CN110438586A - The preparation method and product of super hydrophobic porous fiber with orientation pore structure and application - Google Patents
The preparation method and product of super hydrophobic porous fiber with orientation pore structure and application Download PDFInfo
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- CN110438586A CN110438586A CN201810421225.2A CN201810421225A CN110438586A CN 110438586 A CN110438586 A CN 110438586A CN 201810421225 A CN201810421225 A CN 201810421225A CN 110438586 A CN110438586 A CN 110438586A
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- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
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- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/02—Chemical after-treatment of artificial filaments or the like during manufacture of cellulose, cellulose derivatives, or proteins
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
- D01F11/06—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
- D01F11/08—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
- D01F2/28—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives from organic cellulose esters or ethers, e.g. cellulose acetate
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- 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
- D01F6/52—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 polymers of unsaturated carboxylic acids or unsaturated esters
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- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/74—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles
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- 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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- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
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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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
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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
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
Abstract
It include: the preparation of spinning solution the present invention relates to a kind of preparation method of super hydrophobic porous fiber with orientation pore structure and product and application, preparation method；Spinning solution carries out spinning, and when spinning is oriented freezing, and is collected to fiber is freezed；Freeze fiber removal ice crystal；And surface super hydrophobic processing is carried out to porous fibre.The present invention, which passes through, combines orientation freezing and solution-polymerized SBR, obtains then carrying out surface super hydrophobic processing with the porous fibre of orientation pore structure to it, it being made to have excellent heat-insulated and ultra-hydrophobicity.
Description
Technical field
The present invention relates to the preparation fields of porous fibre, and in particular to a kind of super hydrophobic porous fibre with orientation pore structure
The preparation method and product of dimension and application.
Background technique
Orientation freezing is a kind of movement for being influenced using temperature gradient and controlling raw material and assembling to obtain orientation knot
The method of structure porous material.In recent years, people are successfully prepared the porous material that multiclass has orientation texture using orientation freezing
Material.Deville et al. (S.Deville, E.Saiz, A.P.Tomsia, Biomaterials 2006,27,5480.) successfully makes
For the timbering material of hydroxyapatite, the presence of orientation texture makes this material have the compression bigger than other structures strong
Degree.Wicklein et al. (B.Wicklein, A.Kocjan, G.Salazar-Alvarez, F.Carosio, G.Camino,
M.Antonietti, L. Bergstrom, Nat.Nanotechnol.2014,10,27791) utilize orientation freezing preparation
Graphene/cellulose compound support frame material has better heat-insulated and flame retardant property because of orientation texture.
However, limitation of traditional orientation freezing due to its mold, cannot achieve continuous large-scale preparation, for needing
The occasion of porous fibre is continuously prepared on a large scale, this disadvantage seriously limits orientation freezing and prepares answering for porous fibre
With.In addition, even if material being prepared itself also tends to do not have ultra-hydrophobicity using orientation freezing method.
Super-hydrophobic phenomenon is the common phenomenon in nature, is super-hydrophobic by many plant leaf blade surfaces represented of lotus leaf
Surface, water are in pearl on its surface, and when inclination can tumble under the effect of gravity, have self-cleaning effect, this phenomenon is claimed
For " lotus leaf effect ".The contact angle of water is generally greater than 150 °, surface of the roll angle less than 10 ° is known as super hydrophobic surface, can be with
Super hydrophobic surface is constructed by constructing the surface of micro-nano coarse structure or dropping the modes such as low-surface-energy.
Superhydrophobic fabric is a kind of functional fabric to grow up on the basis of super hydrophobic surface research, because it has
It is good automatically cleaning, antifouling and according to performances such as water, it can be used as protective garment, waterproof cloth etc., all have weight in fields such as industry, medical treatment
The application wanted.
The hydrophobic ability of superhydrophobic fibers and fabric can be closely related with its surface roughness and surface, currently, obtaining
The method of superhydrophobic fibers and fabric mainly has:
(1) in fabric surface coated with nano particle.This method mainly contains nano particle by immersing fiber or fabric
Solution in or the solution spraying containing nano particle obtained into superhydrophobic fibers or fabric in fiber or fabric surface.This
Method frequently with nano particle include nano silica, nano-titanium dioxide etc., main purpose is in fiber or fabric
The coarse micro nano structure of surface construction, to improve the hydrophobic performance on its surface.
(2) low surface energy coat is coated in fiber or fabric surface.This method mainly passes through the side such as dip-coating, vapor deposition
Method enables the surface of fiber or fabric to have lower surface, to obtain the fiber or fabric with super hydrophobic surface.
It would therefore be highly desirable to develop a kind of new porous fibre with orientation pore structure of the technique preparation with ultra-hydrophobicity
Dimension.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of with the super hydrophobic porous of orientation pore structure
The preparation method of fiber orients freezing and solution-polymerized SBR by combining, and obtains the porous fibre with orientation pore structure, then right
It carries out surface super hydrophobic processing, it is made to have excellent heat-insulated and ultra-hydrophobicity.
Technical solution provided by the present invention are as follows:
A kind of preparation method of the super hydrophobic porous fiber with orientation pore structure, comprising:
The preparation of spinning solution；
Spinning solution carries out spinning, and when spinning is oriented freezing, and is collected to fiber is freezed；
Freeze fiber removal ice crystal；
And surface super hydrophobic processing is carried out to porous fibre.
The porous fibre being prepared in the above technical solution has excellent heat-insulated and ultra-hydrophobicity.When spinning is molten
Liquid in extruder pump after squeezing out, and due to the influence of temperature gradient, the nucleation of ice crystal and growth are all taken in extrusion direction
To formation orientation pore structure.Simultaneously as micron-scale phase separation occurs for system, raw material is squeezed by ice crystal, is compressed between ice crystal
Gap among.It is to be frozen completely after, then remove ice crystal, just obtained that there are the more of orientation pore structure using ice crystal as template
Hole fiber.Then to it is resulting have orientation pore structure porous fibre carry out surface super hydrophobic processing, can be obtained have take
To the super hydrophobic porous fiber of pore structure.
There is the preparation method of the super hydrophobic porous fiber of orientation pore structure in the present invention, include the following steps:
1) the natural polymer solution of spinning is prepared；The natural polymer solution includes that sodium carboxymethylcellulose is molten
One or more of liquid, starch solution, chitosan solution, fibroin solutions；
2) natural polymer solution is subjected to solution-polymerized SBR, when spinning is oriented freezing, and receives to fiber is freezed
Collection；
3) freezing fiber carries out freeze-drying removal ice crystal, obtains the porous fibre with orientation pore structure；
4) porous fibre carries out surface super hydrophobic processing, obtains the super hydrophobic porous fiber with orientation pore structure.
Preferably, the carboxymethylcellulose sodium solution is sodium carboxymethyl cellulose solution, the carboxymethyl cellulose
The mass fraction of plain sodium solution is 1%-10%.The preparation of carboxymethylcellulose sodium solution: sodium carboxymethylcellulose powder is molten
Yu Shuizhong is made into carboxymethylcellulose sodium solution.
Preferably, the starch solution is amidin, the mass fraction of the starch solution is 1%-10%.
The preparation of starch solution: water soluble starch powder is soluble in water, it is made into starch solution.
Preferably, the chitosan solution is chitosan acetic acid solution；The concentration of the chitosan solution is 20-
60mg/ml.The preparation of chitosan solution: Chitosan powder is dissolved in acetic acid solution, is made into chitosan solution, acetic acid solution
Mass concentration is 0.5-1.5%.
Preferably, the preparation of the fibroin solutions: natural silk cocoon being sheared, baking is boiled in sodium carbonate liquor
It is dry, it is dissolved in lithium-bromide solution, is made into fibroin solutions after dialysis completely；The mass fraction of the fibroin solutions is
1%-30%.
Preferably, natural polymer solution includes chitosan solution and fibroin solutions, wherein fibroin and shell
The quality proportioning of glycan is 8-10:1.
There is the preparation method of the super hydrophobic porous fiber of orientation pore structure in the present invention, include the following steps:
(1) lotion to be polymerized is prepared；The lotion to be polymerized includes resin monomer, radical polymerization initiator, response type
Emulsifier and thickener or the lotion to be polymerized include performed polymer, radical polymerization initiator, reactive emulsifier and increasing
Thick dose or the lotion to be polymerized include self-emulsifying performed polymer, radical polymerization initiator and thickener；
(2) lotion to be polymerized carries out milk thread, and when spinning is oriented freezing, and is collected to fiber is freezed；
(3) freezing fiber carries out polymerization reaction in low temperature environment；
(4) freezing fiber thaws and dries, and obtains the porous resin fiber with orientation pore structure；
(5) porous resin fiber carries out surface super hydrophobic processing, obtains the super hydrophobic porous fiber with orientation pore structure.
Preferably, according to parts by weight, the lotion to be polymerized include: 10~30 parts of resin monomers or performed polymer, 1~
5 parts of radical polymerization initiators, 1~10 part of reactive emulsifier and 1~10 part of thickener.
Preferably, according to parts by weight, the lotion to be polymerized includes: 5~40 parts of self-emulsifying performed polymers, 1~5 part
Radical polymerization initiator and 1~10 part of thickener.
Resin monomer is the resin monomer that Raolical polymerizable can occur in the present invention.Preferably, the resin
Monomer is selected from styrene, methyl methacrylate, butyl acrylate, acrylic acid, ethyl methacrylate, butyl methacrylate
One or more of.
Preferably, the performed polymer is selected from epoxy FRP pipe or acrylic acid esterification polycarbonate prepolymer body.
Preferably, the self-emulsifying performed polymer is selected from aqueous polyurethane acrylate or waterborne epoxy acrylate.
Thickener in the present invention is primarily to make lotion thickening become sticky, so that lotion to be polymerized is able to carry out lotion spinning
Silk.Preferably, the thickener is selected from nanoclay or hydroxypropyl cellulose sodium.
In the present invention reactive emulsifier can with emulsifying resins monomer or performed polymer, and can under given conditions with resin list
The emulsifier that body or performed polymer are copolymerized, specified conditions such as ultraviolet light and high-energy radiation.Reactive emulsifier
Can selected from ADEKA company, Japan emulsifier ER serial (such as ER-10), SR serial (such as SR-10), NE series (such as NE-10),
SE series (such as SE-10N), COPS-2 (2- acrylamide-2-methylpro panesulfonic acid sodium), HE-1012 (thick the Huanshui River chemistry).As
It is preferred that the reactive emulsifier is selected from ER-10, SR-10, NE-10, SE-10N, 2- acrylamide-2-methylpro panesulfonic acid
One or more of sodium, HE-1012.
Radical polymerization initiator includes organic peroxide evocating agent, inorganic peroxide initiator, idol in the present invention
Nitrogen class initiator, redox initiator and other types of photoinitiator.Preferably, free radical polymerization in the step 1)
Initiator is selected from benzoyl peroxide and N, N- dimethyl benzamide, tert-butyl hydroperoxide and three octyl tertiary amines, 2- hydroxyl
Base-2- methyl-1-phenyl-1- acetone, 1- hydroxy-cyclohexyl phenyl ketone or 2- hydroxyl-4'- (2- hydroxy ethoxy)-2- methylbenzene
Acetone.
Preferably, the lotion to be polymerized further includes crosslinking agent；The crosslinking agent is selected from ethyleneglycol dimethacrylate
One or more of ester, divinylbenzene, diisocyanate, N,N methylene bis acrylamide.
Preferably, the temperature of the low temperature environment is -40~-10 DEG C.Further preferably -20 DEG C.
Preferably, the self-emulsifying performed polymer is aqueous polyurethane acrylate, the radical polymerization initiator is
2- hydroxy-2-methyl -1- phenyl -1- acetone, the polymerization reaction carry out under ultraviolet light.
Preferably, the drying refers to the vacuum drying at 30-60 DEG C.Since resin fibre hydrophily is small, intensity is high,
Vacuum freeze drying is not needed after freezing, it is only necessary to which vacuum drying at 30-60 DEG C after defrosting not will lead to duct
The collapse of structure.
There is the preparation method of the super hydrophobic porous fiber of orientation pore structure in the present invention, include the following steps:
I prepares polyamic acid gel brine；
II polyamic acid gel brine carries out solution-polymerized SBR, and when spinning is oriented freezing, and collects freezing fiber；
III freezing fiber carries out freeze-drying removal ice crystal, obtains the porous fibre with orientation pore structure；
IV porous fibre obtains polyimide foraminous fiber after being overheated sub- amidation；
V polyimide foraminous fiber carries out surface super hydrophobic processing, obtains the super hydrophobic porous fibre with orientation pore structure
Dimension.
Preferably, the mass fraction of the polyamic acid gel brine is 3-20%.Further preferably 5-15%.
Polyamic acid gel brine in the present invention can be prepared using the prior art.Preferably, the polyamides
The preparation of amino acid gel brine includes:
1.1) 4,4'- diaminodiphenyl ether is dissolved in dimethyl acetamide, pyromellitic acid anhydride and three second is added
Amine reaction, obtains polyamic acid salt solid；
1.2) polyamic acid salt solid is mixed with triethylamine, water, obtains polyamic acid gel brine.
Further preferably, the preparation of the polyamic acid gel brine specifically includes:
1.1) 4,4'- diaminodiphenyl ether is dissolved in dimethyl acetamide, pyromellitic acid anhydride and three second is added
Amine is mixed, and obtains polyamic acid salting liquid；Polyamic acid salting liquid is poured into water separation, is washed, freeze-drying obtains
Polyamic acid salt solid；
1.2) polyamic acid salt solid and triethylamine, water are mixed, and standing obtains polyamic acid gel brine.
Preferably, the sub- amidation of heat refers to: porous fibre carries out three Duan Shengwen and three sections of constant temperature processing, heating with
Constant temperature processing is alternately.
Further preferably, the sub- amidation of the heat specifically includes: 1-3 DEG C at room temperature/min is warming up to 90-110 DEG C, keeps
25-35min；It is warming up to 190-210 DEG C with 1-3 DEG C/min, keeps 25-35min；It is warming up to 290-310 DEG C with 1-3 DEG C/min,
Keep 55-65min.
Preferably, the surface super hydrophobic processing includes: dip coating, vapour deposition process or wet-chemical sedimentation.Pass through
Porous fibre surface increase super-hydrophobic coat, can make it have superhydrophobic property, water or other liquid fabric surface can
In pearl, when inclination, can tumble by gravity.
Dip coating is preferred are as follows: porous fibre is immersed into nano silicon dioxide sol, nano titanic oxide sol, 1H, 1H,
2H, 2H- perfluoro capryl triethoxysilane or 1H, 1H, 2H, the silicon fluorides solution, 1H such as 2H- perfluoro decyl triethoxysilane,
1H, 2H, 2H- perfluoro capryl triethoxysilane or 1H, 1H, 2H, silicon fluorides and the nanometer such as 2H- perfluoro decyl triethoxysilane
Titanium dioxide mixed solution, 1H, 1H, 2H, three ethoxy of 2H- perfluoro capryl triethoxysilane or 1H, 1H, 2H, 2H- perfluoro decyl
5-30min in the super-hydrophobic coats solution such as the silicon fluorides such as base silane and nano silica mixed solution, is then dried.
Vapour deposition process is preferred are as follows: porous fibre is placed in 1H, 1H, 2H, 2H- perfluoro capryl triethoxysilane or 1H,
8-12h is deposited in the silicon fluorides atmosphere such as 1H, 2H, 2H- perfluoro decyl triethoxysilane.
Wet-chemical sedimentation is preferred are as follows: by ethyl orthosilicate and 1H, 1H, 2H, 2H- perfluoro capryl triethoxysilane or
The silicon fluorides cohydrolysis such as 1H, 1H, 2H, 2H- perfluoro decyl triethoxysilane obtain super-hydrophobic solution, and porous fibre is immersed should
5-30min in super-hydrophobic solution, or by super-hydrophobic solution spin coating or it is sprayed into fiber surface, then it is dried；Or it will be porous
Fiber immerses poly- (vinylidene fluoride-co- hexafluoropropene) and 1H, 1H, 2H, 2H- perfluoro capryl triethoxysilane or 1H, 1H,
5-30min in the mixing acetone or DMF solution of the silicon fluorides such as 2H, 2H- perfluoro decyl triethoxysilane, is then dried.
Preferably, the orientation freezing specifically includes: spinning solution passes through low temperature copper ring after squeezing out in extruder pump,
It is oriented freezing；The temperature of the low temperature copper ring is -120~0 DEG C.
The present invention provides a kind of super hydrophobic porous fibre with orientation pore structure being prepared such as above-mentioned preparation method
Dimension.The diameter of the porous fibre is 100~1000 μm, and aperture is 10~100 μm.
The present invention, which provides, a kind of to knit such as the above-mentioned super hydrophobic porous fiber with orientation pore structure preparing waterproof and oilproof
Application in object material.Above-mentioned porous fibre further progress surface super hydrophobic processing, can make it have super-hydrophobic property,
When the liquid such as water fall in fabric surface, pearl can be presented and tumbled by gravity, reduce pollution of the liquid to fabric, have certainly
The functions such as cleaning, antifouling, water repellent, can be widely applied to wearable textiles, development prospect is wide.
The present invention provides a kind of such as above-mentioned super hydrophobic porous fiber the answering as heat-barrier material with orientation pore structure
With.
Compared with the existing technology, the beneficial effects of the present invention are embodied in:
(1) preparation method in the present invention is simple, can continuous large scale preparation, be suitble to industry amplification application, while can root
Different materials is designed according to actual needs.
(2) the more of different pore size can be prepared by adjusting the temperature of orientation freezing in the preparation method in the present invention
Hole fiber, furthermore the aperture of fiber multihole structure, porosity and hole pattern can also be adjusted on a large scale.
(3) porous fibre with orientation pore structure is obtained, so by combining orientation freezing and solution-polymerized SBR in the present invention
Surface super hydrophobic processing is carried out to it afterwards, it is made to have excellent heat-insulated and ultra-hydrophobicity.
Detailed description of the invention
Fig. 1 is present invention orientation freezing-spinning process schematic device；
Fig. 2 is the optical picture of porous fibre prepared by embodiment 1；
Fig. 3 is the Micro-CT figure of porous fibre prepared by embodiment 1；
Fig. 4 is the SEM figure of porous fibre prepared by embodiment 2；
Fig. 5 is the SEM figure of porous fibre prepared by embodiment 6；
Fig. 6 is the SEM figure of porous resin fiber prepared by embodiment 7；
Fig. 7 is the SEM figure of porous resin fiber prepared by embodiment 9；
Fig. 8 is the SEM figure of porous fibre prepared by embodiment 12；
Fig. 9 is the infrared figure of porous fibre braided fabric prepared by embodiment 12；
Figure 10 is the temperature statistics of porous fibre braided fabric prepared by embodiment 12 and thermal station substrate；
Figure 11 is the SEM figure of porous fibre prepared by embodiment 13；
Figure 12 is the SEM figure of porous fibre prepared by embodiment 14.
Specific embodiment
The present invention is further explained in the light of specific embodiments:
Used in embodiment orientation freezing-spinning schematic device as shown in Figure 1, its middle and upper part be extrusion device 1,
Mixed solution is after the extrusion of extrusion device 1, and by low temperature copper ring 2, copper ring 2 connect with cold source and (do not provide), and bottom is motor receipts
Acquisition means 3.It is enlarged drawing of the mixed solution after freezing-spinning on the right side of Fig. 1.
Embodiment 1
(1) the natural silk cocoon of 4.5g is sheared, drying is boiled in 1% sodium carbonate liquor, is dissolved in the 9mol/ml bromine of 20ml
Change in lithium solution, it is 22.5% fibroin solutions that dialysis is made into mass fraction afterwards for 24 hours.
0.5g Chitosan powder is dissolved in 1% acetic acid solution of 10ml, stirs 30min under the revolving speed of 800rpm/min
It is uniformly mixed it, being made into concentration is 50mg/ml chitosan solution.
After mixing by 20ml fibroin solutions and 10ml chitosan solution, it is obtained after centrifugation bubble removing uniform molten
Liquid, wherein fibroin and chitosan mass proportion are 9:1.
(2) mixed solution is placed in syringe, by extruder pump extrusion solution, copper ring is placed in low-temp reaction bath (- 100
DEG C) in, solution passes through copper ring and carries out freezing-spinning process, and the fiber after freezing is collected with motor.
(3) the freezing fiber for obtaining step (2) is freeze-dried for 24 hours to remove solvent, obtains porous fibre, has orientation
Porous structure, optical photograph are as shown in Figure 2.And porous fibre carries out Micro-CT characterization, as shown in figure 3, illustrating porous fibre
Dimension has orientation pore structure.
(4) porous fibre that step (3) obtains is placed in 1H, 1H, 2H, in 2H- perfluoro capryl triethoxysilane atmosphere,
Be vapor-deposited 12h, obtains super hydrophobic porous fiber.
(5) by super hydrophobic porous fibrage at fabric, using liquid such as contact angle instrument measurement water, silicone oil in fabric surface
Contact angle, test result show water the fabric surface contact angle be 151.5 °, contact angle of the silicone oil in the fabric surface
It is 150.3 °.
Embodiment 2
(1) the natural silk cocoon of 4.5g is sheared, drying is boiled in 1% sodium carbonate liquor, is dissolved in the 9mol/ml bromine of 20ml
Change in lithium solution, it is 22.5% fibroin solutions that dialysis is made into mass fraction afterwards for 24 hours.
0.5g Chitosan powder is dissolved in 1% acetic acid solution of 10ml, stirs 30min under the revolving speed of 800rpm/min
It is uniformly mixed it, being made into concentration is 50mg/ml chitosan solution.
After mixing by 20ml fibroin solutions and 10ml chitosan solution, it is obtained after centrifugation bubble removing uniform molten
Liquid, wherein fibroin and chitosan mass proportion are 9:1.
(2) mixed solution is placed in syringe, by extruder pump extrusion solution, copper ring is placed in low-temp reaction bath (respectively
It is -40, -60, -80, -100 DEG C) in, solution passes through copper ring and freeze-spinning process, and by the fiber motor after freezing
It collects.
(3) the freezing fiber for obtaining step (2) is freeze-dried for 24 hours to remove solvent, obtains porous fibre, has orientation
Porous structure.SEM characterization is carried out for the porous fibre obtained under different temperatures in the present embodiment, as shown in figure 4, illustrating hole
Fiber has orientation pore structure.
(4) by 1.25g poly- (vinylidene fluoride-co- hexafluoropropene) and 0.75mL 1H, 1H, 2H, 2H- perfluoro capryl three
Ethoxysilane is dissolved in 50mL acetone, and 30min is stirred at 50 DEG C and obtains super-hydrophobic coat solution；
(5) porous fibre for obtaining step (3) immerses 5min in super-hydrophobic coat solution described in step (4), later
Dry 30min, obtains super hydrophobic porous fiber at 130 DEG C.
(6) by super hydrophobic porous fibrage at fabric, using liquid such as contact angle instrument measurement water, silicone oil in fabric surface
Contact angle, test result show water the fabric surface contact angle be 150.8 °, contact angle of the silicone oil in the fabric surface
It is 150.2 °.
Embodiment 3
(1) the natural silk cocoon of 4.5g is sheared, drying is boiled in 1% sodium carbonate liquor, is dissolved in the 9mol/ml bromine of 20ml
Change in lithium solution, it is 22.5% fibroin solutions that dialysis is made into mass fraction afterwards for 24 hours.
0.5g Chitosan powder is dissolved in 1% acetic acid solution of 10ml, stirs 30min under the revolving speed of 800rpm/min
It is uniformly mixed it, being made into concentration is 50mg/ml chitosan solution.
After mixing by 20ml fibroin solutions and 10ml chitosan solution, it is obtained after centrifugation bubble removing uniform molten
Liquid, wherein fibroin and chitosan mass proportion are 9:1.
(2) mixed solution is placed in syringe, by extruder pump extrusion solution, copper ring is placed in low-temp reaction bath (temperature
It is -100 DEG C) in, solution passes through copper ring and carries out freezing-spinning process, and the fiber after freezing is collected with motor.
(3) the freezing fiber for obtaining step (2) is freeze-dried for 24 hours to remove solvent, obtains porous fibre, has orientation
Porous structure.
(4) porous fibre obtained by step (3) is immersed into the drying at 130 DEG C after 5min in nano silicon dioxide sol
Super hydrophobic porous fiber is obtained after 30min.
(5) by super hydrophobic porous fibrage at fabric, using liquid such as contact angle instrument measurement water, silicone oil in fabric surface
Contact angle, test result show water the fabric surface contact angle be 152.1 °, contact angle of the silicone oil in the fabric surface
It is 150.8 °.
Embodiment 4
(1) 0.2g sodium carboxymethylcellulose powder is dissolved in 10ml deionized water, after being completely dissolved, is made into mass fraction
For 2% carboxymethylcellulose sodium solution.
(2) solution is placed in syringe, by extruder pump extrusion solution, copper ring is placed in low-temp reaction bath, copper ring temperature
Degree is -90 DEG C, and solution passes through copper ring and carries out freezing-spinning process, and the fiber after freezing is collected with motor.
(3) the freezing fiber for obtaining step (2) is freeze-dried for 24 hours to remove solvent, obtains porous fibre, has orientation
Porous structure.
(4) porous fibre that step (3) obtains is placed in 1H, 1H, 2H, in 2H- perfluoro capryl triethoxysilane atmosphere,
Be vapor-deposited 12h, obtains super hydrophobic porous fiber.
(5) by super hydrophobic porous fibrage at fabric, using liquid such as contact angle instrument measurement water, silicone oil in fabric surface
Contact angle, test result show water the fabric surface contact angle be 153.1 °, contact angle of the silicone oil in the fabric surface
It is 150.0 °.
Embodiment 5
(1) 0.3g water soluble starch powder is dissolved in 10ml deionized water, after being completely dissolved, being made into mass fraction is
3% starch solution.
(2) solution is placed in syringe, by extruder pump extrusion solution, copper ring is placed in low-temp reaction bath, copper ring temperature
Degree is -90 DEG C, and solution passes through copper ring and carries out freezing-spinning process, and the fiber after freezing is collected with motor.
(3) the freezing fiber for obtaining step (2) is freeze-dried for 24 hours to remove solvent, obtains porous fibre, has orientation
Porous structure.
(4) porous fibre obtained by step (3) is immersed into the drying at 130 DEG C after 5min in nano titanic oxide sol
Super hydrophobic porous fiber is obtained after 30min.
(5) by super hydrophobic porous fibrage at fabric, using liquid such as contact angle instrument measurement water, silicone oil in fabric surface
Contact angle, test result show water the fabric surface contact angle be 150.1 °, contact angle of the silicone oil in the fabric surface
It is 151.2 °.
Embodiment 6
(1) 0.6g Chitosan powder is dissolved in 1% acetic acid solution of 10ml, is stirred under the revolving speed of 800rpm/min
30min is uniformly mixed it, and being made into concentration is 60mg/ml chitosan solution.
(2) mixed solution is placed in syringe, by extruder pump extrusion solution, copper ring is placed in low-temp reaction bath (respectively
Temperature is -90 DEG C) in, solution passes through copper ring and carries out freezing-spinning process, and the fiber after freezing is collected with motor.
(3) the freezing fiber for obtaining step (2) is freeze-dried for 24 hours to remove solvent, porous fibre is obtained, such as Fig. 5 institute
Show that there is orientation porous structure.
(4) porous fibre obtained by step (3) is immersed into 1H, 1H, 2H, 2H- perfluoro capryl triethoxysilane and nanometer two
Super hydrophobic porous fiber is obtained after dry 30min at 130 DEG C after 5min in titanium oxide mixed solution.
(5) by super hydrophobic porous fibrage at fabric, using liquid such as contact angle instrument measurement water, silicone oil in fabric surface
Contact angle, test result show water the fabric surface contact angle be 154.2 °, contact angle of the silicone oil in the fabric surface
It is 152.1 °.
Embodiment 7
(1) 0.15g benzoyl peroxide is dissolved in 6ml methyl methacrylate, is uniformly mixed.By 0.7g ER-10
Being dissolved in 14ml deionized water is uniformly mixed it, and being made into mass fraction is 5%ER-10 solution.By above-mentioned methacrylic acid
Methyl ester mixture is uniformly mixed with ER-10 solution, and being made into volume fraction is 30% methyl methacrylate lotion.
1.2g crosslinking agent ethylene glycol dimethacrylate is added to above-mentioned emulsion, and is uniformly mixed.It is viscous by 0.8 g nanometers
Soil is added in above-mentioned methyl methacrylate lotion, and is uniformly mixed.70 μ l N, N- dimethyl benzenes are added into above-mentioned emulsion
Formamide after mixing, is centrifuged bubble removing.
(2) above-mentioned emulsion is placed in syringe, by extruder pump extrusion solution, copper ring is placed in low-temp reaction bath (- 100
DEG C) in, solution passes through copper ring and carries out freezing-spinning process, and the fiber after freezing is collected with motor.
(3) fiber being collected into is placed in -20 DEG C of refrigerators, placed for 24 hours.
(4) the freezing fiber that step (3) obtains is placed in 45 DEG C of vacuum drying oven 3h drying, obtains porous resin fiber, such as
Shown in Fig. 6, there is orientation pore structure.And thermal conductivity test is carried out, thermal conductivity is 61.3mW/ (m*K).
(5) the porous resin fiber that step (4) obtains is placed in 1H, 1H, 2H, 2H- perfluoro capryl triethoxysilane gas
In atmosphere, be vapor-deposited 12h, obtains super hydrophobic porous resin fibre.
(6) super hydrophobic porous resin fibre is woven into fabric, using liquid such as contact angle instrument measurement water, silicone oil in fabric
The contact angle on surface, test result show water the fabric surface contact angle be 152.4 °, silicone oil is in the fabric surface
Contact angle is 150.3 °.
Embodiment 8
(1) 0.10g benzoyl peroxide is dissolved in 4ml methyl methacrylate, is uniformly mixed.By 0.8g ER-10
Being dissolved in 16ml deionized water is uniformly mixed it, is made into the ER-10 solution that mass fraction is 5%.By above-mentioned metering system
Sour methyl ester mixture is uniformly mixed with ER-10 solution, and being made into volume fraction is 20% methyl methacrylate lotion.
0.8g crosslinking agent ethylene glycol dimethacrylate is added to above-mentioned emulsion, and is uniformly mixed.By 0.53 g nanometers
Clay is added in above-mentioned methyl methacrylate lotion, and is uniformly mixed.50 μ l N, N- dimethyl are added into above-mentioned emulsion
Benzamide after mixing, is centrifuged bubble removing.
(2) above-mentioned emulsion is placed in syringe, by extruder pump extrusion solution, copper ring is placed in low-temp reaction bath (- 100
DEG C) in, solution passes through copper ring and carries out freezing-spinning process, and the fiber after freezing is collected with motor.
(3) fiber being collected into is placed in -20 DEG C of refrigerators, placed for 24 hours.
(4) the freezing fiber that step (3) obtains is placed in 45 DEG C of vacuum drying oven 3h drying, obtains porous resin fiber, has
There is orientation pore structure, and carry out thermal conductivity test, thermal conductivity is 56.7mW/ (m*K).
(5) porous resin fiber obtained by step (4) is immersed into 1H, 1H, 2H, 2H- perfluoro decyl triethoxysilane solution
Super hydrophobic porous resin fibre is obtained after dry 30min at 130 DEG C after middle 5min.
(6) super hydrophobic porous resin fibre is woven into fabric, using liquid such as contact angle instrument measurement water, silicone oil in fabric
The contact angle on surface, test result show water the fabric surface contact angle be 152.6 °, silicone oil is in the fabric surface
Contact angle is 151.3 °.
Embodiment 9
(1) 5ml aqueous polyurethane acrylate lotion (mass fraction 40%) is taken, 15ml deionized water is added, is diluted to
The aqueous polyurethane acrylate lotion that mass fraction is 10% is uniformly mixed.
0.2g 2- hydroxy-2-methyl -1- phenyl -1- acetone is dissolved in 20ml aqueous polyurethane acrylate lotion
(10%) it in, is uniformly mixed.0.4g ethylene glycol dimethacrylate is added to above-mentioned emulsion, and is uniformly mixed.By 0.8 nanometer
Clay, which is added in above-mentioned emulsion, realizes thickening, after mixing, is centrifuged bubble removing.
(2) mixed solution is placed in syringe, by extruder pump extrusion solution, copper ring is placed in low-temp reaction bath (- 100
DEG C) in, solution passes through copper ring and carries out freezing-spinning process, and the fiber after freezing is collected with motor.
(3) fiber being collected into is placed in -20 DEG C of refrigerators, and with ultraviolet light 7h.
(4) the freezing fiber that step (3) obtains is placed in 45 DEG C of vacuum drying oven 3h drying, obtains porous resin fiber, such as
Shown in Fig. 7, there is orientation pore structure.And thermal conductivity test is carried out, thermal conductivity is 45.8mW/ (m*K).
(5) the porous resin fiber that step (4) obtains is placed in 1H, 1H, 2H, 2H- perfluoro capryl triethoxysilane gas
In atmosphere, be vapor-deposited 12h, obtains super hydrophobic porous resin fibre.
(6) super hydrophobic porous resin fibre is woven into fabric, using liquid such as contact angle instrument measurement water, silicone oil in fabric
The contact angle on surface, test result show water the fabric surface contact angle be 150.8 °, silicone oil connects the fabric surface
Feeler is 151.2 °
Embodiment 10
(1) 3ml methyl methacrylate is uniformly mixed with 3ml butyl acrylate.0.15g benzoyl peroxide is dissolved in
In the above-mentioned mixed liquor of 6ml, uniformly mix.0.7g ER-10, which is dissolved in 14ml deionized water, is uniformly mixed it, is made into matter
Amount score is 5wt%ER-10 solution.Above-mentioned methyl methacrylate mixed liquor is uniformly mixed with ER-10 solution, is made into volume
Score is 30% methyl methacrylate/butyl acrylate mixed emulsion.
1.2g crosslinking agent ethylene glycol dimethacrylate is added to above-mentioned emulsion, and is uniformly mixed.It is viscous by 0.8 g nanometers
Soil is added in above-mentioned methyl methacrylate/butyl acrylate mixed emulsion, and is uniformly mixed.70 μ l are added into above-mentioned emulsion
N, N- dimethyl benzamide after mixing, are centrifuged bubble removing.
(2) above-mentioned emulsion is placed in syringe, by extruder pump extrusion solution, copper ring is placed in low-temp reaction bath (- 100
DEG C) in, solution passes through copper ring and carries out freezing-spinning process, and the fiber after freezing is collected with motor.
(3) fiber being collected into is placed in -20 DEG C of refrigerators, placed for 24 hours.
(4) the freezing fiber that step (3) obtains is placed in 45 DEG C of vacuum drying oven 3h drying, obtains porous resin fiber, has
There is orientation pore structure, carry out thermal conductivity test, thermal conductivity is 50.3mW/ (m*K).
(5) the porous resin fiber that step (4) obtains is placed in 1H, 1H, 2H, 2H- perfluoro capryl triethoxysilane gas
In atmosphere, be vapor-deposited 12h, obtains super hydrophobic porous resin fibre.
(6) super hydrophobic porous resin fibre is woven into fabric, using liquid such as contact angle instrument measurement water, silicone oil in fabric
The contact angle on surface, test result show water the fabric surface contact angle be 155.0 °, silicone oil is in the fabric surface
Contact angle is 152.4 °
Embodiment 11
(1) 0.10g tert-butyl hydroperoxide is dissolved in 4ml methyl methacrylate, is uniformly mixed.By 0.8g ER-10
Being dissolved in 16ml deionized water is uniformly mixed it, is made into the ER-10 solution that mass fraction is 5%.By above-mentioned metering system
Sour methyl ester mixture is uniformly mixed with ER-10 solution, and being made into volume fraction is 20% methyl methacrylate lotion.
0.8g crosslinking agent ethylene glycol dimethacrylate is added to above-mentioned emulsion, and is uniformly mixed.By 0.53 g nanometers
Clay is added in above-mentioned methyl methacrylate lotion, and is uniformly mixed.50 μ l, tri- octyl tertiary amine is added into above-mentioned emulsion
After mixing, it is centrifuged bubble removing.
(2) above-mentioned emulsion is placed in syringe, by extruder pump extrusion solution, copper ring is placed in low-temp reaction bath (- 100
DEG C) in, solution passes through copper ring and carries out freezing-spinning process, and the fiber after freezing is collected with motor.
(3) fiber being collected into is placed in -20 DEG C of refrigerators, placed for 24 hours.
(4) the freezing fiber that step (3) obtains is placed in 45 DEG C of vacuum drying oven 3h drying, obtains porous resin fiber, has
There is orientation pore structure, and carry out thermal conductivity test, thermal conductivity is 60.2mW/ (m*K).
(5) by 1.25g poly- (vinylidene fluoride-co- hexafluoropropene) and 0.75mL 1H, 1H, 2H, 2H- perfluoro decyl three
Ethoxysilane is dissolved in 50mL acetone, and 30min is stirred at 50 DEG C and obtains super-hydrophobic coat solution；
(6) by porous resin fiber obtained by step (4) immerse in step (5) described super-hydrophobic coat solution after 5min
Super hydrophobic porous resin fibre is obtained after dry 30min at 130 DEG C.
(7) super hydrophobic porous resin fibre is woven into fabric, using liquid such as contact angle instrument measurement water, silicone oil in fabric
The contact angle on surface, test result show water the fabric surface contact angle be 154.1 °, silicone oil is in the fabric surface
Contact angle is 152.8 °
Embodiment 12
(1) 8.0096g ODA (4,4 '-diaminodiphenyl ether) and 95.57g DMAc (dimethyl acetamide) are sufficiently stirred
It mixes, when ODA is completely dissolved, 8.8556g PMDA (pyromellitic acid anhydride) and 4.0476g TEA (triethylamine) is then added,
4 hours are mixed to generate sticky faint yellow PAS (polyamic acid salt) solution.PAS solution is poured slowly into water, is washed
After washing, freeze-drying obtains light yellow PAS solid.
(2) 5g TEA (triethylamine) and 90g deionized water are added into 5g PAS, gained suspension is continuously stirred several small
When, the static mass fraction that obtains for 24 hours is 5%PAS hydrogel after mixing.
(3) it is that 5% polyamic acid gel brine is placed in syringe by mass fraction, hydrogel is squeezed out by extruder pump,
Copper ring is placed in low-temp reaction bath (- 100 DEG C), and spinning passes through copper ring and carries out freezing-spinning process, and the fiber after freezing is used
Motor is collected.
(4) the freezing fiber for obtaining step (3) is freeze-dried for 24 hours to remove ice crystal, is obtained with orientation pore structure
Porous fibre；
(5) porous fibre is overheated sub- amidation, and specially at room temperature 2 DEG C/min is warming up to 100 DEG C, keeps 30min；With
2 DEG C/min is warming up to 200 DEG C, keeps 30min；300 DEG C are warming up to 2 DEG C/min, 60min is kept, obtains polyimide foraminous
Fiber carries out SEM characterization, as shown in figure 8, illustrating that porous fibre has orientation pore structure, aperture is 50~100 μm.
(6) 5mL ethyl orthosilicate and 0.5mL 1H, 1H, 2H, 2H- perfluoro capryl triethoxysilane are dissolved in 25mL second
In alcohol, by 6mL28%NH3·H2O is dissolved in 25mL ethyl alcohol, and two solution are mixed at room temperature and and are stirred until homogeneous, Zhi Houchao
Sonication 30min obtains super-hydrophobic coat solution.
It (7) will be by porous fibre obtained by super-hydrophobic coat solution spraying obtained by step (6) to step (5), at room temperature
Drying simultaneously further solidifies at 110 DEG C, obtains super hydrophobic porous fiber.
(8) by super hydrophobic porous fibrage at fabric, using liquid such as contact angle instrument measurement water, silicone oil in fabric surface
Contact angle, test result show water the fabric surface contact angle be 151.3 °, contact angle of the silicone oil in the fabric surface
It is 151.2 °
(9) heat-proof quality of the high temperature insulating flame-retardant textile of test braiding.Fabric is placed in the same thermal station and is carried out
Compare.When thermal station is from when being heated to 220 DEG C for 50 DEG C, obtain a series of infrared images, when thermal station temperature is respectively 50 DEG C, 100 DEG C,
At 150 DEG C, 200 DEG C, 220 DEG C, tool there are five typical image, as shown in figure 9, infrared image can be obtained substrate ambient temperature and
The mean temperature of fabric surface.Figure 10 has counted thermal station base reservoir temperature and fabric surface temperature, and temperature difference is bigger, then thermal insulation
It can be better.
Embodiment 13
(1) 8.0096g ODA (4,4 '-diaminodiphenyl ether) and 95.57g DMAc (dimethyl acetamide) are sufficiently stirred
It mixes, when ODA is completely dissolved, 8.8556g PMDA (pyromellitic acid anhydride) and 4.0476g TEA (triethylamine) is then added,
4 hours are mixed to generate sticky faint yellow PAS (polyamic acid salt) solution.PAS solution is poured slowly into water, is washed
After washing, freeze-drying obtains light yellow PAS solid.
(2) 5g TEA (triethylamine) and 85g deionized water are added into 10g PAS, gained suspension is continuously stirred into number
Hour, the static mass fraction that obtains for 24 hours is 10%PAS hydrogel after mixing.
(3) it is that 10% polyamic acid gel brine is placed in syringe by mass fraction, hydrogel is squeezed out by extruder pump,
Copper ring is placed in low-temp reaction bath (- 80 DEG C), and spinning passes through copper ring and carries out freezing-spinning process, and the fiber after freezing is used
Motor is collected.
(4) the freezing fiber for obtaining step (3) is freeze-dried for 24 hours to remove ice crystal, is obtained with orientation pore structure
Porous fibre；
(5) porous fibre is overheated sub- amidation, and specially at room temperature 2 DEG C/min is warming up to 100 DEG C, keeps 30min；With
2 DEG C/min is warming up to 200 DEG C, keeps 30min；300 DEG C are warming up to 2 DEG C/min, 60min is kept, obtains polyimide foraminous
Fiber has orientation porous structure, and SEM photograph is as shown in Figure 11.
(6) step (5) resulting porous fibre is placed in 1H, 1H, 2H, in 2H- perfluoro capryl triethoxysilane atmosphere,
Be vapor-deposited 12h, obtains super hydrophobic porous fiber.
(7) by super hydrophobic porous fibrage at fabric, using liquid such as contact angle instrument measurement water, silicone oil in fabric surface
Contact angle, test result show water the fabric surface contact angle be 153.2 °, contact angle of the silicone oil in the fabric surface
It is 151.3 °
Embodiment 14
(1) 8.0096g ODA (4,4 '-diaminodiphenyl ether) and 95.57g DMAc (dimethyl acetamide) are sufficiently stirred
It mixes, when ODA is completely dissolved, 8.8556g PMDA (pyromellitic acid anhydride) and 4.0476g TEA (triethylamine) is then added,
4 hours are mixed to generate sticky faint yellow PAS (polyamic acid salt) solution.PAS solution is poured slowly into water, is washed
After washing, freeze-drying obtains light yellow PAS solid.
(2) 5g TEA (triethylamine) and 90g deionized water are added into 5g PAS, gained suspension is continuously stirred several small
When, the static mass fraction that obtains for 24 hours is 5%PAS hydrogel after mixing.
(3) it is that 5% polyamic acid gel brine is placed in syringe by mass fraction, hydrogel is squeezed out by extruder pump,
Copper ring is placed in low-temp reaction bath (- 40 DEG C), and spinning passes through copper ring and carries out freezing-spinning process, and the fiber after freezing is used
Motor is collected.
(4) the freezing fiber for obtaining step (3) is freeze-dried for 24 hours to remove ice crystal, is obtained with orientation pore structure
Porous fibre；
(5) porous fibre is overheated sub- amidation, and specially at room temperature 2 DEG C/min is warming up to 100 DEG C, keeps 30min；With
2 DEG C/min is warming up to 200 DEG C, keeps 30min；300 DEG C are warming up to 2 DEG C/min, 60min is kept, obtains polyimide foraminous
Fiber has orientation porous structure, and SEM photograph is as shown in Figure 12.
(6) step (5) resulting porous fibre is placed in 1H, 1H, 2H, in 2H- perfluoro capryl triethoxysilane atmosphere,
Be vapor-deposited 12h, obtains super hydrophobic porous fiber.
(7) by super hydrophobic porous fibrage at fabric, using liquid such as contact angle instrument measurement water, silicone oil in fabric surface
Contact angle, test result show water the fabric surface contact angle be 153.2 °, contact angle of the silicone oil in the fabric surface
It is 154.2 °.
Claims (9)
1. a kind of preparation method of the super hydrophobic porous fiber with orientation pore structure characterized by comprising
The preparation of spinning solution；
Spinning solution carries out spinning, and when spinning is oriented freezing, and is collected to fiber is freezed；
Freeze fiber removal ice crystal；
And surface super hydrophobic processing is carried out to porous fibre.
2. the preparation method of the super hydrophobic porous fiber with orientation pore structure according to claim 1, which is characterized in that
Include the following steps:
1) the natural polymer solution of spinning is prepared；The natural polymer solution includes carboxymethylcellulose sodium solution, forms sediment
One or more of powder solution, chitosan solution, fibroin solutions；
2) natural polymer solution is subjected to solution-polymerized SBR, when spinning is oriented freezing, and is collected to fiber is freezed；
3) freezing fiber carries out freeze-drying removal ice crystal, obtains the porous fibre with orientation pore structure；
4) porous fibre carries out surface super hydrophobic processing, obtains the super hydrophobic porous fiber with orientation pore structure.
3. the preparation method of the super hydrophobic porous fiber with orientation pore structure according to claim 1, which is characterized in that
Include the following steps:
(1) lotion to be polymerized is prepared；The lotion to be polymerized includes resin monomer, radical polymerization initiator, response type emulsification
Agent and thickener or the lotion to be polymerized include performed polymer, radical polymerization initiator, reactive emulsifier and thickening
Agent or the lotion to be polymerized include self-emulsifying performed polymer, radical polymerization initiator and thickener；
(2) lotion to be polymerized carries out milk thread, and when spinning is oriented freezing, and is collected to fiber is freezed；
(3) freezing fiber carries out polymerization reaction in low temperature environment；
(4) freezing fiber thaws and dries, and obtains the porous resin fiber with orientation pore structure；
(5) porous resin fiber carries out surface super hydrophobic processing, obtains the super hydrophobic porous fiber with orientation pore structure.
4. the preparation method of the super hydrophobic porous fiber with orientation pore structure according to claim 1, which is characterized in that
Include the following steps:
I prepares polyamic acid gel brine；
II polyamic acid gel brine carries out solution-polymerized SBR, and when spinning is oriented freezing, and collects freezing fiber；
III freezing fiber carries out freeze-drying removal ice crystal, obtains the porous fibre with orientation pore structure；
IV porous fibre obtains polyimide foraminous fiber after being overheated sub- amidation；
V polyimide foraminous fiber carries out surface super hydrophobic processing, obtains the super hydrophobic porous fiber with orientation pore structure.
5. the preparation method of the super hydrophobic porous fiber with orientation pore structure according to claim 1, which is characterized in that
The surface super hydrophobic processing includes: dip coating, vapour deposition process or wet-chemical sedimentation.
6. the preparation method of the super hydrophobic porous fiber with orientation pore structure according to claim 1, which is characterized in that
The orientation freezing specifically includes: spinning solution passes through low temperature copper ring, is oriented freezing after squeezing out in extruder pump；It is described
The temperature of low temperature copper ring is -120~0 DEG C.
7. what a kind of preparation method as described in claim 1~6 is any was prepared has the super-hydrophobic more of orientation pore structure
Hole fiber.
8. a kind of super hydrophobic porous fiber as claimed in claim 7 with orientation pore structure is preparing waterproof and oilproof fabric material
Application in material.
9. a kind of application of super hydrophobic porous fiber as claimed in claim 7 with orientation pore structure as heat-barrier material.
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