CN109208108A - A kind of class spider silk polymer fiber and preparation method thereof based on porous silica microballoon - Google Patents
A kind of class spider silk polymer fiber and preparation method thereof based on porous silica microballoon Download PDFInfo
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- CN109208108A CN109208108A CN201710528419.8A CN201710528419A CN109208108A CN 109208108 A CN109208108 A CN 109208108A CN 201710528419 A CN201710528419 A CN 201710528419A CN 109208108 A CN109208108 A CN 109208108A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/50—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyalcohols, polyacetals or polyketals
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/20—Formation of filaments, threads, or the like with varying denier along their length
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
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Abstract
The present invention relates to a kind of class spider silk polymer fibers and preparation method thereof based on porous silica microballoon of chemobionics technical field.The polymer fiber of the class spider silk includes following components based on parts by weight: 100 parts of fibrous matrix polymer；1~45 part of porous silica microballoon.Its monofilament of the polymer fiber has the microstructure of the class spider silk of spindle section structure unit interval distribution, the spindle section structure unit radial height is 10~300 microns, the axial length of the spindle section structure unit is 10~1000 microns, and the spacing of the spindle section structure unit is 10~5000 microns.Method of the invention is not necessarily to substantially change existing spinning technique and equipment is without change, simple process and low cost.Water droplet may be implemented in the displacement of the fiber surface in the polymer fiber for the class spider silk that the present invention obtains, and has water collecting function, and better mechanical property.
Description
Technical field
The present invention relates to chemobionics technical fields, furtherly, are related to a kind of based on porous silica microballoon
Class spider silk polymer fiber and preparation method thereof.
Background technique
Water resource is the important natural resources of human social development.Tellurian water can direct quilt although enormous amount
People's production and life utilize pitiably little, about only account for the 0.26% of earth total Water.The sustainable use of water resource is
A most important problem in all natural resources Sustainable Development and Utilizations.Today's society, freshwater resources situation in short supply is
Gradually show.About 1,500,000,000 populations of more than 80 countries in the whole world face fresh water deficiency, wherein 26 300,000,000 national populations are lived completely
In exsiccosis.It expects 2025, the whole world will have 3,000,000,000 population water shortages, and the countries and regions being related to are up to more than 40.Fresh water
Shortage of resources oneself through restrict society development, solve the problems, such as that freshwater resources are extremely urgent.Solution may be present in air
In -- here collection be knotted 12.9 trillion tons of vaporous waters -- air is likely to become important " water source " of following mankind's domestic water.
Spider is one of the pioneer that air water source is utilized in nature.When cobweb is placed in moist environment, steam exists
Capture silk table face therein condenses, forms small water droplet；And periodic spindle nodule present in the fiber is configured to capture silk
Radius of curvature generating period variation, generate Laplce's pressure difference, cause water droplet along fiber radial direction unbalance stress, push away
It is mobile that orientation (being directed toward spindle section) occurs for dynamic water droplet.This displacement of water droplet is conducive to droplet quick collecting and forms flood
Pearl weakens transpiration, conducive to the quick collection of moisture in air.Spider collects moisture guarantee in air by the above process
The mode of existence solves fresh water crisis for us and provides new thinking: developing the imitative spider silk fiber with spindle section structure,
The quick collection for realizing moisture in air, has broad application prospects in areas such as desert, islands, is also expected to be used for airport etc.
Code in Hazardous Special Locations steam disperses.
There are mainly three types of the methods for preparing the imitative spider silk fiber of similar structures in the prior art.
First is that infusion process: the Chinese patent of Publication No. CN102776785A (application No. is 201110223679.7) discloses
The polymer filament of catchmenting of imitative spider silk structure a kind of use this kind of method, after existing fiber is immersed Polymer Solution, take
Out in drying process, Polymer Solution hangs on fiber surface since Rayleigh unstability forms a string of drops in fiber surface,
The spindle section of axial alignment is obtained through dry solidification, obtains the fiber of similar spider silk structure.Publication No. CN102587139A
The Chinese patent of (application No. is 201210004686.2), for patent basis, is furthermore achieved with above-mentioned and prepares resulting fiber
Uniform, controllable, surface have more microcosmic protrusion or micropore, improve the collection of fiber the height of the protrusion section on surface from small to large
Water efficiency.This method belongs to the post-processing to existing fiber.
Second is that using electrospinning process, the high requirements on the equipment: Publication No. CN103334244A (application No. is
201710227113.0) Chinese patent discloses a kind of self-assembly preparation method thereof of electrospinning bead string fiber, and the invention is using quiet
Electrospinning forms micron order bead string structure in the surface self-organization of staple fibre, obtains imitative spider silk fiber.But Static Spinning
Costly, and the type of polymer for being able to use electrostatic spinning is less for the equipment of silk.
Third is that utilizing wet spinning process: application No. is one kind that 201710166815.0 Chinese patent provides to have collection
The polymer fiber and preparation method thereof of the bionical spider silk of water characteristic, which uses solution-polymerized SBR technology, in spinning solution
Middle introducing micron order spray-dried powders rubber, fibre solidification form periodic spindle section in the process, and one-step method is imitated
Spider silk fiber.But since the interaction of additive and fibrous matrix is weaker, the mechanicalness of fiber is affected to a certain extent
Energy.
Summary of the invention
In order to solve the above-mentioned problems in the prior art, the present invention proposes a kind of based on porous silica microballoon
Class spider silk polymer fiber.Relate in particular to a kind of class spider silk polymer fiber based on porous silica microballoon and
Preparation method.The present processes by being added porous silica microballoon during the spinning process, in fiber manufacturing process
It can be obtained spindle section structure, and microfiber network can be formed inside porous structure in fiber forming process, in certain journey
It solves the problems, such as that interaction force is weaker between additive and fibrous matrix on degree, reduces additive to the shadow of fiber mechanical performance
It rings, this method is not necessarily to substantially change existing spinning technique and equipment is without change, from technique, more simply, at
This is also lower.
The application first purpose is to propose a kind of class spider silk polymer fiber based on porous silica microballoon.It is described
Its monofilament of polymer fiber has the microstructure of the class spider silk of spindle section structure unit interval distribution, and water droplet may be implemented and exist
The displacement of the fiber surface has water collecting function.Described herein is spaced apart, and refers to adjacent two be distributed on monofilament
It is connected between a spindle section structure unit for monofilament.
A kind of class spider silk polymer fiber based on porous silica microballoon, comprising in parts by weight with
Lower component:
A. 100 parts by weight of fibrous matrix polymer；
B. 1~45 parts by weight of porous silica microballoon, preferably 3~40 parts, more preferably 5~30 parts by weight, more more
Preferably 5~25 parts by weight.
The component a fibrous matrix polymer is as fibrous matrix, and the component b porous silica microballoon is as addition
Agent forms spindle section structure.
The spindle section structure unit radial height is 10~300 microns, preferably 20~200 microns, more preferably 30
~150 microns；The axial length of the spindle section structure unit be 10~1000 microns, preferably 20~700 microns, more preferably
It is 100~300 microns；The spacing of the spindle section structure unit is 10~5000 microns, preferably 50~3000 microns, more excellent
It is selected as 100~1000 microns.
The average grain diameter of the porous silica microballoon is 500 nanometers~200 microns, and preferably 10 microns~150 is micro-
Rice, more preferably 20~100 microns.
The porosity of the porous silica microballoon be 10~80%, preferably 20~60%, more preferably 20~
50%.
The aperture of the porous silica microballoon be 0.1~200 nanometer, preferably 0.5~150 nanometer, more preferably 1~
50 nanometers.
The porous silica microballoon, selected from the commercially available various porous silica microballoons for meeting the above parameter,
It can be made by oneself by the method for the prior art.
The fibrous body diameter is 5~250 microns, preferably 10~150 microns, more preferably 20~50 microns.
The fibrous matrix polymer is selected from the existing various polymer that can form fiber in the prior art, such as poly-
Acrylonitrile, polyurethanes, polyvinyl alcohol, viscose fiber, nylon, cellulose sulfonate, cellulose acetate, polychlorostyrene second
At least one of alkene, poly- isophtalamide, poly, poly(p-phenylene terephthalamide)；It is preferred that
For polyacrylonitrile, polyurethanes, polyvinyl alcohol, viscose fiber, poly, poly- paraphenylene terephthalamide couple
At least one of phenylenediamine, polyvinyl chloride, more preferably polyacrylonitrile, polyurethanes, at least one in polyvinyl alcohol
Kind, yet more preferably polyvinyl alcohol.
When the fibrous matrix polymeric oxidizer polyvinyl alcohol is as fibrous body, the degree of polymerization of the polyvinyl alcohol is
400~4000, preferably 500~3000, more preferably 1000~2500；Alcoholysis degree be 55%~99%, preferably 88%~
99%.
The application second purpose is to provide a kind of system of class spider silk polymer fiber based on porous silica microballoon
Preparation Method.This method is by using wet spinning technology, by polymer and the common spinning of porous silica microballoon additive, two
Silica porous microsphere is scattered in polymer solution, and polymer solution diffuses into inside porous silica microballoon；It is spinning
Silk stock solution miniflow forms fiber by coagulating bath, during posterior drawing, since solvent is constantly precipitated and radial drawing, fiber master
The generation of body volume is significantly shunk, and Silica microspheres product is unaffected, therefore at microballoon presence, fiber can occur micro-
Protrusion is seen, fusellal fabric is formed；Into the polymer solution inside porous silica microballoon through supersolidification, fento net is formed
Microballoon is bundled in fibrous inside by network, and it is weaker to efficiently solve interaction force between silicon dioxide microsphere and fibrous matrix
Problem reduces influence of the additive to fiber mechanical performance.This method simple process, without largely being changed to prior art
Into easy to industrialized production.
A kind of preparation method of the class spider silk polymer fiber based on porous silica microballoon, including it is following
Step:
(1) solvent is dispersed by the fibrous matrix polymer and porous silica microballoon additive by the dosage
In, heating, stirring are dissolved in solvent to fibrous matrix polymer, and porous silica microballoon is evenly dispersed in the solution, obtains
Uniform spinning solution；Wherein, the heating temperature be 30~95 degrees Celsius, preferably 50~95 degrees Celsius, more preferably 70~
95 degrees Celsius；
(2) corresponding used polymer and solvent, prepare corresponding coagulating bath；
(3) spinning solution is squeezed into coagulating bath by wet-spinning frame or peristaltic pump etc., through supersolidification, drying, is collected
Obtain as-spun fibre；
(4) by stretching as-spun fibre, the bionic fiber with the spindle section structure being spaced apart is obtained.
It is preferred that after the above step, comprising: (5) above-mentioned gained bionic fiber is placed in certain time in crosslinked fluid；Water
It washes, dry, collect, obtain fiber.Cross-linking process can change the water resistance of the fiber, but not influence the base of fiber
This physical structure, the spindle section structure being spaced apart, therefore, cross-linking process are selection process, and the reality for not influencing fiber is answered
With.
Specifically,
It is in terms of 100 parts by weight of solvent, the dosage of the fibrous matrix polymer is 5~50 weight in the step (1)
Part, preferably 10~40 parts, more preferably 10~25 parts；The dosage of the porous silica microballoon is poly- with the fibrous matrix
The dosage for closing object is 100 parts by weight meters, and the dosage of the silicon dioxide microsphere is 1~45 parts by weight, preferably 3~40 parts, more
Preferably 5~30 parts by weight, yet more preferably 5~25 parts by weight.
In the step (1), the solvent is polymer used common wet spinning solvent accordingly, specifically may be used
Selected from least one of Isosorbide-5-Nitrae-dioxane, n,N-Dimethylformamide, tetrahydrofuran, water, sulfuric acid, more preferably N, N- bis-
At least one of methylformamide, Isosorbide-5-Nitrae-dioxane.
In the step (2), coagulating bath is that common wet spinning coagulating bath is equal accordingly for fibrous matrix polymer used
It can.Mixed process can use existing any liquid liquid mixing apparatus, such as mechanical stirring, ultrasonic disperse.The coagulating bath
Specifically can be selected from aqueous sodium persulfate solution, methanol, ethyl acetate, water, Isosorbide-5-Nitrae-dioxane, in n,N-Dimethylformamide at least
A kind of or mixed solvent, preferably sulfuric acid sodium water solution, methanol, water, Isosorbide-5-Nitrae-dioxane, in n,N-Dimethylformamide at least
A kind of or mixed solvent；The concentration of the aqueous sodium persulfate solution is 300~500g/L, preferably 350~450g/L.
If the aqueous solution of polyvinyl alcohol is selected to be used as spinning solution, optional aqueous sodium persulfate solution, methanol, in ethyl acetate
At least one as coagulating bath, wherein the concentration of the aqueous sodium persulfate solution is 300~500g/L, preferably 350~450g/
L；At least one of preferably sulfuric acid sodium water solution, methanol；More preferably aqueous sodium persulfate solution.If selecting the 1 of polyvinyl alcohol,
At least one of methanol, ethyl acetate or selection methanol and Isosorbide-5-Nitrae-can be selected as spinning solution in 4- dioxane solution
The binary solution of dioxane composition is as coagulating bath, wherein the content of the Isosorbide-5-Nitrae-dioxane is with methanol weight for 100 weights
Part meter is measured, Isosorbide-5-Nitrae-dioxane parts by weight are 0.1~50 part, preferably 5~40 parts, more preferably 10~30 parts；It is preferred that
For methanol or methanol and Isosorbide-5-Nitrae-dioxane composition binary solution；More preferably methanol.
When carrying out spinning using the spinning solution, spinneret orifice is usually used spinneret orifice in spinning process, described
Spinneret orifice internal diameter can be 10~1000 microns, preferably 50~500 microns, more preferably 50~300 microns；Receiving silk rate can be
0.01~100 meter per minute, and preferably 0.05~10 meter per minute, and more preferable 0.1~1 meter per minute.
In the step (4), draft temperature is fibrous matrix polymer used common draft temperature accordingly.If
Using polyvinyl alcohol as fibrous matrix polymer, draft temperature is 100~220 degrees Celsius, preferably 120~200 degrees Celsius, more
Preferably 150~180 degrees Celsius.
In the step (5), the crosslinked fluid is fibrous matrix polymer used common wet spinning crosslinking accordingly
Liquid.
According to polyvinyl alcohol as fibrous matrix polymer, crosslinked fluid can by acids and aldehydes and/or sodium sulphate, with
The solution of water is constituted, that is to say, that crosslinked fluid is the aqueous solution of acids and aldehydes, may be optionally added sodium sulphate.Acids can be common
Inorganic acid, preferably at least one of hydrochloric acid, sulfuric acid, more preferably sulfuric acid；Aldehydes be preferably formaldehyde, in glutaraldehyde extremely
Few one kind.Specifically, the aqueous solution of crosslinked fluid preferably sulfuric acid, glutaraldehyde (or formaldehyde) and sodium sulphate and water, wherein sulfuric acid is dense
Degree can be 100~500 gram per liters, preferably 200~350 gram per liters；The concentration of glutaraldehyde can be 1~80 gram per liter, preferably
30~60 gram per liters；The concentration of formaldehyde can be 1~50 gram per liter, preferably 20~35 gram per liters；The concentration of sodium sulphate can for 0~
350 gram per liters, preferably 50~200 gram per liters.
A kind of class spider silk polymer fiber and preparation method thereof based on porous silica microballoon proposed by the present invention,
In high humility, steam coagulates in fiber surface obtained staple fibre, subsequent droplet is to spindle section structure portion
Division simultaneously, accelerate collect to form big water droplet, be conducive to collect.
Advantages of the present invention:
(1) present invention solves the boundary of additive Yu basis material using porous silica microballoon as additive
The weaker problem of face interaction: porous silica microballoon is firmly bundled in by the netted fento formed in process of setting
Fibrous inside reduces influence of the additive to fiber mechanical performance；
(2) present invention process is simple, can be realized using traditional spinning equipment, increases optional equipment without additional, fits
Preferably continuously prepared on a large scale；
(3) fiber for the class spider silk with the spindle section structure being spaced apart that the present invention obtains is low in cost, tool
There is good stability；
(4) fiber of the class spider silk with the spindle section structure being spaced apart that the present invention obtains can be used for island,
The thick fog that the area such as desert and foggy mountain area is collected around water droplet and the Code in Hazardous Special Locations such as airport in air that borders on the sea disperses.
Detailed description of the invention
Fig. 1 is that the microscope of the class spider silk polymer fiber based on porous silica microballoon made from embodiment 1 shines
Piece.
It is shown in Fig. 1, fiber has the spindle section structure being spaced apart, and color deeper portion is titanium dioxide in spindle section
Silicon microballoon, translucency is weaker, and the formation of spindle section is the influence of microballoon.
Specific embodiment
Below with reference to embodiment, the present invention is further illustrated.But the present invention is not restricted by the embodiments.In embodiment
The following instrument and equipment of experimental data and measuring method measurement:
(1) experiment basis equipment: extrusion equipment is the SPLab01 type peristaltic pump of Baoding Shen Chenbeng industry Co., Ltd production,
Hot-stretch equipment is 3366 universal testing machine of INSTRON.
(2) instrument of experimental data measurement: microscope photo is shown by NIKON ECLIPSE lC100N POL type in experiment
Micro mirror obtain, water droplet fiber surface displacement process by German dataphysics company SCA20 type Contact-angle measurement
Instrument observation.
The tensile property test of fiber uses monofilament method, according to ASTM D3379-1975 " Standard Test Method
for Tensile Strength and Young’s Modulus for High-Modulus Single-Filament
Materials " it executes.
Embodiment 1
By 7 grams of polyvinyl alcohol (PVA 1799, Aladdin, the degree of polymerization 1700, alcoholysis degree 99%), 1.05 grams of titanium dioxides
Silicon porous microsphere is scattered in 43 grams of Isosorbide-5-Nitrae-dioxane (DMSO), at 80 degrees celsius heating stirring 2 hours, is obtained uniform
Spinning solution.At room temperature, above-mentioned spinning solution is squeezed by peristaltic pump and carries out spinning in methanol: is practical to squeeze out speed
Per minute, spinning head model 25G (diameter is 260 microns), receive silk rate is 0.1 meter per minute to 0.02 milliliter of rate, and fiber exists
At least 5 minutes in coagulating bath；By sufficiently dry, collection, as-spun fibre is obtained；Hot-drawn is carried out under 180 degrees Celsius extends to original
There are 8 times of length, obtains class spider silk fiber, tested, test result is shown in Fig. 1.The main diameter of gained fiber is 27 micro-
Rice, spindle section radial height are 40~70 microns, and axial length is 50~400 microns, and spindle internode spacing is 70~2000 micro-
Rice.Measuring mechanical property is carried out to above-mentioned fiber, tensile break strength is 342 ± 22MPa.
The preparation method of above-mentioned porous silica microballoon: by silicone rubber latex (Beijing bohr new material of 1kg solid content 28%
Science and Technology Ltd., model 302) it is placed in a container, Isooctyl acrylate monomer 15g is added dropwise under stiring, continues after being added dropwise to complete
Stirring one hour, is irradiated with cobalt source, dosage 2.5Mrad, dosage rate 50Gy/min later, and the latex after radiation passes through spraying
Drier spray drying, the inlet temperature of spray dryer are 140~160 degrees Celsius, and outlet temperature is 60~70 degrees Celsius, are received
Silicone rubber powder after collection is dry, by 600 degrees Celsius calcine 6 hours (be followed successively by oxygen-free environment 3 hours, oxygen atmosphere 3 it is small
When) after, by screening, partial size is obtained at 20~50 microns, aperture is 20~100 nanometers, the dioxy that porosity is 20~60%
SiClx porous microsphere is used for the present embodiment.
Comparative example 1
By 7 grams of polyvinyl alcohol (PVA 1799, Aladdin, the degree of polymerization 1700, alcoholysis degree 99%), 0.7 gram of carboxyl fourth
Benzene spray-dried powders rubber is scattered in 43 grams of Isosorbide-5-Nitrae-dioxane (DMSO), heating stirring 2 hours at 80 DEG C, is obtained
Uniform spinning solution.At room temperature, above-mentioned spinning solution is squeezed into coagulating bath by peristaltic pump (methanol and DMSO's is mixed
Close solution, based on 100 parts by weight of methanol, DMSO20 parts by weight) in carry out spinning: 0.01 milliliter of practical rate of extrusion per minute,
Spinning head model 25G (round, diameter be 260 microns), receive silk rate be 0.42 meter per minute, fiber in coagulating bath at least
5 minutes.Obtained fiber after sufficiently drying, is collected in air, obtains the polymer fiber of class spider silk, carries out machine
Tool performance test, tensile break strength are 94 ± 12MPa.
The preparation method of above-mentioned Carboxy spray-dried powders rubber: by the carboxylic styrene butadiene latex of 1kg solid content 50%, the Yanshan Mountain
Petrochemical iy produced, trade mark XSBRL-54B1 are placed in a container, and Isooctyl acrylate monomer 15g is added dropwise under stiring, is added dropwise to complete subsequent
Continuous stirring one hour, is irradiated with cobalt source, dosage 2.5Mrad, dosage rate 50Gy/min, the latex after radiation passes through spray later
The spray drying of mist drier, the inlet temperature of spray dryer are 140 DEG C~160 DEG C, and outlet temperature is 60 DEG C~70 DEG C, are collected
Carboxylic styrene-butadiene rubber powder after drying obtains the carboxylic styrene-butadiene rubber powder sample that average grain diameter is 30 microns by screening
For this comparative example.
Comparative example 2
By 7 grams of polyvinyl alcohol (PVA 1799, Aladdin, the degree of polymerization 1700, alcoholysis degree 99%), 2.1 grams of carboxyl fourths
Benzene spray-dried powders rubber (with comparative example 1) is scattered in 43 grams of Isosorbide-5-Nitrae-dioxane (DMSO), the heating stirring at 80 DEG C
2 hours, obtain uniform spinning solution.At room temperature, above-mentioned spinning solution is squeezed into coagulating bath (methanol by peristaltic pump
With the mixed solution of DMSO, based on 100 parts by weight of methanol, 20 parts by weight of DMSO) in carry out spinning: practical rate of extrusion 0.01
Milliliter is per minute, and spinning head model 25G (round, diameter is 260 microns), receiving silk rate is 0.42 meter per minute, and fiber exists
At least 5 minutes in coagulating bath.Obtained fiber after sufficiently drying, is collected in air, obtains the polymerization of class spider silk
Fibres, carry out measuring mechanical property, and tensile break strength is 36 ± 6MPa.
Comparative example 3
7 grams of polyvinyl alcohol (PVA 1799, Aladdin, the degree of polymerization 1700, alcoholysis degree 99%), 1.4 grams of glass are micro-
Ball (is purchased from Suzhou Hua Nixi Chemical Co., Ltd., non-porous solid glass microballoon, 15~30 microns), is scattered in 43 grams of Isosorbide-5-Nitrae-dioxies
In six rings (DMSO), heating stirring 2 hours at 80 DEG C obtain uniform spinning solution.At room temperature, by above-mentioned spinning
Stoste by peristaltic pump squeeze into coagulating bath (mixed solution of methanol and DMSO, based on 100 parts by weight of methanol, 20 weight of DMSO
Part) in carry out spinning: 0.01 milliliter of practical rate of extrusion per minute, spinning head model 25G (round, diameter is 260 microns),
Receiving silk rate is 0.42 meter per minute, and fiber is at least 5 minutes in coagulating bath.Obtained fiber is in air by sufficiently dry
It after dry, collect, obtains the polymer fiber of class spider silk, carry out measuring mechanical property, tensile break strength is 54 ±
10MPa。
Embodiment 2
By 7 grams of polyvinyl alcohol (PVA 1799, Aladdin, the degree of polymerization 1700, alcoholysis degree 99%), 2.1 grams of titanium dioxides
Silicon porous microsphere (with embodiment 1) is scattered in 43 grams of Isosorbide-5-Nitrae-dioxane (DMSO), and heating stirring 2 is small at 80 degrees celsius
When, obtain uniform spinning solution.At room temperature, above-mentioned spinning solution is squeezed into methanol by peristaltic pump and is spun
Silk: per minute, spinning head model 25G (diameter is 260 microns), receive silk rate is 0.1 meter to 0.02 milliliter of practical rate of extrusion
Per minute, fiber is at least 5 minutes in coagulating bath；By sufficiently dry, collection, as-spun fibre is obtained；Under 180 degrees Celsius into
Row hot-drawn extends to 8 times of original length, obtains class spider silk fiber.The main diameter of gained fiber is 27 microns, spindle pitch diameter
It is 40~75 microns to height, axial length is 50~400 microns, and spindle internode spacing is 60~1000 microns.To above-mentioned fibre
Dimension carries out measuring mechanical property, and tensile break strength is 154 ± 15MPa.
Contact angle measurement observation, the fiber is in high humility, fiber surface formation droplet random first, with
Drop is to displacement at central protuberance, forming big drop around fusellal fabric afterwards.
Embodiment 3
By 6 grams of polyvinyl alcohol (PVA 2499, Aladdin, the degree of polymerization 2400, alcoholysis degree 99%), 0.9 gram of titanium dioxide
Silicon porous microsphere (with embodiment 1) is scattered in 44 grams of Isosorbide-5-Nitrae-dioxane (DMSO), and heating stirring 3 is small at 80 degrees celsius
When, obtain uniform spinning solution.At room temperature, above-mentioned spinning solution is squeezed into methanol by peristaltic pump and is spun
Silk: per minute, spinning head model 25G (diameter is 260 microns), receive silk rate is 0.1 meter to 0.02 milliliter of practical rate of extrusion
Per minute, fiber is at least 5 minutes in coagulating bath；By sufficiently dry, collection, as-spun fibre is obtained；Under 180 degrees Celsius into
Row hot-drawn extends to 6 times of original length, obtains class spider silk fiber.The main diameter of gained fiber is 25 microns, spindle pitch diameter
It is 35~80 microns to height, axial length is 50~450 microns, and spindle internode spacing is 70~2000 microns.
Embodiment 4
By 6 grams of polyvinyl alcohol (PVA 2499, Aladdin, the degree of polymerization 2400, alcoholysis degree 99%), 0.9 gram of titanium dioxide
Silicon porous microsphere (with embodiment 1) is scattered in 44 grams of Isosorbide-5-Nitrae-dioxane (DMSO), and heating stirring 2 is small at 80 degrees celsius
When, obtain uniform spinning solution.At room temperature, by above-mentioned spinning solution by peristaltic pump squeeze into coagulating bath (methanol and
The mixed solution of DMSO, based on 100 parts by weight of methanol, 20 parts by weight of DMSO) in carry out spinning: practical 0.02 milli of rate of extrusion
Liter Per Minute, spinning head model 25G (diameter is 260 microns), receiving silk rate is 0.4 meter per minute, and fiber is in coagulating bath
At least 5 minutes；By sufficiently dry, collection, as-spun fibre is obtained；Hot-drawn is carried out under 180 degrees Celsius extends to original length
12 times, obtain class spider silk fiber.The main diameter of gained fiber is 15 microns, and spindle section radial height is 40~70 microns,
Axial length is 50~350 microns, and spindle internode spacing is 90~2000 microns.
Embodiment 5
By 7 grams of polyvinyl alcohol (PVA 1799, Aladdin, the degree of polymerization 1700, alcoholysis degree 99%), 1.05 grams of titanium dioxides
Silicon porous microsphere (with embodiment 1) is scattered in 43 grams of Isosorbide-5-Nitrae-dioxane (DMSO), small in 70 degrees Celsius of lower heating stirrings 4
When, obtain uniform spinning solution.At room temperature, above-mentioned spinning solution is squeezed into methanol by peristaltic pump and is spun
Silk: per minute, spinning head model 25G (diameter is 260 microns), receive silk rate is 0.1 meter to 0.02 milliliter of practical rate of extrusion
Per minute, fiber is at least 5 minutes in coagulating bath；By sufficiently dry, collection, as-spun fibre is obtained；Under 180 degrees Celsius into
After row hot-drawn extends to 8 times of original length, it is placed in crosslinked fluid (11.48 gram of 98% concentrated sulfuric acid, 3.5 grams of sodium sulphate, 4.16 gram 50%
Glutaraldehyde water solution, 50 milliliters of aqueous solutions that constant volume obtains) in 10 minutes.Washing, dry, collection, obtain class spider silk fiber.Institute
The main diameter for obtaining fiber is 27 microns, and spindle section radial height is 40~70 microns, and axial length is 50~400 microns, is spun
Spacing is 70~2000 microns between club.
It is observed through contact angle measurement, the fiber is in high humility, fiber surface formation droplet random first,
Subsequent drop is to displacement at central protuberance, forming big drop around fusellal fabric.
Embodiment 6
By 8 grams of polyvinyl alcohol (PVA 1788, Aladdin, the degree of polymerization 1700, alcoholysis degree 88%), 0.8 gram of titanium dioxide
Silicon porous microsphere (50 microns, be purchased from microspheres-nanospheres, average pore size 10nm, porosity be 20~
40%), be scattered in 42 grams of Isosorbide-5-Nitrae-dioxane (DMSO), 75 degrees Celsius lower heating stirring 3 hours, obtain uniform spinning
Stoste.At room temperature, above-mentioned spinning solution is squeezed by peristaltic pump and carries out spinning in methanol: practical rate of extrusion 0.02
Per minute, spinning head model 25G (diameter is 260 microns), per minute for 0.1 meter, fiber is in coagulating bath for receipts silk rate for milliliter
In at least 5 minutes；By sufficiently dry, collection, as-spun fibre is obtained；Hot-drawn is carried out under 180 degrees Celsius extends to original length
8 times after, obtain class spider silk fiber.The main diameter of gained fiber is 30 microns, and spindle section radial height is 60~80 micro-
Rice, axial length are 80~400 microns, and spindle internode spacing is 110~3300 microns.
Embodiment 7
By 8 grams of polyvinyl alcohol (PVA 2499, Aladdin, the degree of polymerization 2400, alcoholysis degree 99%), 0.8 gram of titanium dioxide
Silicon porous microsphere (75 microns, be purchased from microspheres-nanospheres, average pore size 10nm, porosity be 20~
40%), be scattered in 42 grams of Isosorbide-5-Nitrae-dioxane (DMSO), 75 degrees Celsius lower heating stirring 3 hours, obtain uniform spinning
Stoste.At room temperature, above-mentioned spinning solution is squeezed by peristaltic pump and carries out spinning in methanol: practical rate of extrusion 0.04
Per minute, spinning head model 22G (diameter is 410 microns), per minute for 0.05 meter, fiber is in coagulating bath for receipts silk rate for milliliter
In at least 5 minutes；By sufficiently dry, collection, as-spun fibre is obtained；Hot-drawn is carried out under 180 degrees Celsius extends to original length
8 times after, obtain class spider silk fiber.The main diameter of gained fiber is 50 microns, and spindle section radial height is 80~100 micro-
Rice, axial length are 120~500 microns, and spindle internode spacing is 130~3000 microns.
Embodiment 8
By 7 grams of polyvinyl alcohol (PVA 1799, Aladdin, the degree of polymerization 1700, alcoholysis degree 99%), 1.05 grams of titanium dioxides
Silicon porous microsphere (50 microns, be purchased from microspheres-nanospheres, average pore size 10nm, porosity be 20~
40%), be scattered in 43 grams of water, 75 degrees Celsius lower heating stirring 3 hours, obtain uniform spinning solution.In room temperature condition
Under, above-mentioned spinning solution is squeezed by peristaltic pump and carries out spinning: practical rate of extrusion in aqueous sodium persulfate solution (420 gram per liters)
0.02 milliliter per minute, and spinning head model 25G (diameter is 260 microns), receiving silk rate is 0.1 meter per minute, and fiber is solidifying
Gu at least 5 minutes in bath；By sufficiently dry, collection, as-spun fibre is obtained；Progress hot-drawn extends to original under 180 degrees Celsius
After 10 times of length, be placed in crosslinked fluid (11.48 gram of 98% concentrated sulfuric acid, 3.5 grams of sodium sulphate, 4.16 gram of 50% glutaraldehyde water solution,
50 milliliters of aqueous solutions that constant volume obtains) in 10 minutes, washing, it is dry, collect, obtain class spider silk fiber.The main body of gained fiber
Diameter is 28 microns, and spindle section radial height is 60~90 microns, and axial length is 120~460 microns, and spindle internode spacing is
130~3700 microns.
Embodiment 9
10 grams of polyacrylonitrile (are purchased from Sigma-Aldrich Sigma-Aldrich (Shanghai) trade Co., Ltd, weight is equal
Molecular weight be 150000), 1.5 grams of porous silica microballoons (with embodiment 1), be scattered in 40 grams of n,N-Dimethylformamide
(DMF) in, heating stirring 3 hours, obtain uniform spinning solution at 60 c.At room temperature, by above-mentioned spinning
Stoste is squeezed into coagulating bath (mixed solution of water and DMF, based on 100 parts by weight of water, DMF50 parts by weight) by peristaltic pump and is carried out
Spinning: per minute, spinning head model 25G (diameter is 260 microns), receive silk rate is 0.1 to 0.02 milliliter of practical rate of extrusion
Per minute, fiber is at least 5 minutes in coagulating bath for rice；By sufficiently dry, collection, as-spun fibre is obtained；In 95 DEG C waters
8 times that hot-drawn extends to original length are carried out, class spider silk fiber is obtained.The main diameter of gained fiber is 25 microns, spindle section
Radial height is 40~80 microns, and axial length is 80~380 microns, and spindle internode spacing is 90~2600 microns.
Embodiment 10
By 7 grams of polyvinyl alcohol (PVA 1799, Aladdin, the degree of polymerization 1700, alcoholysis degree 99%), 0.35 gram of titanium dioxide
Silicon porous microsphere (with embodiment 1) is scattered in 43 grams of Isosorbide-5-Nitrae-dioxane (DMSO), and heating stirring 2 is small at 80 degrees celsius
When, obtain uniform spinning solution.At room temperature, above-mentioned spinning solution is squeezed into methanol by peristaltic pump and is spun
Silk: per minute, spinning head model 25G (diameter is 260 microns), receive silk rate is 0.1 meter to 0.02 milliliter of practical rate of extrusion
Per minute, fiber is at least 5 minutes in coagulating bath；By sufficiently dry, collection, as-spun fibre is obtained；Under 180 degrees Celsius into
Row hot-drawn extends to 10 times of original length, obtains class spider silk fiber.The main diameter of gained fiber is 24 microns, spindle pitch diameter
It is 37~70 microns to height, axial length is 50~350 microns, and spindle internode spacing is 200~4000 microns.
Embodiment 11
By 7 grams of polyvinyl alcohol (PVA 1799, Aladdin, the degree of polymerization 1700, alcoholysis degree 99%), 2.8 grams of titanium dioxides
Silicon porous microsphere (with embodiment 1) is scattered in 43 grams of Isosorbide-5-Nitrae-dioxane (DMSO), and heating stirring 2 is small at 80 degrees celsius
When, obtain uniform spinning solution.At room temperature, above-mentioned spinning solution is squeezed into methanol by peristaltic pump and is spun
Silk: per minute, spinning head model 25G (diameter is 260 microns), receive silk rate is 0.1 meter to 0.02 milliliter of practical rate of extrusion
Per minute, fiber is at least 5 minutes in coagulating bath；By sufficiently dry, collection, as-spun fibre is obtained；Under 180 degrees Celsius into
Row hot-drawn extends to 6 times of original length, obtains class spider silk fiber.The main diameter of gained fiber is 24 microns, spindle pitch diameter
It is 45~90 microns to height, axial length is 70~550 microns, and spindle internode spacing is 70~800 microns.
Embodiment 12
10 grams of polyurethanes (being purchased from ShanDong DongChen Engineering Plastic Co., Ltd.), 1.5 grams of porous silicas are micro-
Ball (with embodiment 1) is scattered in 30 grams of n,N-Dimethylformamide (DMF), heating stirring 2 hours at 80 DEG C, is obtained equal
Even spinning solution.At room temperature, above-mentioned spinning solution is squeezed into coagulating bath by peristaltic pump (mixing of water and DMF is molten
Liquid, based on 100 parts by weight of water, DMF40 parts by weight) in carry out spinning: 0.01 milliliter of practical rate of extrusion per minute, spinneret head dummy
Number be 25G (diameter is 260 microns), receive silk rate be 0.4 meter per minute, fiber is at least 5 minutes in coagulating bath.By abundant
Dry, collection, obtains as-spun fibre；10 times that are stretched to original length are carried out, the polymer fiber of class spider silk is obtained.Gained
The main diameter of fiber is 26 microns, and spindle section radial height is 35~77 microns, and axial length is 60~400 microns, spindle
Internode spacing is 220~2600 microns.
Claims (19)
1. a kind of class spider silk polymer fiber based on porous silica microballoon, it is characterised in that the polymer fiber its
Monofilament has the microstructure of the class spider silk of spindle section structure unit interval distribution, the spindle section structure unit radial height
It is 10~300 microns, preferably 20~200 microns, more preferably 30~150 microns；The axial direction of the spindle section structure unit
Length is 10~1000 microns, preferably 20~700 microns, more preferably 100~300 microns；The spindle section structure unit
Spacing be 10~5000 microns, preferably 50~3000 microns, more preferably 100~1000 microns；
The polymer fiber includes following components based on parts by weight:
A. 100 parts of fibrous matrix polymer；
B. 1~45 parts by weight of porous silica microballoon, preferably 3~40 parts, more preferably 5~30 parts by weight, most preferably
5~25 parts by weight；
The aperture of the porous silica microballoon is 0.1~200 nanometer；
The porosity of the porous silica microballoon is 10~80%；
The average grain diameter of the porous silica microballoon is 0.5~200 micron, preferably 10~150 microns, more preferably 20
~100 microns.
2. a kind of class spider silk polymer fiber based on porous silica microballoon according to claim 1, feature
It is:
The porosity of the porous silica microballoon is 20~60%, preferably 20~50%.
3. a kind of class spider silk polymer fiber based on porous silica microballoon according to claim 1, feature
It is:
The aperture of the porous silica microballoon is 0.5~150 nanometer, more preferably 1~50 nanometer.
4. a kind of class spider silk polymer fiber based on porous silica microballoon according to claim 1, feature
It is:
The polymer fiber main diameter is 5~250 microns, preferably 10~150 microns, more preferably 20~50 microns.
5. a kind of class spider silk polymer fiber based on porous silica microballoon according to claim 1, feature
It is:
The fibrous matrix polymer is selected from polyacrylonitrile, polyurethanes, polyvinyl alcohol, viscose fiber, nylon, cellulose
Sulphonic acid ester, cellulose acetate, polyvinyl chloride, poly- isophtalamide, poly, poly- paraphenylene terephthalamide
At least one of p-phenylenediamine；Preferably polyacrylonitrile, polyurethanes, polyvinyl alcohol, viscose fiber, poly- isophthalic diformazan
At least one of acyl m-phenylene diamine (MPD), poly(p-phenylene terephthalamide), polyvinyl chloride, more preferably polyacrylonitrile, poly- amino
At least one of formic acid esters, polyvinyl alcohol.
6. a kind of class spider silk polymer fiber based on porous silica microballoon according to claim 1, feature
It is:
The fibrous matrix polymer is selected from polyvinyl alcohol；The degree of polymerization of the polyvinyl alcohol is 400~4000, preferably 500
~3000, more preferably 1000~2500；Alcoholysis degree is 55%~99%, preferably 88%~99%.
7. described in any item a kind of class spider silk polymer based on porous silica microballoon according to claim 1~6
Fiber is prepared by method comprising the following steps:
(1) it disperses the fibrous matrix polymer and porous silica microballoon additive in solvent by the dosage, adds
Heat, stirring are dissolved in solvent to fibrous matrix polymer, and porous silica microballoon is evenly dispersed in the solution, obtain uniform
Spinning solution；
(2) corresponding coagulating bath is prepared；
(3) spinning solution is squeezed into coagulating bath, through supersolidification, drying, collection obtains as-spun fibre；
(4) by stretching as-spun fibre, the polymer fiber of class spider silk is obtained.
8. a kind of described in any item class spider silk polymer based on porous silica microballoon according to claim 1~7
The preparation method of fiber, it is characterised in that the following steps are included:
(1) it disperses the fibrous matrix polymer and porous silica microballoon in solvent by the dosage, heating, stirring
It is dissolved in solvent to fibrous matrix polymer, porous silica microballoon is evenly dispersed in the solution, obtains spinning solution；
(2) corresponding coagulating bath is prepared；
(3) spinning solution is squeezed into coagulating bath, through supersolidification, drying, collects, obtain as-spun fibre；
(4) by stretching as-spun fibre, the polymer fiber of the class spider silk with the spindle section structure being spaced apart is obtained.
9. a kind of preparation side of class spider silk polymer fiber based on porous silica microballoon according to claim 8
Method, it is characterised in that:
It is in terms of 100 parts by weight of solvent in the step (1), the dosage of the fibrous matrix polymer is 5~50 parts by weight,
Preferably 10~40 parts, more preferably 10~25 parts.
10. a kind of preparation of class spider silk polymer fiber based on porous silica microballoon according to claim 8
Method, it is characterised in that:
In the step (1), the solvent is selected from Isosorbide-5-Nitrae-dioxane, n,N-Dimethylformamide, tetrahydrofuran, water, sulfuric acid
At least one of, more preferably at least one of n,N-Dimethylformamide, Isosorbide-5-Nitrae-dioxane.
11. a kind of preparation of class spider silk polymer fiber based on porous silica microballoon according to claim 8
Method, it is characterised in that:
In the step (1), the heating temperature is 30~95 degrees Celsius, preferably 50~95 degrees Celsius, more preferably 70~95
Degree Celsius.
12. a kind of preparation of class spider silk polymer fiber based on porous silica microballoon according to claim 8
Method, it is characterised in that:
In the step (2), the coagulating bath is selected from aqueous sodium persulfate solution, methanol, ethyl acetate, water, Isosorbide-5-Nitrae-dioxane, N,
At least one of dinethylformamide or mixed solvent, preferably sulfuric acid sodium water solution, methanol, water, Isosorbide-5-Nitrae-dioxane, N,
At least one of dinethylformamide or mixed solvent；The concentration of the aqueous sodium persulfate solution is 300~500g/L, preferably
For 350~450g/L.
13. a kind of preparation of class spider silk polymer fiber based on porous silica microballoon according to claim 8
Method, it is characterised in that:
The fibrous matrix polymer is polyvinyl alcohol, and the solvent is Isosorbide-5-Nitrae-dioxane, and the coagulating bath is selected from methanol, second
Acetoacetic ester, methanol and Isosorbide-5-Nitrae-dioxane composition at least one of binary solution；Preferably methanol or methanol and Isosorbide-5-Nitrae-
The binary solution of dioxane composition；More preferably methanol, wherein the methanol and Isosorbide-5-Nitrae-dioxane composition binary solution
In, it is that the parts by weight of the Isosorbide-5-Nitrae-dioxane are 0.1~50 part in terms of 100 parts by methanol weight, preferably 5~40 parts, more
Preferably 10~30 parts.
14. a kind of preparation of class spider silk polymer fiber based on porous silica microballoon according to claim 8
Method, it is characterised in that:
When carrying out spinning using the spinning solution, the spinneret orifice internal diameter is 10~1000 microns, and preferably 50~500 is micro-
Rice, more preferably 50~300 microns.
15. a kind of preparation of class spider silk polymer fiber based on porous silica microballoon according to claim 8
Method, it is characterised in that:
When carrying out spinning using the spinning solution, receiving silk rate is 0.01~100 meter per minute, and preferably 0.05~10 meter every
Minute, more preferable 0.1~1 meter is per minute.
16. a kind of preparation of class spider silk polymer fiber based on porous silica microballoon according to claim 8
Method, it is characterised in that:
In the step (4), the fibrous matrix polymer is polyvinyl alcohol, and draft temperature is 100~220 degrees Celsius, preferably
120~200 degrees Celsius, more preferably 150~180 degrees Celsius.
17. according to a kind of described in any item class spider silk polymerizations based on porous silica microballoon of claim 8~16
The preparation method of fibres, it is characterised in that further comprising the steps of:
Fiber obtained by step (4) is placed in crosslinked fluid and is impregnated, through washing, drying, collection to get.
18. a kind of preparation of class spider silk polymer fiber based on porous silica microballoon according to claim 17
Method, it is characterised in that:
The fibrous matrix polymer is polyvinyl alcohol, and the crosslinked fluid is acids and aldehydes and/or sodium sulphate, molten with water
Liquid；The acids is inorganic acid, preferably at least one of hydrochloric acid, sulfuric acid, more preferably sulfuric acid；The aldehydes is selected from first
At least one of aldehyde, glutaraldehyde.
19. a kind of preparation of class spider silk polymer fiber based on porous silica microballoon according to claim 18
Method, it is characterised in that:
Acids is selected from sulfuric acid in the crosslinked fluid, and aldehydes is selected from glutaraldehyde and formaldehyde；Wherein:
The concentration of the sulfuric acid is 100~500 gram per liters, preferably 200~350 gram per liters；
The concentration of the glutaraldehyde is 1~80 gram per liter, preferably 30~60 gram per liters；
The concentration of the formaldehyde is 1~50 gram per liter, preferably 20~35 gram per liters；
The concentration of the sodium sulphate is 0~350 gram per liter, preferably 50~200 gram per liters.
Priority Applications (10)
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|---|---|---|---|
| CN201710528419.8A CN109208108B (en) | 2017-07-01 | 2017-07-01 | Spider silk-like polymer fiber based on silica porous microspheres and preparation method thereof |
| EP18828449.1A EP3650587A4 (en) | 2017-07-01 | 2018-06-25 | Spider-silk-like polymer fiber, preparation method therefor and use thereof |
| CA3068755A CA3068755A1 (en) | 2017-07-01 | 2018-06-25 | Spider-silk-like polymer fiber, preparation method therefor and use thereof |
| CN201880043553.1A CN110914488B (en) | 2017-07-01 | 2018-06-25 | Spider silk-like polymer fibers, method for producing same, and use thereof |
| JP2020500159A JP7353262B2 (en) | 2017-07-01 | 2018-06-25 | Spider-like polymer fibers, their production methods and their uses |
| PCT/CN2018/092645 WO2019007217A1 (en) | 2017-07-01 | 2018-06-25 | Spider-silk-like polymer fiber, preparation method therefor and use thereof |
| AU2018296341A AU2018296341B2 (en) | 2017-07-01 | 2018-06-25 | Spider-silk-like polymer fiber, preparation method therefor and use thereof |
| US16/627,929 US11572638B2 (en) | 2017-07-01 | 2018-06-25 | Spider-silk-like polymer fiber, preparation method therefor and use thereof |
| KR1020207002521A KR102538295B1 (en) | 2017-07-01 | 2018-06-25 | Spider-silk-like polymer fibers, methods for their preparation and uses thereof |
| TW107122475A TWI786144B (en) | 2017-07-01 | 2018-06-29 | Spider silk-like polymer fiber, its preparation method and its use |
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| CN111850722A (en) * | 2020-07-16 | 2020-10-30 | 浙江理工大学 | Preparation method of strawberry-shaped organic/inorganic crosslinked microsphere oriented filling reinforced chemical fiber |
| CN113493943A (en) * | 2020-03-18 | 2021-10-12 | 中国科学院山西煤炭化学研究所 | Si/C composite fiber material and preparation method and application thereof |
| CN113546565A (en) * | 2021-07-20 | 2021-10-26 | 南京工业大学 | Mesoscopic magnetic stirrer and preparation method thereof |
| CN115354409A (en) * | 2022-08-30 | 2022-11-18 | 南开大学 | Preparation method of super-strong artificial spider silk based on nanogel |
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| CN1807707A (en) * | 2006-01-13 | 2006-07-26 | 清华大学 | Core-shell composite micron/nano fiber and preparation method thereof |
| CN102587139A (en) * | 2012-01-09 | 2012-07-18 | 北京航空航天大学 | Preparation method of freshwater collecting fibers with transmission function and application thereof |
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Patent Citations (2)
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| CN1807707A (en) * | 2006-01-13 | 2006-07-26 | 清华大学 | Core-shell composite micron/nano fiber and preparation method thereof |
| CN102587139A (en) * | 2012-01-09 | 2012-07-18 | 北京航空航天大学 | Preparation method of freshwater collecting fibers with transmission function and application thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113493943A (en) * | 2020-03-18 | 2021-10-12 | 中国科学院山西煤炭化学研究所 | Si/C composite fiber material and preparation method and application thereof |
| CN111850722A (en) * | 2020-07-16 | 2020-10-30 | 浙江理工大学 | Preparation method of strawberry-shaped organic/inorganic crosslinked microsphere oriented filling reinforced chemical fiber |
| CN111850722B (en) * | 2020-07-16 | 2021-08-13 | 浙江理工大学 | Preparation method of strawberry-shaped organic/inorganic crosslinked microsphere oriented filling reinforced chemical fiber |
| CN113546565A (en) * | 2021-07-20 | 2021-10-26 | 南京工业大学 | Mesoscopic magnetic stirrer and preparation method thereof |
| CN113546565B (en) * | 2021-07-20 | 2022-07-12 | 南京工业大学 | Mesoscopic magnetic stirrer and preparation method thereof |
| CN115354409A (en) * | 2022-08-30 | 2022-11-18 | 南开大学 | Preparation method of super-strong artificial spider silk based on nanogel |
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