CN109208108B

CN109208108B - Spider silk-like polymer fiber based on silica porous microspheres and preparation method thereof

Info

Publication number: CN109208108B
Application number: CN201710528419.8A
Authority: CN
Inventors: 乔金樑; 姜超; 戚桂村; 张晓红; 宋志海; 赖金梅; 蔡传伦; 李秉海; 王湘; 蒋海斌; 张江茹; 茹越; 高建明; 张红彬; 韩朋
Original assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Current assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Priority date: 2017-07-01
Filing date: 2017-07-01
Publication date: 2020-06-09
Anticipated expiration: 2037-07-01
Also published as: CN109208108A

Abstract

The invention relates to a spider silk-like polymer fiber based on silica porous microspheres and a preparation method thereof, belonging to the technical field of chemical bionics. The spider silk-like polymer fiber comprises the following components in parts by weight: 100 parts of fiber matrix polymer; 1-45 parts of silicon dioxide porous microspheres. The monofilament of the polymer fiber has a spider silk-like microstructure with spindle knot structural units distributed at intervals, the radial height of the spindle knot structural units is 10-300 microns, the axial length of the spindle knot structural units is 10-1000 microns, and the distance between the spindle knot structural units is 10-5000 microns. The method of the invention does not need to greatly change the prior spinning process, does not need to change equipment, and has simple process and low cost. The spider silk-like polymer fiber obtained by the invention can realize the directional movement of water drops on the surface of the fiber, has a water collecting function and has better mechanical property.

Description

Spider silk-like polymer fiber based on silica porous microspheres and preparation method thereof

Technical Field

The invention relates to the technical field of chemical bionics, in particular to a spider silk-like polymer fiber based on silica porous microspheres and a preparation method thereof.

Background

Water resources are an important natural resource for the development of human society. The water on earth, although in huge quantities, is directly utilizable but poor for production and living, occupying about 0.26% of the total water volume of the sphere. Sustainable utilization of water resources is one of the most important problems in sustainable development and utilization of all natural resources. In the modern society, the shortage of fresh water resources is gradually appearing. Approximately 15 million of the world's 80 countries face a shortage of fresh water, with 3 million of the 26 countries living entirely in a water-deficient state. By 2025, it is expected that 30 billion people worldwide will run short of water, with over 40 countries and regions involved. The shortage of fresh water resources restricts the development of society and the problem of fresh water resources is urgently solved. The solution may exist in the air where 12.9 trillion tons of gaseous water accumulate, which may become an important "water source" for future human domestic water.

Spiders are one of the pioneers in nature who utilize air and water sources. When the spider web is placed in a humid environment, water vapor is condensed on the surface of the capture silk in the spider web to form small water drops; the curvature radius of the captured filament is periodically changed due to the periodic spindle knot structure in the fiber, Laplace pressure difference is generated, the stress of the water drops along the radial direction of the fiber is uneven, and the water drops are pushed to move directionally (towards the spindle knots). The directional movement of the water drops is beneficial to the small liquid drops to be quickly gathered to form large water drops, the transpiration is weakened, and the quick collection of moisture in the air is facilitated. The spider collects water in the air through the process to guarantee survival, and a new idea is provided for solving the freshwater crisis: the spider silk-like fiber with the spindle knot structure is developed, so that the rapid collection of water in the air is realized, the spider silk-like fiber has a wide application prospect in desert, island and other areas, and is expected to be used for dispersing water vapor in airport and other special places.

There are three main methods for preparing spider silk-like fibers of similar structure in the prior art.

The first is the dipping method: the method is adopted for a water-collecting polymer silk imitating a spider silk structure disclosed in Chinese patent with publication No. CN102776785A (application No. 201110223679.7). after existing fibers are immersed in a high molecular solution, the high molecular solution forms a string of liquid drops on the fiber surface due to Rayleigh instability in the drying process, and the liquid drops are hung on the fiber surface, and are dried and solidified to obtain spindle knots which are axially arranged, so that the fibers similar to the spider silk structure are obtained. Based on 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 microscopic protrusions or micropores, thereby improving the water collection efficiency of the fiber. The method belongs to post-processing of the existing fibers.

Secondly, the electrostatic spinning method has higher requirements on equipment: chinese patent with publication number CN103334244A (application number 201710227113.0) 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.

Thirdly, a wet spinning method is utilized: the invention provides a bionic spider silk polymer fiber with water collection characteristic and a preparation method thereof, which is provided by Chinese patent with application number 201710166815.0. But the mechanical properties of the fibres are affected to some extent due to the weaker interaction of the additives with the fibre matrix.

Disclosure of Invention

In order to solve the problems in the prior art, the invention provides a spider silk-like polymer fiber based on silica porous microspheres. In particular to a spider silk-like polymer fiber based on silica porous microspheres and a preparation method thereof. According to the method, the porous silica microspheres are added in the spinning process, the spindle knot structure can be obtained in the fiber preparation process, the microfiber network can be formed in the porous structure in the fiber forming process, the problem that the interaction force between the additive and a fiber matrix is weak is solved to a certain extent, and the influence of the additive on the mechanical properties of the fiber is reduced.

One of the objectives of the present application is to propose a spider silk-like polymer fiber based on silica porous microspheres. The monofilament of the polymer fiber has a spider-like silk microstructure with spindle knot structural units distributed at intervals, can realize the directional movement of water drops on the surface of the fiber, and has a water collecting function. The interval distribution refers to that the two adjacent spindle knot structural units distributed on the monofilament are connected by the monofilament.

The spider silk-like polymer fiber based on the silica porous microspheres comprises the following components in parts by weight:

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

b. 1-45 parts of silicon dioxide porous microspheres, preferably 3-40 parts, more preferably 5-30 parts, and more preferably 5-25 parts.

The component a fiber matrix polymer is used as a fiber matrix, and the component b silicon dioxide porous microspheres are used as additives to form a spindle knot structure.

The radial height of the spindle section structural unit is 10-300 micrometers, preferably 20-200 micrometers, and more preferably 30-150 micrometers; the axial length of the spindle section structural unit is 10-1000 microns, preferably 20-700 microns, and more preferably 100-300 microns; the interval of the spindle node structural units is 10-5000 micrometers, preferably 50-3000 micrometers, and more preferably 100-1000 micrometers.

The average particle size of the silicon dioxide porous microspheres is 500 nanometers to 200 micrometers, preferably 10 micrometers to 150 micrometers, and more preferably 20 micrometers to 100 micrometers.

The porosity of the porous silica microspheres is 10-80%, preferably 20-60%, and more preferably 20-50%.

The aperture of the silicon dioxide porous microsphere is 0.1-200 nanometers, preferably 0.5-150 nanometers, and more preferably 1-50 nanometers.

The silica porous microspheres are selected from various commercially available silica porous microspheres meeting the above parameters, and can also be prepared by the methods in the prior art.

The diameter of the fiber main body is 5-250 micrometers, preferably 10-150 micrometers, and more preferably 20-50 micrometers.

The fiber matrix polymer is selected from various fiber forming polymers in the prior art, such as 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 paraphenylene diamine; 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 400-4000, preferably 500-3000, and more preferably 1000-2500; the alcoholysis degree is 55-99%, preferably 88-99%.

Another purpose of the application is to provide a preparation method of the spider silk-like polymer fiber based on the silica porous microspheres. The method adopts a wet spinning process to spin a polymer and a silicon dioxide porous microsphere additive together, the silicon dioxide porous microspheres are dispersed in a polymer solution, and the polymer solution is diffused into the silicon dioxide porous microspheres; in the subsequent stretching process of forming fibers by spinning stock solution microflow through a coagulating bath, as the solvent is continuously separated out and radially stretched, the volume of the fiber main body is greatly shrunk, and the silica microsphere volume is not influenced, so that the fibers are microscopically protruded at the existence position of the microspheres to form a spindle structure; the polymer solution entering the inside of the porous silica microspheres is solidified to form a microfiber network, and the microspheres are bound inside the fibers, so that the problem that the interaction force between the silica microspheres and the fiber matrix is weak is effectively solved, and the influence of the additive on the mechanical properties of the fibers is reduced. The method has simple process, does not need to greatly improve the prior process, and is easy for industrialized production.

The preparation method of the spider silk-like polymer fiber based on the silica porous microspheres comprises the following steps:

(1) dispersing the fiber matrix polymer and the silica porous microsphere additive into a solvent according to the using amount, heating and stirring until the fiber matrix polymer is dissolved in the solvent, and uniformly dispersing the silica porous microspheres 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 polymers and solvents;

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

(4) and stretching the nascent fiber to obtain the bionic fiber with the spindle knot structure distributed at intervals.

Preferably after the above steps, comprising: (5) putting the bionic fiber in a cross-linking solution for a certain time; and (4) washing, drying and collecting to obtain the fiber. The crosslinking process can change the water resistance of the fiber, but does not affect the basic physical structure of the fiber, namely the spindle knot structure distributed at intervals, so the crosslinking 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 silica porous microspheres is 1-45 parts by weight, preferably 3-40 parts by weight, more preferably 5-30 parts by weight, and more preferably 5-25 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 sodium sulfate aqueous solution and methanol; more preferably an aqueous solution of sodium sulphate. If a 1, 4-dioxane solution of polyvinyl alcohol is selected as a spinning stock solution, at least one of methanol and ethyl acetate or a binary solution consisting of methanol and 1, 4-dioxane can be selected as a coagulating bath, wherein the 1, 4-dioxane content 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; preferably methanol or a binary solution consisting of methanol and 1, 4-dioxane; more preferably methanol.

When the spinning solution is used for spinning, the spinneret orifices can be commonly used in the spinning process, and the inner diameter of each spinneret orifice can be 10-1000 micrometers, preferably 50-500 micrometers, and more preferably 50-300 micrometers; the filament receiving rate can be 0.01-100 meters per minute, preferably 0.05-10 meters per minute, and more preferably 0.1-1 meter per minute.

In the step (4), the drawing temperature may be a drawing temperature commonly used for the fiber matrix polymer. If polyvinyl alcohol is adopted as the fiber matrix polymer, the stretching temperature is 100-220 ℃, preferably 120-200 ℃, and more preferably 150-180 ℃.

In the step (5), 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 (or formaldehyde), sodium sulfate and water, wherein the concentration of the sulfuric acid can be 100-500 grams per liter, and is 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.

According to the spider silk-like polymer fiber based on the silica porous microspheres and the preparation method thereof, water vapor is condensed on the surface of the fiber of the obtained artificial fiber under the condition of high humidity, and then small liquid drops are combined to a spindle knot structure part and are accelerated to converge to form large water drops, so that the collection is facilitated.

The invention has the advantages that:

(1) the invention utilizes the silicon dioxide porous microspheres as the additive, solves the problem that the interface interaction between the additive and the matrix material is weak: the silicon dioxide porous microspheres are firmly bound in the fibers through the reticular microfibers formed in the solidification process, so that the influence of the additive on the mechanical properties of the fibers is weakened;

(2) the method has simple process, can be realized by adopting the traditional spinning equipment without additionally adding additional equipment, and is suitable for continuous large-scale preparation;

(3) the spider silk-like fiber with the spindle knot structures distributed at intervals is low in cost and good in stability;

(4) the spider silk-like fiber with the spindle knot structures distributed at intervals can be used for collecting water drops in air in islands, coastal deserts, foggy mountainous areas and other areas and dispersing dense fog around airport and other special places.

Drawings

FIG. 1 is a photomicrograph of a spider silk-like polymer fiber based on silica porous microspheres made in example 1.

Fig. 1 shows that the fiber has a spindle knot structure distributed at intervals, the deeper part of the spindle knot is the silica microsphere, the light transmittance is weaker, and the formation of the spindle knot is the influence of the microsphere.

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 equipment was a model SPLab01 peristaltic pump manufactured by baodinchen pump company ltd, and the thermal stretching equipment was an INSTRON 3366 universal tester.

(2) Experimental data determination apparatus: in the experiment, a microscope photograph was taken with a NIKON ECLIPSE lC100N POL type microscope, and the directional movement of the water droplets on the fiber surface was observed with a contact angle measuring apparatus model SCA20 from Dataphysics, Germany.

The Tensile properties of the fibers were measured by the monofilament method in accordance with ASTM D3379-1975 Standard Test method for Tensile Strength and Young's Module for High-Module Single-fiber materials.

Example 1

7 g of polyvinyl alcohol (PVA 1799, avastin with a polymerization degree of 1700 and an alcoholysis degree of 99%) and 1.05 g of porous silica microspheres 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. Extruding the spinning solution into methanol for spinning through a peristaltic pump at room temperature: actual extrusion rate 0.02 ml per minute, spinneret size 25G (260 micron diameter), take-up rate 0.1 meter per minute, fiber in coagulation bath for at least 5 minutes; fully drying and collecting to obtain nascent fiber; hot-stretching at 180 ℃ to 8 times of the original length to obtain spider silk-like fibers, and testing, wherein the test result is shown in figure 1. The diameter of the main body of the obtained fiber is 27 micrometers, the radial height of spindle joints is 40-70 micrometers, the axial length is 50-400 micrometers, and the distance between the spindle joints is 70-2000 micrometers. The fiber is tested for mechanical property, and the tensile breaking strength is 342 +/-22 MPa.

The preparation method of the silica porous microsphere comprises the following steps: 1kg of silicone rubber latex (model 302, new material science and technology ltd, beijing porl) with a solid content of 28% is placed in a container, 15g of isooctyl acrylate is dropwise added under stirring, stirring is continued for one hour after the dropwise addition is completed, then a cobalt source is used for irradiation, the dose is 2.5Mrad, the dose 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 silicone rubber powder is collected, and after being calcined at 600 ℃ for 6 hours (sequentially in an oxygen-free environment for 3 hours and an oxygen environment for 3 hours), the silicon dioxide porous microspheres with the particle size of 20-50 micrometers, the pore size of 20-100 nanometers and the porosity of 20-60% are obtained by screening.

Comparative example 1

7 g 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 fully drying the obtained fibers in the air, collecting to obtain the spider silk-like polymer fibers, and testing the mechanical properties of the spider silk-like polymer fibers, wherein the tensile breaking strength of the spider silk-like polymer fibers is 94 +/-12 MPa.

The preparation method of the carboxylic styrene-butadiene spray-dried powder rubber comprises the following steps: 1kg of carboxylated styrene-butadiene latex with 50 percent of solid content, Yanshan petrochemical production, the brand 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 the sample of the carboxylated styrene-butadiene rubber powder with the average particle size of 30 microns is obtained by screening and is used in the comparative example.

Comparative example 2

7 g 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 comparative 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, 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, collecting to obtain the spider silk-like polymer fibers, and testing the mechanical properties of the spider silk-like polymer fibers to obtain the spider silk-like polymer fibers with the tensile breaking strength of 36 +/-6 MPa.

Comparative example 3

7 g of polyvinyl alcohol (PVA 1799, Allantin with a polymerization degree of 1700 and an alcoholysis degree of 99%) and 1.4 g of glass microspheres (obtained from Wallace chemical engineering Co., Ltd., Suzhou, non-porous solid glass microspheres, 15-30 microns) 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, collecting to obtain the spider silk-like polymer fibers, and testing the mechanical properties of the spider silk-like polymer fibers to obtain the spider silk-like polymer fibers with tensile breaking strength of 54 +/-10 MPa.

Example 2

7 g of polyvinyl alcohol (PVA 1799, Allantin, degree of polymerization 1700, degree of alcoholysis 99%) and 2.1 g of porous silica microspheres (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 uniform spinning dope. Extruding the spinning solution into methanol for spinning through a peristaltic pump at room temperature: actual extrusion rate 0.02 ml per minute, spinneret size 25G (260 micron diameter), take-up rate 0.1 meter per minute, fiber in coagulation bath for at least 5 minutes; fully drying and collecting to obtain nascent fiber; and hot-drawing at 180 ℃ to 8 times of the original length to obtain the spider silk-like fiber. The diameter of the main body of the obtained fiber is 27 micrometers, the radial height of spindle joints is 40-75 micrometers, the axial length is 50-400 micrometers, and the distance between the spindle joints is 60-1000 micrometers. The fiber is tested for mechanical property, and the tensile breaking strength is 154 +/-15 MPa.

And observing by a contact angle measuring instrument, wherein small liquid drops are randomly formed on the surface of the fiber under the condition of high humidity, and then the liquid drops directionally move from the periphery of the spindle structure to the central bulge to form large liquid drops.

Example 3

6 g of polyvinyl alcohol (PVA 2499, Allantin, degree of polymerization 2400, degree of alcoholysis 99%), 0.9 g of porous silica microspheres (same as in example 1) were dispersed in 44 g of 1, 4-Dioxane (DMSO), and heated and stirred at 80 ℃ for 3 hours to obtain a uniform spinning dope. Extruding the spinning solution into methanol for spinning through a peristaltic pump at room temperature: actual extrusion rate 0.02 ml per minute, spinneret size 25G (260 micron diameter), take-up rate 0.1 meter per minute, fiber in coagulation bath for at least 5 minutes; fully drying and collecting to obtain nascent fiber; and hot-drawing at 180 ℃ to 6 times of the original length to obtain the spider silk-like fiber. The diameter of the main body of the obtained fiber is 25 micrometers, the radial height of spindle joints is 35-80 micrometers, the axial length is 50-450 micrometers, and the interval between the spindle joints is 70-2000 micrometers.

Example 4

6 g of polyvinyl alcohol (PVA 2499, Allantin, degree of polymerization 2400, degree of alcoholysis 99%), 0.9 g of porous silica microspheres (same as in example 1) were dispersed in 44 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: actual extrusion rate 0.02 ml per minute, spinneret size 25G (260 micron diameter), take-up rate 0.4 meter per minute, fiber in coagulation bath for at least 5 minutes; fully drying and collecting to obtain nascent fiber; and hot-drawing at 180 ℃ to 12 times of the original length to obtain the spider silk-like fiber. The diameter of the main body of the obtained fiber is 15 micrometers, the radial height of spindle joints is 40-70 micrometers, the axial length is 50-350 micrometers, and the interval between the spindle joints is 90-2000 micrometers.

Example 5

7 g of polyvinyl alcohol (PVA 1799, Allantin, degree of polymerization 1700, degree of alcoholysis 99%) and 1.05 g of porous silica microspheres (same as in example 1) were dispersed in 43 g of 1, 4-Dioxane (DMSO), and heated and stirred at 70 ℃ for 4 hours to obtain a uniform spinning dope. Extruding the spinning solution into methanol for spinning through a peristaltic pump at room temperature: actual extrusion rate 0.02 ml per minute, spinneret size 25G (260 micron diameter), take-up rate 0.1 meter per minute, fiber in coagulation bath for at least 5 minutes; fully drying and collecting to obtain nascent fiber; after hot-drawing at 180 ℃ to 8 times the original length, the resultant was placed in a crosslinking solution (11.48 g of 98% concentrated sulfuric acid, 3.5 g of sodium sulfate, 4.16 g of 50% glutaraldehyde aqueous solution, and 50 ml of aqueous solution obtained by constant volume) for 10 minutes. And (5) washing, drying and collecting to obtain the spider silk-like fiber. The diameter of the main body of the obtained fiber is 27 micrometers, the radial height of spindle joints is 40-70 micrometers, the axial length is 50-400 micrometers, and the distance between the spindle joints is 70-2000 micrometers.

Observed by a contact angle measuring instrument, the surface of the fiber randomly forms small drops under the condition of high humidity, and then the drops directionally move from the periphery of the spindle structure to the central bulge to form large drops.

Example 6

8 g of polyvinyl alcohol (PVA 1788, avastin with the polymerization degree of 1700 and the alcoholysis degree of 88%), 0.8 g of silica porous microspheres (50 microns, purchased from microspheres-nanospheres, the average pore diameter of 10nm and the porosity of 20-40%) are dispersed in 42 g of 1, 4-Dioxane (DMSO), and the mixture is heated and stirred for 3 hours at the temperature of 75 ℃ to obtain uniform spinning stock solution. Extruding the spinning solution into methanol for spinning through a peristaltic pump at room temperature: actual extrusion rate 0.02 ml per minute, spinneret size 25G (260 micron diameter), take-up rate 0.1 meter per minute, fiber in coagulation bath for at least 5 minutes; fully drying and collecting to obtain nascent fiber; and hot-drawing at 180 ℃ to 8 times of the original length to obtain the spider silk-like fiber. The diameter of a main body of the obtained fiber is 30 micrometers, the radial height of spindle joints is 60-80 micrometers, the axial length is 80-400 micrometers, and the distance between the spindle joints is 110-3300 micrometers.

Example 7

8 g of polyvinyl alcohol (PVA 2499, avastin with a polymerization degree of 2400 and an alcoholysis degree of 99%) and 0.8 g of silica porous microspheres (75 micrometers, purchased from microspheres-nanospheres, with an average pore diameter of 10nm and a porosity of 20-40%) are dispersed in 42 g of 1, 4-Dioxane (DMSO), and heated and stirred at 75 ℃ for 3 hours to obtain a uniform spinning stock solution. Extruding the spinning solution into methanol for spinning through a peristaltic pump at room temperature: the actual extrusion rate was 0.04 ml per minute, the spinneret size was 22G (diameter 410 microns), the take-up rate was 0.05 meters per minute, and the fibers were in the coagulation bath for at least 5 minutes; fully drying and collecting to obtain nascent fiber; and hot-drawing at 180 ℃ to 8 times of the original length to obtain the spider silk-like fiber. The diameter of the main body of the obtained fiber is 50 micrometers, the radial height of spindle joints is 80-100 micrometers, the axial length is 120-500 micrometers, and the distance between the spindle joints is 130-3000 micrometers.

Example 8

Dispersing 7 g of polyvinyl alcohol (PVA 1799, avastin with the polymerization degree of 1700 and the alcoholysis degree of 99%) and 1.05 g of silica porous microspheres (50 micrometers, purchased from microspheres-nanospheres, the average pore diameter of 10nm and the porosity of 20-40%) in 43 g of water, heating and stirring at 75 ℃ for 3 hours to obtain a uniform spinning solution. The spinning stock solution was extruded into an aqueous sodium sulfate solution (420 g per liter) by a peristaltic pump for spinning at room temperature: actual extrusion rate 0.02 ml per minute, spinneret size 25G (260 micron diameter), take-up rate 0.1 meter per minute, fiber in coagulation bath for at least 5 minutes; fully drying and collecting to obtain nascent fiber; and (2) performing hot drawing at 180 ℃ to 10 times of the original length, then placing the fiber in a crosslinking solution (11.48 g of 98% concentrated sulfuric acid, 3.5 g of sodium sulfate, 4.16 g of 50% glutaraldehyde aqueous solution, and fixing the volume to obtain 50 ml of aqueous solution) for 10 minutes, and washing, drying and collecting the fiber to obtain the spider silk-like fiber. The diameter of the main body of the obtained fiber is 28 micrometers, the radial height of spindle joints is 60-90 micrometers, the axial length is 120-460 micrometers, and the distance between the spindle joints is 130-3700 micrometers.

Example 9

10 g of polyacrylonitrile (purchased from Sigma-Aldrich Sigma Aldrich trade Co., Ltd., weight average molecular weight of 150000) and 1.5 g of porous silica microspheres (same as in example 1) were dispersed in 40 g of N, N-Dimethylformamide (DMF), and heated and stirred at 60 ℃ for 3 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: actual extrusion rate 0.02 ml per minute, spinneret size 25G (260 micron diameter), take-up rate 0.1 meter per minute, fiber in coagulation bath for at least 5 minutes; fully drying and collecting to obtain nascent fiber; and hot-drawing the fiber to 8 times of the original length at 95 ℃ to obtain the spider silk-like fiber. The diameter of the main body of the obtained fiber is 25 micrometers, the radial height of spindle joints is 40-80 micrometers, the axial length is 80-380 micrometers, and the interval between the spindle joints is 90-2600 micrometers.

Example 10

7 g of polyvinyl alcohol (PVA 1799, Allantin, degree of polymerization 1700, degree of alcoholysis 99%) and 0.35 g of porous silica microspheres (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 uniform spinning dope. Extruding the spinning solution into methanol for spinning through a peristaltic pump at room temperature: actual extrusion rate 0.02 ml per minute, spinneret size 25G (260 micron diameter), take-up rate 0.1 meter per minute, fiber in coagulation bath for at least 5 minutes; fully drying and collecting to obtain nascent fiber; and hot-drawing at 180 ℃ to 10 times of the original length to obtain the spider silk-like fiber. The diameter of the main body of the obtained fiber is 24 micrometers, the radial height of spindle sections is 37-70 micrometers, the axial length is 50-350 micrometers, and the space between the spindle sections is 200-4000 micrometers.

Example 11

7 g of polyvinyl alcohol (PVA 1799, Allantin, degree of polymerization 1700, degree of alcoholysis 99%) and 2.8 g of porous silica microspheres (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 uniform spinning dope. Extruding the spinning solution into methanol for spinning through a peristaltic pump at room temperature: actual extrusion rate 0.02 ml per minute, spinneret size 25G (260 micron diameter), take-up rate 0.1 meter per minute, fiber in coagulation bath for at least 5 minutes; fully drying and collecting to obtain nascent fiber; and hot-drawing at 180 ℃ to 6 times of the original length to obtain the spider silk-like fiber. The diameter of the main body of the obtained fiber is 24 micrometers, the radial height of spindle joints is 45-90 micrometers, the axial length is 70-550 micrometers, and the space between the spindle joints is 70-800 micrometers.

Example 12

10 g of polyurethane (purchased from Shandongteng engineering plastics Co., Ltd.) and 1.5 g of porous silica microspheres (same as in example 1) were dispersed in 30 g 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 25G (260 micron diameter), the take-up rate was 0.4 meter per minute, and the fibers were in the coagulation bath for at least 5 minutes. Fully drying and collecting to obtain nascent fiber; stretching to 10 times of the original length to obtain the spider silk-like polymer fiber. The diameter of the main body of the obtained fiber is 26 micrometers, the radial height of spindle joints is 35-77 micrometers, the axial length is 60-400 micrometers, and the interval between the spindle joints is 220-2600 micrometers.

Claims

1. A spider silk-like polymer fiber based on silica porous microspheres is characterized in that the monofilament of the polymer fiber has a spider silk-like microstructure with spindle knot structural units distributed at intervals, and the radial height of the spindle knot structural units is 10-300 microns; the axial length of the spindle section structural unit is 10-1000 microns; the distance between the spindle section structural units is 10-5000 micrometers;

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

a. 100 parts of fiber matrix polymer;

b. 1-45 parts by weight of silica porous microspheres;

the aperture of the silicon dioxide porous microsphere is 0.1-200 nanometers;

the porosity of the silica porous microspheres is 10-80%;

the average particle size of the silicon dioxide porous microspheres is 0.5-200 microns.

2. A silica porous microsphere based spider silk-like polymer fiber according to claim 1, characterized in that:

the radial height of the spindle section structural unit is 20-200 microns; the axial length of the spindle section structure unit is 20-700 micrometers; the interval between the spindle section structural units is 50-3000 microns; and/or the presence of a gas in the gas,

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

a. 100 parts of fiber matrix polymer;

b. 3-40 parts of silicon dioxide porous microspheres; and/or the presence of a gas in the gas,

the aperture of the silicon dioxide porous microsphere is 0.5-150 nanometers; and/or the presence of a gas in the gas,

the porosity of the silica porous microspheres is 20-60%; and/or the presence of a gas in the gas,

the average particle size of the silicon dioxide porous microspheres is 10-150 micrometers; and/or the presence of a gas in the gas,

the diameter of the polymer fiber main body is 5-250 micrometers.

3. A silica porous microsphere based spider silk-like polymer fiber according to claim 2, characterized in that:

the radial height of the spindle section structural unit is 30-150 micrometers; the axial length of the spindle section structural unit is 100-300 microns; the distance between the spindle section structural units is 100-1000 microns; and/or the presence of a gas in the gas,

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

a. 100 parts of fiber matrix polymer;

b. 5-30 parts by weight of porous silica microspheres; and/or the presence of a gas in the gas,

the aperture of the silicon dioxide porous microsphere is 1-50 nanometers; and/or the presence of a gas in the gas,

the porosity of the silica porous microspheres is 20-50%; and/or the presence of a gas in the gas,

the average particle size of the silicon dioxide porous microspheres is 20-100 micrometers; and/or the presence of a gas in the gas,

the diameter of the polymer fiber main body is 10-150 micrometers.

4. A silica porous microsphere based spider silk-like polymer fiber according to claim 3, characterized in that:

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

a. 100 parts of fiber matrix polymer;

b. 5-25 parts by weight of porous silica microspheres; and/or the presence of a gas in the gas,

the diameter of the polymer fiber main body is 20-50 micrometers.

5. A silica porous microsphere based spider silk-like polymer fiber 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, polyisophthaloyl amide, polyisophthaloyl metaphenylene diamine and poly terephthaloyl p-phenylenediamine.

6. A silica porous microsphere based spider silk-like polymer fiber according to claim 1, characterized in that:

the fiber matrix polymer is selected from polyvinyl alcohol; the polymerization degree of the polyvinyl alcohol is 400-4000; the alcoholysis degree is 55-99%.

7. A silica porous microsphere based spider silk-like polymer fiber according to claim 6, characterized in that:

the polymerization degree of the polyvinyl alcohol is 500-3000; the alcoholysis degree is 88-99%.

8. A silica porous microsphere based spider silk-like polymer fiber according to claim 7, characterized in that:

the polymerization degree of the polyvinyl alcohol is 1000-2500.

9. A spider silk-like polymer fiber based on silica porous microspheres according to any one of claims 1 to 8, prepared by a method comprising the steps of:

(1) dispersing the fiber matrix polymer and the silica porous microsphere additive into a solvent according to the using amount, heating and stirring until the fiber matrix polymer is dissolved in the solvent, and uniformly dispersing the silica porous microspheres in the solution to obtain a uniform spinning solution;

(2) preparing corresponding coagulating baths;

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

(4) and stretching the nascent fiber to obtain the spider silk-like polymer fiber.

10. A method for preparing a spider silk-like polymer fiber based on silica porous microspheres according to any one of claims 1-9, characterized by comprising the steps of:

(1) dispersing the fiber matrix polymer and the silica porous microspheres in a solvent according to the dosage, heating and stirring until the fiber matrix polymer is dissolved in the solvent, and uniformly dispersing the silica porous microspheres in the solution to obtain a spinning solution;

(2) preparing corresponding coagulating baths;

(4) by drawing the nascent fiber, spider silk-like polymer fiber with spindle knot structure distributed at intervals is obtained.

11. The method of preparing a spider silk-like polymer fiber based on silica porous microspheres according to claim 10, 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; and/or the presence of a gas in the gas,

in the step (1), the solvent is at least one selected from 1, 4-dioxane, N-dimethylformamide, tetrahydrofuran, water and sulfuric acid; and/or the presence of a gas in the gas,

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

12. The method of preparing a spider silk-like polymer fiber based on silica porous microspheres according to claim 11, 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; and/or the presence of a gas in the gas,

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

13. The method of preparing a spider silk-like polymer fiber based on silica porous microspheres according to claim 12, 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; and/or the presence of a gas in the gas,

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

14. The method of preparing a spider silk-like polymer fiber based on silica porous microspheres according to claim 10, 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.

15. The method of preparing a spider silk-like polymer fiber based on silica porous microspheres according to claim 14, characterized in that:

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

16. The method of preparing a spider silk-like polymer fiber based on silica porous microspheres according to claim 10, 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 binary solutions consisting of methanol, ethyl acetate, 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.

17. The method of preparing a spider silk-like polymer fiber based on silica porous microspheres according to claim 16, characterized in that:

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.

18. The method of preparing a spider silk-like polymer fiber based on silica porous microspheres according to claim 17, characterized in that:

in the binary solution composed of methanol and 1, 4-dioxane, the weight portion of the 1, 4-dioxane is 10-30 parts based on 100 parts of methanol.

19. The method of preparing a spider silk-like polymer fiber based on silica porous microspheres according to claim 10, characterized in that:

when the spinning solution is used for spinning, the inner diameter of a spinneret orifice is 10-1000 microns; and/or the presence of a gas in the gas,

and when the spinning solution is used for spinning, the yarn collecting speed is 0.01-100 meters per minute.

20. The method of preparing a spider silk-like polymer fiber based on silica porous microspheres according to claim 19, characterized in that:

when the spinning solution is used for spinning, the inner diameter of the spinneret orifice is 50-500 microns; and/or the presence of a gas in the gas,

and when the spinning solution is used for spinning, the yarn collecting speed is 0.05-10 meters per minute.

21. The method of preparing a spider silk-like polymer fiber based on silica porous microspheres according to claim 20, characterized in that:

when the spinning solution is used for spinning, the inner diameter of the spinneret orifice is 50-300 microns; and/or the presence of a gas in the gas,

when the spinning solution is used for spinning, the yarn collecting speed is 0.1-1 meter per minute

22. The method of preparing a spider silk-like polymer fiber based on silica porous microspheres according to claim 10, characterized in that:

in the step (4), the fiber matrix polymer is polyvinyl alcohol, and the stretching temperature is 100-220 ℃.

23. The method of preparing a spider silk-like polymer fiber based on silica porous microspheres of claim 22, characterized in that:

in the step (4), the stretching temperature is 120-200 ℃.

24. The method of preparing a spider silk-like polymer fiber based on silica porous microspheres according to claim 23, characterized in that:

in the step (4), the stretching temperature is 150-180 ℃.

25. The method for preparing a spider silk-like polymer fiber based on silica porous microspheres according to any one of claims 10 to 24, characterized by further comprising the steps of:

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

26. The method of preparing a spider silk-like polymer fiber based on silica porous microspheres of claim 25, characterized in that:

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

27. The method of preparing a spider silk-like polymer fiber based on silica porous microspheres of claim 26, characterized in that:

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

28. The method of preparing a spider silk-like polymer fiber based on silica porous microspheres of claim 27, characterized in that:

the acid in the crosslinking liquid is selected from sulfuric acid, and the aldehyde is selected from 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.

29. The method of preparing a spider silk-like polymer fiber based on silica porous microspheres of claim 28, characterized in that:

the concentration of the sulfuric acid is 200-350 g per liter; and/or the presence of a gas in the gas,

the concentration of the glutaraldehyde is 30-60 grams per liter; and/or the presence of a gas in the gas,

the concentration of the formaldehyde is 20-35 grams per liter; and/or the presence of a gas in the gas,

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