRL-54B1 is placed in a container, 15g of isooctyl acrylate is dropwise added under stirring, the stirring is continued for one hour after the dropwise addition is finished, then a cobalt source is used for irradiation, the dosage is 2.5Mrad, the dosage rate is 50Gy/min, the irradiated latex is spray-dried by a spray dryer, the inlet temperature of the spray dryer is 140-160 ℃, the outlet temperature is 60-70 ℃, the dried carboxylated styrene-butadiene rubber powder is collected, and a sample of the carboxylated styrene-butadiene rubber powder with the average particle size of 30 micrometers is obtained by screening.

Comparative example 1

7g of polyvinyl alcohol (PVA 1799, Allantin, degree of polymerization 1700, degree of alcoholysis 99%) were dispersed in 43 g of 1, 4-Dioxane (DMSO), and heated and stirred at 80 ℃ for 2 hours to obtain a homogeneous dope. The spinning dope was extruded into a coagulation bath (a mixed solution of methanol and DMSO, based on 100 parts by weight of methanol, and DMSO20 parts by weight) by a peristaltic pump at room temperature to spin: the actual extrusion rate was 0.01 ml per minute, the spinneret size was 25G (round, 260 micron diameter), the take-up rate was 0.42 meters per minute, and the fibers were in the coagulation bath for at least 5 minutes. The resulting fibers were subjected to testing after being sufficiently dried in air, and the results of the testing are shown in FIG. 4.

Example 2

7g of polyvinyl alcohol (PVA 1799, Allantin, degree of polymerization 1700, degree of alcoholysis 99%) and 1.4 g of carboxylated styrene-butadiene spray-dried powder rubber (same as in example 1) were dispersed in 43 g of 1, 4-Dioxane (DMSO) and heated and stirred at 80 ℃ for 2 hours to obtain a homogeneous dope. The spinning dope was extruded into a coagulation bath (a mixed solution of methanol and DMSO, based on 100 parts by weight of methanol, and DMSO20 parts by weight) by a peristaltic pump at room temperature to spin: the actual extrusion rate was 0.01 ml per minute, the spinneret size was 25G (round, 260 micron diameter), the take-up rate was 0.42 meters per minute, and the fibers were in the coagulation bath for at least 5 minutes. And (3) fully drying the obtained fibers in the air, collecting to obtain the polymer fibers of the bionic spider silk with the water-collecting property, and testing, wherein the test result is shown in figure 2. The diameter of a link structure unit of the obtained fiber is 30 micrometers, the radial height of a protrusion structure unit is 40-100 micrometers, the axial length of the protrusion structure unit is 50-200 micrometers, and the length of the link structure unit is 50-2200 micrometers.

Example 3

7g of polyvinyl alcohol (PVA 1799, Allantin, degree of polymerization 1700, degree of alcoholysis 99%) and 2.1 g of carboxylated styrene-butadiene spray-dried powder rubber (same as in example 1) were dispersed in 43 g of 1, 4-Dioxane (DMSO) and heated and stirred at 80 ℃ for 2 hours to obtain a homogeneous dope. The spinning dope was extruded into a coagulation bath (a mixed solution of methanol and DMSO, based on 100 parts by weight of methanol, and DMSO20 parts by weight) by a peristaltic pump at room temperature to spin: extrusion rate 0.01 ml per minute, spinneret size 25G (round, 260 micron diameter), take-up rate 0.42 meter per minute, and fiber in coagulation bath for at least 5 minutes. And (3) fully drying the obtained fibers in the air, collecting to obtain the polymer fibers of the bionic spider silk with the water-collecting property, and testing, wherein the test result is shown in figure 3. The diameter of a link structure unit of the obtained fiber is 30 micrometers, the radial height of a protrusion structure unit is 40-100 micrometers, the axial length of the protrusion structure unit is 50-200 micrometers, and the length of the link structure unit is 50-1200 micrometers.

Example 4

7g of polyvinyl alcohol (PVA 1799, Allantin, degree of polymerization 1700, degree of alcoholysis 99%) and 0.7 g of carboxylated styrene-butadiene spray-dried powder rubber (same as in example 1) were dispersed in 43 g of 1, 4-Dioxane (DMSO) and heated and stirred at 80 ℃ for 2 hours to obtain a homogeneous dope. The spinning dope was extruded into a coagulation bath (a mixed solution of methanol and DMSO, based on 100 parts by weight of methanol, and DMSO20 parts by weight) by a peristaltic pump at room temperature to spin: the actual extrusion rate was 0.01 ml per minute, the spinneret size was 25G (round, 260 micron diameter), the take-up rate was 0.42 meters per minute, and the fibers were in the coagulation bath for at least 5 minutes. The fiber obtained above was placed in a crosslinking solution (11.48 g of 98% concentrated sulfuric acid, 3.5g of sodium sulfate, 4.16 g of 50% glutaraldehyde aqueous solution, 50 ml of aqueous solution obtained by constant volume) for 5 minutes. And (3) washing, drying and collecting to obtain the polymer fiber of the bionic spider silk with water collection characteristic. The diameter of a link structure unit of the obtained fiber is 30 micrometers, the radial height of a protrusion structure unit is 40-100 micrometers, the axial length of the protrusion structure unit is 50-200 micrometers, and the length of the link structure unit is 70-3000 micrometers.

Example 5

7g of polyvinyl alcohol (PVA 1799, Allantin, degree of polymerization 1700, degree of alcoholysis 99%) and 1.4 g of carboxylated styrene-butadiene spray-dried powder rubber (same as in example 1) were dispersed in 43 g of 1, 4-Dioxane (DMSO) and heated and stirred at 80 ℃ for 2 hours to obtain a homogeneous dope. The spinning dope was extruded into a coagulation bath (a mixed solution of methanol and DMSO, based on 100 parts by weight of methanol, and DMSO20 parts by weight) by a peristaltic pump at room temperature to spin: the actual extrusion rate was 0.01 ml per minute, the spinneret size was 25G (round, 260 micron diameter), the take-up rate was 0.42 meters per minute, and the fibers were in the coagulation bath for at least 5 minutes. The fiber obtained above was placed in a crosslinking solution (11.48 g of 98% concentrated sulfuric acid, 3.5g of sodium sulfate, 4.16 g of 50% glutaraldehyde aqueous solution, 50 ml of aqueous solution obtained by constant volume) for 5 minutes. And (3) washing, drying and collecting to obtain the polymer fiber of the bionic spider silk with water collection characteristic. The diameter of a link structure unit of the obtained fiber is 30 micrometers, the radial height of a protrusion structure unit is 40-100 micrometers, the axial length of the protrusion structure unit is 50-200 micrometers, and the length of the link structure unit is 50-2200 micrometers.

Example 6

7g of polyvinyl alcohol (PVA 1799, Allantin, degree of polymerization 1700, degree of alcoholysis 99%) and 2.1 g of carboxylated styrene-butadiene spray-dried powder rubber (same as in example 1) were dispersed in 43 g of 1, 4-Dioxane (DMSO) and heated and stirred at 80 ℃ for 2 hours to obtain a homogeneous dope. The spinning dope was extruded into a coagulation bath (a mixed solution of methanol and DMSO, based on 100 parts by weight of methanol, and DMSO20 parts by weight) by a peristaltic pump at room temperature to spin: extrusion rate 0.01 ml per minute, spinneret size 25G (round, 260 micron diameter), take-up rate 0.42 meter per minute, and fiber in coagulation bath for at least 5 minutes. The fiber obtained above was placed in a crosslinking solution (11.48 g of 98% concentrated sulfuric acid, 3.5g of sodium sulfate, 4.16 g of 50% glutaraldehyde aqueous solution, 50 ml of aqueous solution obtained by constant volume) for 5 minutes. And (3) washing, drying and collecting to obtain the polymer fiber of the bionic spider silk with the water collection characteristic, and testing, wherein the test result is shown in figure 5. The diameter of a link structure unit of the obtained fiber is 30 micrometers, the radial height of a protrusion structure unit is 40-100 micrometers, the axial length of the protrusion structure unit is 50-200 micrometers, and the length of the link structure unit is 50-1200 micrometers.

Example 7

10 g of polyvinyl alcohol (PVA 1799, Allantin, degree of polymerization 1700, degree of alcoholysis 99%) and 1 g of carboxylated styrene-butadiene spray-dried powder rubber (same as in example 1) were dispersed in 25g of 1, 4-Dioxane (DMSO) and heated and stirred at 80 ℃ for 2 hours to obtain a homogeneous dope. The spinning dope was extruded into a coagulation bath (a mixed solution of methanol and DMSO, 20 parts by weight of DMSO based on 100 parts by weight of methanol) by a peristaltic pump at room temperature to carry out spinning: the actual extrusion rate was 0.01 ml per minute, the spinneret size was 25G (round, 260 micron diameter), the take-up rate was 0.42 meters per minute, and the fibers were in the coagulation bath for at least 5 minutes. And fully drying the obtained fibers in the air, and collecting to obtain the polymer fibers of the bionic spider silk with the water collection characteristic. The diameter of a link structure unit of the obtained fiber is 40 micrometers, the radial height of a protrusion structure unit is 50-100 micrometers, the axial length of the protrusion structure unit is 70-250 micrometers, and the length of the link structure unit is 50-2800 micrometers.

Example 8

10 g of polyvinyl alcohol (PVA 1799, Allantin, degree of polymerization 1700, degree of alcoholysis 99%), 1 g of carboxylated styrene-butadiene spray-dried powder rubber (preparation method is the same as example 1, but a sample of carboxylated styrene-butadiene spray-dried powder rubber with an average particle size of 40 μm after volume sieving) was dispersed in 40 g of 1, 4-Dioxane (DMSO), and heated and stirred at 80 ℃ for 2 hours to obtain a homogeneous spinning dope. The spinning dope was extruded into a coagulation bath (a mixed solution of methanol and DMSO, 20 parts by weight of DMSO based on 100 parts by weight of methanol) by a peristaltic pump at room temperature to carry out spinning: the actual extrusion rate was 0.01 ml per minute, the spinneret size was 25G (round, 260 micron diameter), the take-up rate was 0.42 meters per minute, and the fibers were in the coagulation bath for at least 5 minutes. And fully drying the obtained fibers in the air, and collecting to obtain the polymer fibers of the bionic spider silk with the water collection characteristic. The diameter of a link structure unit of the obtained fiber is 34 micrometers, the radial height of a protrusion structure unit is 45-100 micrometers, the axial length of the protrusion structure unit is 50-200 micrometers, and the length of the link structure unit is 50-3000 micrometers.

Example 9

10 g of polyvinyl alcohol (PVA 1788, Allantin, degree of polymerization 1700, degree of alcoholysis 88%), 1 g of carboxylated styrene-butadiene spray-dried powder rubber (same as in example 1) were dispersed in 40 g of 1, 4-Dioxane (DMSO), and heated and stirred at 70 ℃ for 2 hours to obtain a uniform spinning dope. The spinning dope was extruded into a coagulation bath (a mixed solution of methanol and DMSO, 20 parts by weight of DMSO based on 100 parts by weight of methanol) by a peristaltic pump at room temperature to carry out spinning: the actual extrusion rate was 0.01 ml per minute, the spinneret size was 25G (round, 260 micron diameter), the take-up rate was 0.40 meter per minute, and the fibers were in the coagulation bath for at least 5 minutes. And fully drying the obtained fibers in the air, and collecting to obtain the polymer fibers of the bionic spider silk with the water collection characteristic. The diameter of a link structure unit of the obtained fiber is 40 micrometers, the radial height of a protrusion structure unit is 45-100 micrometers, the axial length of the protrusion structure unit is 50-200 micrometers, and the length of the link structure unit is 60-3000 micrometers.

Example 10

10 g of polyvinyl alcohol (PVA CP1000, available from Coly, having a degree of polymerization of about 400 and a degree of alcoholysis of about 70%), 1 g of carboxylated styrene-butadiene spray-dried powder rubber (same as in example 8) were dispersed in 40 g of 1, 4-Dioxane (DMSO), and heated and stirred at 60 ℃ for 2 hours to obtain a uniform dope. The spinning dope was extruded into a coagulation bath (a mixed solution of methanol and DMSO, 20 parts by weight of DMSO based on 100 parts by weight of methanol) by a peristaltic pump at room temperature to carry out spinning: the actual extrusion rate was 0.01 ml per minute, the spinneret size was 25G (round, 260 micron diameter), the take-up rate was 0.30 meters per minute, and the fibers were in the coagulation bath for at least 5 minutes. And fully drying the obtained fibers in the air, and collecting to obtain the polymer fibers of the bionic spider silk with the water collection characteristic. The diameter of a link structure unit of the obtained fiber is 40 micrometers, the radial height of a protrusion structure unit is 45-100 micrometers, the axial length of the protrusion structure unit is 50-250 micrometers, and the length of the link structure unit is 80-3500 micrometers.

Example 11

7g of polyvinyl alcohol (PVA 1799, Allantin, degree of polymerization 1700, degree of alcoholysis 99%) and 0.7 g of butyronitrile spray-dried powder rubber were dispersed in 43 g of 1, 4-Dioxane (DMSO), and heated and stirred at 80 ℃ for 2 hours to obtain a uniform spinning dope. The spinning dope was extruded into a coagulation bath (a mixed solution of methanol and DMSO, 20 parts by weight of DMSO based on 100 parts by weight of methanol) by a peristaltic pump at room temperature to carry out spinning: the actual extrusion rate was 0.01 ml per minute, the spinneret size was 25G (round, 260 micron diameter), the take-up rate was 0.42 meters per minute, and the fibers were in the coagulation bath for at least 5 minutes. And fully drying the obtained fibers in the air, and collecting to obtain the polymer fibers of the bionic spider silk with the water collection characteristic. The diameter of a link structure unit of the obtained fiber is 30 micrometers, the radial height of a protrusion structure unit is 60-130 micrometers, the axial length of the protrusion structure unit is 70-300 micrometers, and the length of the link structure unit is 50-3000 micrometers.

The preparation method of the butyronitrile spray-dried powder rubber comprises the following steps: 1kg of nitrile rubber latex with a solid content of 45 percent is subjected to bluing production, the nitrile rubber latex is placed in a container, 15g of trimethylolpropane triacrylate is dropwise added under stirring, the mixture is continuously stirred for one hour after the dropwise addition is finished, then a cobalt source is used for irradiation, the dosage is 2.5Mrad, the dosage rate is 50Gy/min, the irradiated latex is subjected to spray drying by a spray dryer, the inlet temperature of the spray dryer is 140-160 ℃, the outlet temperature is 60-70 ℃, the dried nitrile rubber powder is collected, and a nitrile spray drying powder rubber sample with the average particle size of 60 micrometers is obtained by screening.

Example 12

7g of polyvinyl alcohol (PVA 1799, Allantin, degree of polymerization 1700, degree of alcoholysis 99%), 0.7 g of butyronitrile spray-dried powder rubber (preparation method is the same as example 11, but butyronitrile spray-dried powder rubber sample with average particle size of 15 μm after volume sieving) were dispersed in 43 g of 1, 4-Dioxane (DMSO), and heated and stirred at 80 ℃ for 2 hours to obtain a homogeneous dope. The spinning dope was extruded into a coagulation bath (a mixed solution of methanol and DMSO, 20 parts by weight of DMSO based on 100 parts by weight of methanol) by a peristaltic pump at room temperature to carry out spinning: the actual extrusion rate was 0.006 ml per minute, the spinneret size was 30G (round, 160 micron diameter), the take-up rate was 0.6 meter per minute, and the fibers were in the coagulation bath for at least 5 minutes. And fully drying the obtained fibers in the air, and collecting to obtain the polymer fibers of the bionic spider silk with the water collection characteristic. The diameter of a link structure unit of the obtained fiber is 15 micrometers, the radial height of a protrusion structure unit is 20-50 micrometers, the axial length of the protrusion structure unit is 20-150 micrometers, and the length of the link structure unit is 120-3700 micrometers.

Example 13

7g of polyvinyl alcohol (PVA 1799, Allantin, degree of polymerization 1700, degree of alcoholysis 99%), 0.7 g of butyronitrile spray-dried powder rubber (preparation method is the same as example 11, but butyronitrile spray-dried powder rubber sample with average particle size of 90 μm after volume sieving) were dispersed in 43 g of 1, 4-Dioxane (DMSO), and heated and stirred at 80 ℃ for 2 hours to obtain a homogeneous dope. The spinning dope was extruded into a coagulation bath (a mixed solution of methanol and DMSO, 20 parts by weight of DMSO based on 100 parts by weight of methanol) by a peristaltic pump at room temperature to carry out spinning: the actual extrusion rate was 0.01 ml per minute, the spinneret size was 22G (round, 410 micron diameter), the take-up rate was 0.15 meters per minute, and the fibers were in the coagulation bath for at least 5 minutes. And fully drying the obtained fibers in the air, and collecting to obtain the polymer fibers of the bionic spider silk with the water collection characteristic. The diameter of the chain structure unit of the obtained fiber is 50 micrometers, the radial height of the protrusion structure unit is 80-150 micrometers, the axial length of the protrusion structure unit is 80-400 micrometers, and the length of the chain structure unit is 150-3200 micrometers.

Example 14

8g of polyvinyl alcohol (PVA 1799, Allantin, degree of polymerization 1700, degree of alcoholysis 99%), 0.7 g of butyronitrile spray-dried powder rubber (preparation method is the same as example 11, but butyronitrile spray-dried powder rubber sample with average particle size of 30 μm after volume sieving) were dispersed in 42 g of water, heated and stirred at 80 ℃ for 2 hours to obtain a uniform spinning dope. The spinning dope was extruded into a coagulation bath (aqueous sodium sulfate solution, 420g/L) by a peristaltic pump at room temperature to spin: the actual extrusion rate was 0.01 ml per minute, the spinneret size was 25G (round, 260 micron diameter), the take-up rate was 0.42 meters per minute, and the fibers were in the coagulation bath for at least 5 minutes. And fully drying the obtained fibers in the air, and collecting to obtain the polymer fibers of the bionic spider silk with the water collection characteristic. The diameter of a link structure unit of the obtained fiber is 28 micrometers, the radial height of a protrusion structure unit is 30-80 micrometers, the axial length of the protrusion structure unit is 30-200 micrometers, and the length of the link structure unit is 60-2500 micrometers.

Example 15

8g of polyvinyl alcohol (PVA 1799, Allantin, degree of polymerization 1700, degree of alcoholysis 99%) and 0.7 g of butyronitrile spray-dried powder rubber (same as in example 12) were dispersed in 42 g of water and heated and stirred at 85 ℃ for 2 hours to obtain a homogeneous dope. The spinning dope was extruded into a coagulation bath (aqueous sodium sulfate solution, 420g/L) by a peristaltic pump at room temperature to spin: the actual extrusion rate was 0.01 ml per minute, the spinneret size was 25G (round, 260 micron diameter), the take-up rate was 0.6 meter per minute, and the fibers were in the coagulation bath for at least 5 minutes. And fully drying the obtained fibers in the air, and collecting to obtain the polymer fibers of the bionic spider silk with the water collection characteristic. The diameter of a link structure unit of the obtained fiber is 22 micrometers, the radial height of a protrusion structure unit is 30-80 micrometers, the axial length of the protrusion structure unit is 30-200 micrometers, and the length of the link structure unit is 120-4000 micrometers.

Example 16

8g of polyvinyl alcohol (PVA 1799, avastin, degree of polymerization 1700, degree of alcoholysis 99%) and 0.7 g of carboxylated nitrile butadiene spray-dried powder rubber were dispersed in 42 g of water and heated and stirred at 90 ℃ for 2 hours to obtain a uniform spinning dope. The spinning dope was extruded into a coagulation bath (aqueous sodium sulfate solution, 420g/L) by a peristaltic pump at room temperature to spin: the actual extrusion rate was 0.06 ml per minute, the spinneret size was 25G (round, 260 micron diameter), the take-up rate was 0.42 meters per minute, and the fibers were in the coagulation bath for at least 5 minutes. And fully drying the obtained fibers in the air, and collecting to obtain the polymer fibers of the bionic spider silk with the water collection characteristic. The diameter of the chain structure unit of the obtained fiber is 24 micrometers, the radial height of the protrusion structure unit is 30-80 micrometers, the axial length of the protrusion structure unit is 30-200 micrometers, and the length of the chain structure unit is 160-3200 micrometers.

The preparation method of the carboxylated butyronitrile spray-dried powder rubber comprises the following steps: 1kg of carboxylated nitrile latex with a solid content of 45 percent, the carboxylated nitrile latex with the brand number XNBRL is placed in a container, 13.5g of isooctyl acrylate is dropwise added under stirring, the mixture is continuously stirred for one hour after the dropwise addition, then the mixture is irradiated by a cobalt source, the dosage is 2.5Mrad, the dosage rate is 50Gy/min, the irradiated latex is spray-dried by a spray dryer, the inlet temperature of the spray dryer is 140-160 ℃, the outlet temperature is 60-70 ℃, the dried carboxylated nitrile rubber powder is collected, and the screened carboxylated nitrile spray-dried powder rubber sample with the average particle size of 30 microns is obtained and used in the embodiment.

Example 17

10 g of polyacrylonitrile (purchased from Sigma-Aldrich Sigma Aldrich trade Co., Ltd., weight average molecular weight of 150000) and 1 g of carboxylated styrene-butadiene spray-dried powder rubber (same as in example 1) were dispersed in 40 g of N, N-Dimethylformamide (DMF), and stirred with heating at 50 ℃ for 2 hours to obtain a uniform dope. The spinning stock solution was extruded into a coagulation bath (a mixed solution of water and DMF in 100 parts by weight of water, DMF50 parts by weight) by a peristaltic pump at room temperature to spin: the actual extrusion rate was 0.01 ml per minute, the spinneret size was 25G (round, 260 micron diameter), the take-up rate was 0.42 meters per minute, and the fibers were in the coagulation bath for at least 5 minutes. And fully drying the obtained fibers in the air, and collecting to obtain the polymer fibers of the bionic spider silk with the water collection characteristic. The diameter of the chain structure unit of the obtained fiber is 35 micrometers, the radial height of the protruding structure unit is 40-100 micrometers, the axial length of the protruding structure unit is 50-200 micrometers, and the length of the chain structure unit is 90-3100 micrometers.

Example 18

10 g of polyparaphenylene terephthalamide (weight average molecular weight: 60000) and 1 g of carboxylated styrene-butadiene spray-dried powder rubber (same as in example 8) were dispersed in 40 g of 98% sulfuric acid, and heated and stirred at 80 ℃ for 2 hours to obtain a uniform spinning dope. Extruding the spinning solution into a coagulating bath (water) for spinning through a peristaltic pump at room temperature: the actual extrusion rate was 0.01 ml per minute, the spinneret size was 27G (round, 210 micron diameter), the take-up rate was 1 meter per minute, and the fibers were in the coagulation bath for at least 5 minutes. And fully drying the obtained fibers in the air, and collecting to obtain the polymer fibers of the bionic spider silk with the water collection characteristic. The diameter of a link structure unit of the obtained fiber is 25 micrometers, the radial height of a protrusion structure unit is 40-100 micrometers, the axial length of the protrusion structure unit is 50-200 micrometers, and the length of the link structure unit is 200-4500 micrometers.

Example 19

10 g of polyurethane (purchased from Shandongteng engineering plastics Co., Ltd.) and 1 g of spray-dried powder natural rubber were dispersed in 30g of N, N-Dimethylformamide (DMF), and heated and stirred at 80 ℃ for 2 hours to obtain a uniform spinning dope. The spinning stock solution was extruded into a coagulation bath (a mixed solution of water and DMF in 100 parts by weight of water, DMF40 parts by weight) by a peristaltic pump at room temperature to spin: the actual extrusion rate was 0.01 ml per minute, the spinneret size was 28G (round, 180 micron diameter), the take-up rate was 1 meter per minute, and the fibers were in the coagulation bath for at least 5 minutes. And fully drying the obtained fibers in the air, and collecting to obtain the polymer fibers of the bionic spider silk with the water collection characteristic. The diameter of a link structure unit of the obtained fiber is 27 micrometers, the radial height of a protrusion structure unit is 45-120 micrometers, the axial length of the protrusion structure unit is 50-220 micrometers, and the length of the link structure unit is 180-3600 micrometers.

The preparation method of the spray-dried natural rubber powder comprises the following steps: 1kg of natural rubber latex with a solid content of 60%, provided by Beijing latex factory, was placed in a container, 30g of trimethylolpropane triacrylate was added dropwise under stirring, after the addition was completed, stirring was continued for one hour, then irradiation was performed with a cobalt source at a dose of 15Mrad at a dose rate of 50Gy/min, the irradiated latex was spray-dried by a spray dryer at an inlet temperature of 140 ℃ to 160 ℃ and an outlet temperature of 60 ℃ to 70 ℃, and the dried natural rubber powder was collected and sieved to obtain a spray-dried natural rubber powder sample with an average particle size of 50 μm, which was used in this example.

Claims (48)

1. A polymer fiber of a bionic spider silk with water collection characteristics is characterized in that a monofilament of the polymer fiber has a microstructure of a spider silk-like structure with protruding structural units and linking structural units distributed at intervals, the radial height of each protruding structural unit is 10-300 microns, the axial length of each protruding structural unit is 10-1000 microns, the diameter range of each linking structural unit is 5-200 microns, and the length of each linking structural unit is 10-5000 microns;

the polymer fiber comprises the following components in parts by weight:

a. 100 parts by weight of a fiber matrix polymer;

b. 1-50 parts by weight of spray-dried powder rubber;

the average particle size of the spray-dried powder rubber is 10-200 microns.

2. A polymer fibre of biomimetic spider silk with water-collecting properties according to claim 1, characterized in that:

the radial height of the protrusion structural unit is 20-200 microns;

the axial length of the protrusion structural unit is 20-700 micrometers.

3. A polymer fibre of biomimetic spider silk with water-collecting properties according to claim 1, characterized in that:

the radial height of the protrusion structural unit is 30-150 micrometers;

the axial length of the protruding structure unit is 40-300 microns.

4. A polymer fibre of biomimetic spider silk with water-collecting properties according to claim 1, characterized in that:

the diameter range of the linking structure unit is 10-100 microns,

the length of the link structure unit is 50-3000 microns.

5. A polymer fibre of biomimetic spider silk with water-collecting properties according to claim 1, characterized in that:

the diameter range of the linking structure unit is 20-50 microns,

the length of the link structure unit is 100-1000 microns.

6. A polymer fibre of biomimetic spider silk with water-collecting properties according to claim 1, characterized in that:

based on 100 parts by weight of the fiber matrix polymer,

10-40 parts of spray-dried powder rubber.

7. A polymer fibre of biomimetic spider silk with water-collecting properties according to claim 1, characterized in that:

based on 100 parts by weight of the fiber matrix polymer,

the spray-dried powder rubber is 10-30 parts by weight.

8. A polymer fibre of biomimetic spider silk with water-collecting properties according to claim 1, characterized in that:

based on 100 parts by weight of the fiber matrix polymer,

the spray-dried powder rubber is 20-30 parts by weight.

9. A polymer fibre of biomimetic spider silk with water-collecting properties according to claim 1, characterized in that:

the fiber matrix polymer is at least one selected from polyacrylonitrile, polyurethane, polyvinyl alcohol, viscose fiber, nylon, cellulose sulfonate, cellulose acetate, polyvinyl chloride, poly-m-phthalic amide and poly-p-phenylene terephthamide.

10. A polymer fibre of biomimetic spider silk with water-collecting properties according to claim 9, characterized in that:

the polyisophthaloyl amide is selected from polyisophthaloyl metaphenylene diamine.

11. A polymer fibre of biomimetic spider silk with water-collecting properties according to claim 10, characterized in that:

the fiber matrix polymer is at least one selected from polyacrylonitrile, polyurethane, polyvinyl alcohol, viscose fiber, poly (m-phenylene isophthalamide), poly (p-phenylene terephthalamide) and polyvinyl chloride.

12. A polymer fibre of biomimetic spider silk having water-collecting properties according to claim 11, characterized in that:

the fiber matrix polymer is at least one of polyacrylonitrile, polyurethane and polyvinyl alcohol.

13. A polymer fibre of biomimetic spider silk with water-collecting properties according to claim 9, characterized in that:

the fiber matrix polymer is selected from polyvinyl alcohol; the polymerization degree of the polyvinyl alcohol is 400-2600, and the alcoholysis degree is 55-99%.

14. A polymer fibre of biomimetic spider silk having water-collecting properties according to claim 13, characterized in that:

the polymerization degree of the polyvinyl alcohol is 500-2000.

15. A polymer fibre of biomimetic spider silk having water-collecting properties according to claim 13, characterized in that:

the polymerization degree of the polyvinyl alcohol is 1000-1700.

16. A polymer fibre of biomimetic spider silk having water-collecting properties according to claim 13, characterized in that:

the alcoholysis degree is 88-99%.

17. A polymer fibre of biomimetic spider silk with water-collecting properties according to claim 1, characterized in that:

the average particle size of the spray-dried powder rubber is 10-100 microns.

18. A polymer fibre of biomimetic spider silk having water-collecting properties according to claim 17, characterized in that:

the average particle size of the spray-dried powder rubber is 20-50 microns.

19. A polymer fibre of biomimetic spider silk with water-collecting properties according to any of claims 1-18, prepared by a method comprising the steps of:

(1) dispersing the fiber matrix polymer and the spray-dried powder rubber into a solvent according to the dosage, heating and stirring until the fiber matrix polymer is dissolved in the solvent, and uniformly dispersing the powder rubber into the solution to obtain a spinning solution;

(2) preparing a coagulating bath;

(3) and extruding the spinning solution into a coagulating bath, coagulating, drying and collecting to obtain the polymer fiber of the bionic spider silk with the water collection characteristic.

20. The method of preparing a polymer fiber of biomimetic spider silk with water-collecting properties according to any of claims 1-19, characterized by comprising the steps of:

(1) dispersing the fiber matrix polymer and the spray-dried powder rubber into a solvent according to the dosage, heating and stirring until the fiber matrix polymer is dissolved in the solvent, and uniformly dispersing the powder rubber into the solution to obtain a spinning solution;

(2) preparing a coagulating bath;

(3) and extruding the spinning solution into a coagulating bath, coagulating, drying and collecting to obtain the fiber.

21. A method of preparing a polymer fibre of biomimetic spider silk with water-collecting properties according to claim 20, characterized in that:

in the step (1), the amount of the fiber matrix polymer is 5-50 parts by weight based on 100 parts by weight of the solvent.

22. A method of preparing a polymer fibre of biomimetic spider silk with water-collecting properties according to claim 20, characterized in that:

in the step (1), the amount of the fiber matrix polymer is 10-40 parts by weight based on 100 parts by weight of the solvent.

23. A method of preparing a polymer fibre of biomimetic spider silk with water-collecting properties according to claim 20, characterized in that:

in the step (1), the amount of the fiber matrix polymer is 10-25 parts by weight based on 100 parts by weight of the solvent.

24. A method of preparing a polymer fibre of biomimetic spider silk with water-collecting properties according to claim 20, characterized in that:

in the step (1), the solvent is at least one selected from 1, 4-dioxane, N-dimethylformamide, tetrahydrofuran, water and sulfuric acid.

25. A method of preparing a polymer fibre of biomimetic spider silk with water-collecting properties according to claim 24, characterized in that:

in the step (1), the solvent is at least one selected from the group consisting of N, N-dimethylformamide and 1, 4-dioxane.

26. A method of preparing a polymer fibre of biomimetic spider silk with water-collecting properties according to claim 20, characterized in that:

in the step (1), the heating temperature is 30-95 ℃.

27. A method of preparing a polymer fibre of biomimetic spider silk with water-collecting properties according to claim 20, characterized in that:

in the step (1), the heating temperature is 50-95 ℃.

28. A method of preparing a polymer fibre of biomimetic spider silk with water-collecting properties according to claim 20, characterized in that:

in the step (1), the heating temperature is 70-95 ℃.

29. A method of preparing a polymer fibre of biomimetic spider silk with water-collecting properties according to claim 20, characterized in that:

in the step (2), the coagulating bath is at least one or a mixed solvent selected from sodium sulfate aqueous solution, methanol, ethyl acetate, water, 1, 4-dioxane and N, N-dimethylformamide; the concentration of the sodium sulfate aqueous solution is 300-500 g/L.

30. A method of preparing a polymer fibre of biomimetic spider silk with water-collecting properties according to claim 29, characterized in that:

in the step (2), the coagulating bath is at least one selected from sodium sulfate aqueous solution, methanol, water, 1, 4-dioxane and N, N-dimethylformamide or a mixed solvent.

31. A method of preparing a polymer fibre of biomimetic spider silk with water-collecting properties according to claim 30, characterized in that:

the concentration of the sodium sulfate aqueous solution is 350-450 g/L.

32. A method of preparing a polymer fibre of biomimetic spider silk with water-collecting properties according to claim 20, characterized in that:

the fiber matrix polymer is polyvinyl alcohol, the solvent is 1, 4-dioxane, and the coagulating bath is at least one selected from methanol, ethyl acetate and water or a binary solution consisting of methanol and 1, 4-dioxane; in the binary solution composed of methanol and 1, 4-dioxane, the weight portion of the 1, 4-dioxane is 0.1-50 parts based on 100 parts of methanol.

33. A method of preparing a polymer fibre of biomimetic spider silk with water-collecting properties according to claim 32, characterized in that:

the coagulating bath is selected from a binary solution consisting of methanol and 1, 4-dioxane; in the binary solution composed of methanol and 1, 4-dioxane, the weight portion of the 1, 4-dioxane is 5-40 parts based on 100 parts of methanol.

34. A method of preparing a polymer fibre of biomimetic spider silk with water-collecting properties according to claim 32, characterized in that:

the coagulating bath is selected from a binary solution consisting of methanol and 1, 4-dioxane, wherein in the binary solution consisting of the methanol and the 1, 4-dioxane, the weight part of the 1, 4-dioxane is 10-30 parts by weight based on 100 parts by weight of the methanol.

35. A method of preparing a polymer fibre of biomimetic spider silk with water-collecting properties according to claim 20, characterized in that:

when the spinning solution is used for spinning, the spinneret orifices are square, circular, triangular or pentagonal.

36. A method of preparing a polymer fibre of biomimetic spider silk with water-collecting properties according to claim 35, characterized in that:

the spinneret orifices are selected from circular, square or triangular.

37. A method of preparing a polymer fibre of biomimetic spider silk with water-collecting properties according to claim 20, characterized in that:

when the spinning solution is used for spinning, the inner diameter of a spinneret orifice is 10-1000 microns.

38. A method of preparing a polymer fibre of biomimetic spider silk with water-collecting properties according to claim 37, characterized in that:

the inner diameter of the spinneret orifice is 50-500 microns.

39. A method of preparing a polymer fibre of biomimetic spider silk with water-collecting properties according to claim 37, characterized in that:

the inner diameter of the spinneret orifice is 50-300 microns.

40. A method of preparing a polymer fibre of biomimetic spider silk with water-collecting properties according to claim 20, characterized in that:

and when the spinning solution is used for spinning, the yarn collecting speed is 0.1-100 meters per minute.

41. A method of making a biomimetic spider silk polymer fiber with water-collecting properties according to claim 40, characterized in that:

the filament winding speed is 0.1-10 meters per minute.

42. A method of making a biomimetic spider silk polymer fiber with water-collecting properties according to claim 40, characterized in that:

the filament winding speed is 0.2-1 meter per minute.

43. A method of preparing a polymer fibre of biomimetic spider silk with water-collecting properties according to any of claims 20-42, characterized by further comprising the steps of:

and (4) soaking the fiber prepared in the step (3) in a crosslinking solution, washing with water, drying and collecting to obtain the fiber.

44. A method of making a biomimetic spider silk polymer fiber with water-collecting properties according to claim 43, characterized in that:

the fiber matrix polymer is polyvinyl alcohol; the cross-linking liquid is a solution of acids, aldehydes, sodium sulfate and water, or the cross-linking liquid is a solution of acids, aldehydes and water; the acid is inorganic acid; the aldehyde is at least one of formaldehyde and glutaraldehyde.

45. A method of making a biomimetic spider silk polymer fiber with water-collecting properties according to claim 44, characterized in that:

the acid is at least one of hydrochloric acid and sulfuric acid.

46. A method of making a biomimetic spider silk polymer fiber with water-collecting properties according to claim 45, characterized in that:

the acid is sulfuric acid.

47. A method of making a biomimetic spider silk polymer fiber with water-collecting properties according to claim 44, characterized in that:

the acid in the cross-linking liquid is selected from sulfuric acid, and the aldehyde is glutaraldehyde and formaldehyde; wherein:

the concentration of the sulfuric acid is 100-500 g/L;

the concentration of the glutaraldehyde is 1-80 grams per liter;

the concentration of the formaldehyde is 1-50 grams per liter;

the concentration of the sodium sulfate is 0-350 g/L.

48. A method of making a biomimetic spider silk polymer fiber with water-collecting properties according to claim 47, characterized in that:

the concentration of the sulfuric acid is 200-350 g per liter;

the concentration of the glutaraldehyde is 30-60 grams per liter;

the concentration of the formaldehyde is 20-35 grams per liter;

the concentration of the sodium sulfate is 50-200 grams per liter.

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