CN116905111A - Transparent physical gel fiber and preparation method and application thereof - Google Patents
Transparent physical gel fiber and preparation method and application thereof Download PDFInfo
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- CN116905111A CN116905111A CN202311035393.5A CN202311035393A CN116905111A CN 116905111 A CN116905111 A CN 116905111A CN 202311035393 A CN202311035393 A CN 202311035393A CN 116905111 A CN116905111 A CN 116905111A
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- 239000000835 fiber Substances 0.000 title claims abstract description 134
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 99
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 99
- 238000000034 method Methods 0.000 claims abstract description 38
- 238000010257 thawing Methods 0.000 claims abstract description 30
- 238000007710 freezing Methods 0.000 claims abstract description 25
- 230000008014 freezing Effects 0.000 claims abstract description 24
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 20
- 230000002528 anti-freeze Effects 0.000 claims abstract description 9
- 239000011540 sensing material Substances 0.000 claims abstract description 5
- 239000011162 core material Substances 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 38
- 239000007788 liquid Substances 0.000 claims description 36
- 238000004804 winding Methods 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 15
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 13
- 238000002347 injection Methods 0.000 claims description 12
- 239000007924 injection Substances 0.000 claims description 12
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 5
- 235000011089 carbon dioxide Nutrition 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 25
- 239000002994 raw material Substances 0.000 abstract description 7
- 239000013307 optical fiber Substances 0.000 abstract description 4
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 239000000499 gel Substances 0.000 description 110
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000000017 hydrogel Substances 0.000 description 15
- 230000008961 swelling Effects 0.000 description 12
- 238000002834 transmittance Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- 235000002639 sodium chloride Nutrition 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 4
- 239000002657 fibrous material Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000010382 chemical cross-linking Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000012792 core layer Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005185 salting out Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 230000002459 sustained effect Effects 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000009777 vacuum freeze-drying Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
The invention provides a transparent physical gel fiber and a preparation method and application thereof, wherein the preparation method of the transparent physical gel fiber comprises the following steps: extruding the polyvinyl alcohol gel solution into a condensing bath for cold forming, drawing out the formed product, and then thawing; wherein, the polyvinyl alcohol gel solution contains salt-soluble and antifreeze inorganic salt. The material involved in the method is nontoxic and harmless, the raw materials are simple, the preparation method is simple and easy to implement, the fiber is formed rapidly, the preparation process is green and environment-friendly, and the method is an efficient method for preparing the transparent physical gel fiber. The transparent physical gel fiber prepared by the method has the excellent performances of high elasticity, high transparency, high ductility, water retention, adhesiveness, freezing resistance, ion conductivity, light conductivity and the like, and further expands the fields of flexible sensing materials and optical fiber core materials of the polyvinyl alcohol gel fiber.
Description
Technical Field
The invention relates to the field of preparation of high polymer materials, in particular to a transparent physical gel fiber and a preparation method and application thereof.
Background
Any discussion of the prior art throughout the specification should in no way be considered as an admission that such prior art is widely known or forms part of common general knowledge in the field.
The polymer gel fiber is a polymer fiber of a system formed by a three-dimensional network formed by crosslinking polymerization of molecular chains and a solvent, has higher water content, certain water retention capacity or better mechanical property compared with other types of fibers, can have different properties according to different solvent types, and has great potential to be widely applied to the fields of agriculture, industry, medical and health, intelligent materials and the like.
At present, the traditional gel fiber preparation method comprises wet spinning, mold forming and other methods, and mainly comprises two major types of physical gel fibers and chemical gel fibers, wherein the chemical gel fibers have potential application value in the emerging field due to the high transparency, flexibility and other advantages, but have the defects of complex process steps, complex raw materials, chemical residues and the like, and become the main problems in the practical application process; for example, polyacrylamide gel fibers require ultraviolet light equipment for crosslinking, and the gel fibers have residual chemical reagents such as unreacted initiator and crosslinking agent. Chinese patent application CN201910634863.7 discloses a preparation method of hydrogel fiber, which comprises polymerizing a polymerization system of reactive monomer containing quadruple hydrogen bond and double bond, cross-linking agent, and acrylamide, and injecting the solution into deionized water by needle to obtain hydrogel fiber. However, the crosslinking method adopted by the gel fiber is chemical crosslinking, and the used chemical crosslinking agent is at least one selected from the block copolymers F127, so that the prepared gel fiber has residual crosslinking agent, has potential safety hazards and is limited to be applied to biomedicine and the like. The Chinese patent application CN202210227801.6 discloses a preparation method of stretchable elastic conductive polymer-based hydrogel fiber, which comprises the steps of mixing an elastic polymer matrix, aniline monomer, acid solution, sodium alginate solution and initiator solution to obtain spinning solution, extruding the spinning solution into a coagulating bath in which divalent or trivalent non-oxidant metal salt is dissolved to obtain hydrogel fiber, performing instant freezing on the hydrogel fiber, performing in-situ polymerization and crosslinking reaction, and thawing to obtain stretchable elastic conductive polymer-based hydrogel fiber, wherein the prepared gel fiber has certain mechanical strength, ductility and conductivity. However, the gel fiber prepared by the method is still not high enough in elasticity, low in stretching multiple, complex in preparation steps and easy to produce residues of other substances, and the prepared gel fiber is in an opaque state. The physical gel fibers are few in variety, are poor in opacity and flexibility, have single functions and the like, and cannot meet the performance requirements of practical application. Therefore, high performance, multifunctional physical gel fibers are in need of development.
Disclosure of Invention
Accordingly, the invention aims to provide a transparent physical gel fiber, and a preparation method and application thereof. The transparent physical gel fiber is obtained by taking polyvinyl alcohol, salt-soluble/antifreeze inorganic salt and water as raw materials, forming in a transient freezing mode and rapidly thawing, and has the advantages of high elasticity, high transparency and adhesiveness, high ductility, water retention, antifreeze property, ionic conductivity and the like, and greatly expands the application of the polyvinyl alcohol gel fiber in the fields of flexible sensing materials and optical fiber core layer materials. In addition, the material related to the preparation method is nontoxic and harmless, the raw materials are simple, the preparation method is simple and easy to implement, the fiber is rapidly formed, the gel fiber finished product can be obtained after about 10 minutes, the preparation process is environment-friendly, and the method is an efficient and stable method for preparing the transparent physical gel fiber. In addition, the diameter and mechanical properties of the transparent physical gel fiber can be effectively regulated and controlled by regulating and controlling the concentration of polyvinyl alcohol, the content of inorganic salt with salt solubility/freezing resistance, the pushing speed and pulling speed of an injection device, the aperture of the injection device and the like, so that the method is more flexible.
Specifically, the invention provides the following technical scheme.
In a first aspect of the present invention, there is provided a method of preparing transparent physical gel fibers comprising: extruding the polyvinyl alcohol gel precursor liquid into a condensing bath for cold forming, drawing out a formed product, thawing, winding and collecting;
wherein the polyvinyl alcohol gel solution contains a salt-soluble/antifreeze inorganic salt (also referred to herein as a salt-soluble/antifreeze inorganic salt).
In an embodiment of the invention, the condensation bath is liquid nitrogen or dry ice, more preferably liquid nitrogen. Compared with other freezing environments or freezing modes, the condensing bath provided by the invention can be used for instantly freezing and forming the polyvinyl alcohol gel precursor liquid, and liquid nitrogen or dry ice can provide more stable temperature and faster freezing speed, and particularly, when liquid nitrogen is frozen, the ice crystals formed by water are tiny and uniform, and a homogeneous microstructure is more easily obtained.
Unlike chemical crosslinking, the present invention prepares gel fiber through physical crosslinking, and has simplified technological process, high efficiency, no toxicity and no chemical solvent residue.
In addition, the inventor tries to prepare the polyvinyl alcohol/inorganic salt hydrogel by using a circulating freeze-thaw method in the research process, and then obtains gel fibers by stretching and fixing orientation, so that the prepared fibers have certain excellent characteristics, such as special-shaped cross section, high mechanical strength and high water content, however, the method cannot prepare the gel long fibers, the time required for freezing and thawing the polyvinyl alcohol/inorganic salt precursor liquid is long, often exceeds 1 day, continuous and large-scale preparation cannot be realized, and the obtained polyvinyl alcohol fibers are opaque and non-adhesive, which can limit the application of the polyvinyl alcohol fibers in the requirements of transparency and adhesiveness. The invention adopts a low-temperature condensing bath mode to carry out quick freezing molding on the extruded polyvinyl alcohol gel solution, and pulls out and quick defreezes, the method can obtain a fiber finished product about 10 minutes, the preparation steps are simple, the efficiency is high, the microstructure of the prepared gel fiber presents a homogeneous state, the prepared gel fiber has good flexibility, and a plurality of excellent properties including excellent properties such as high elasticity, high transparency, adhesiveness, high ductility, water retention, freezing resistance, ion conductivity, light conductivity and the like can be considered, so that the application field is greatly expanded. In some embodiments of the present invention, the number average molecular weight of the raw material polyvinyl alcohol is 7000 to 200000, the alcoholysis degree is 80 to 99.9%, and the polyvinyl alcohol raw material may be 1799, 2099, 2299, 2499, 2699, 1788 type polyvinyl alcohol, etc.; in embodiments of the invention, the molecular weight of the polyvinyl alcohol affects the mechanical properties of the fibers, and relatively higher molecular weights of the polyvinyl alcohol result in relatively stronger mechanical properties. The salt-soluble inorganic salt is one or more selected from calcium chloride, lithium chloride, zinc chloride and magnesium chloride. The salt-soluble and freeze-resistant inorganic salt is different from inorganic salts commonly used for salting out, such as sodium sulfate, magnesium sulfate, ammonium sulfate, sodium chloride, sodium citrate and the like, and the inventor finds that the salting-out inorganic salt often induces water loss of hydrogel to reduce the water content of the hydrogel in research, so that the technical effect of the invention cannot be realized.
In some embodiments of the invention, the concentration of polyvinyl alcohol in the polyvinyl alcohol gel solution is 10wt% to 35wt%, and the concentration of the salt-soluble, freeze-resistant inorganic salt is 1mol/L to 5mol/L. In a more preferred embodiment, the concentration of polyvinyl alcohol in the polyvinyl alcohol gel solution is 15wt% to 20wt%; the concentration of the salt-soluble and freezing-resistant inorganic salt is 2mol/L to 3mol/L. The concentration of the polyvinyl alcohol refers to the concentration of the polyvinyl alcohol in the solvent after the polyvinyl alcohol is dissolved in the solvent, for example, for a ternary system, assuming that the mass of salt-soluble, antifreeze inorganic salt, polyvinyl alcohol and water (solvent) are a, b and c respectively, the concentration of the polyvinyl alcohol solution is [ b/(b+c) ]. 100%. In some embodiments of the invention, the concentration of polyvinyl alcohol affects the mechanical properties of the fibers, and relatively higher concentrations of polyvinyl alcohol result in relatively stronger mechanical properties. In some embodiments of the invention, the concentration of the salt-soluble, freeze-resistant inorganic salt affects the flexibility, transparency, and freeze resistance of the resulting fiber, and a relatively higher concentration of the salt-soluble, freeze-resistant inorganic salt helps to achieve relatively better flexibility, transparency, and freeze resistance.
In some embodiments of the invention, the extrusion may employ a push injection device having a nozzle tip with an inner diameter of 5 μm to 2500 μm, preferably 500 μm to 2000 μm; the diameter of the formed object can be adjusted by adjusting the inner diameter of the spray head. For example, in some embodiments, the push injection device may be a spinneret plate or a syringe, or the like, but is not limited thereto. Compared with an injector, the spinneret plate has higher yield, and a proper pushing injection device can be selected according to the requirement.
In some embodiments of the invention, the extrusion is carried out at a uniform speed, wherein the speed of advance is from 0.1mm/s to 100mm/s, preferably from 0.2mm/s to 10mm/s.
In some embodiments of the invention, the speed at extraction is from 0.1mm/s to 100mm/s.
In embodiments of the present invention, the diameter of the fibers may be adjusted by adjusting the injection rate and the withdrawal rate.
In some embodiments of the invention, normal temperature thawing is adopted for thawing, the thawing time is 0.5-5 min, and the thawing is rapid, thereby greatly improving the gel fiber preparation efficiency. The normal temperature is defined to cover a temperature range of 5-30 deg.c, such as thawing in an environment conforming to the temperature, such as thawing at room temperature of 15-25 deg.c, unless specified otherwise.
In some embodiments of the invention, the time of cold forming in the condensing bath is from 0.5min to 15min, preferably from 1min to 5min.
In some embodiments of the present invention, the method for preparing the high elasticity polyvinyl alcohol gel fiber comprises: preparing a salt-soluble and freezing-resistant inorganic salt aqueous solution, adding polyvinyl alcohol, stirring and uniformly mixing, and then defoaming to obtain a polyvinyl alcohol gel precursor solution; and (3) uniformly extruding the polyvinyl alcohol gel solution to a condensing bath for cold forming, uniformly pulling out the formed product, thawing, and finally winding and collecting. The speed of the winding is 0.1mm/s to 150mm/s. In some embodiments of the invention, the polyvinyl alcohol may be pre-swollen, stirred at elevated temperature, and the process may be operated in a manner conventional in the art. The defoaming mode can be ultrasonic, vacuum or static.
In a second aspect of the present invention, there is provided a transparent physical gel fiber prepared by the preparation method described in the first aspect. The microstructure of the high-elasticity polyvinyl alcohol gel is in a homogeneous state, has flexibility and high transparency, overcomes the defects of low flexibility and poor transparency caused by a traditional physical gel heterogeneous structure, ensures that the elongation at break of the obtained fiber can reach 1200%, the light transmittance is as high as 90%, the water content is only lost by 10% within 7 days to be constant, and simultaneously has adhesiveness, ion conductivity and excellent light conductivity, and the freezing resistance temperature reaches minus 60 ℃.
In addition, the transparent physical gel fiber can be used for preparing the high-elasticity polyvinyl alcohol gel functional fiber by further compounding functional particles (such as graphene, carbon nano tubes, MXene and the like), and the preparation method of the gel functional fiber mainly comprises the steps of adding the functional particles into the prepared polyvinyl alcohol gel precursor liquid or adding the functional particles in the process of preparing the polyvinyl alcohol gel precursor liquid (such as after adding the polyvinyl alcohol), stirring uniformly, then carrying out defoaming treatment, then carrying out uniform-speed extrusion to a condensing bath for freezing molding, and uniformly pulling out and thawing a molded product to obtain the transparent high-elasticity polyvinyl alcohol gel functional fiber. In some embodiments of the present invention, the resulting functional fibers have good overall properties, and the addition of the composite functional particles can further improve the conductivity of the fibers, but the transparency is somewhat reduced, but still good.
In a third aspect of the present invention, the present invention provides the use of the transparent physical gel fiber described in the second aspect in the field of flexible sensing materials, gel fiber optical fiber core materials, such as skin-like sensors, soft robots, biomedical and the like, in particular in the field of flexible materials where there is a need for properties of transparency, adhesion, high elasticity, light conduction and the like.
Compared with the prior art, the invention has the advantages that:
the material involved in the method for preparing the high-elasticity polyvinyl alcohol gel fiber is nontoxic and harmless, the raw materials are simple, the preparation method is simple and easy to implement, the fiber is rapidly formed, the preparation process is environment-friendly, and the method is an efficient method for preparing the high-elasticity polyvinyl alcohol gel fiber. In addition, according to the method provided by the invention, the diameter and mechanical properties of the high-elasticity polyvinyl alcohol gel fiber can be effectively regulated and controlled only by regulating and controlling the concentration of the polyvinyl alcohol, the salt solubility, the content of the antifreeze inorganic salt, the pushing speed and pulling speed of the injection device and the aperture of the injection device.
In addition, the high-elasticity polyvinyl alcohol gel fiber prepared by the method has the excellent performances of high elasticity, high transparency, high ductility, water retention, adhesiveness, freezing resistance, ion conductivity, light conductivity and the like, and the application of the polyvinyl alcohol gel fiber in the fields of flexible sensing materials and gel fiber optical fiber core layer materials is further expanded.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. Embodiments of the present invention are described in detail below with reference to the attached drawing figures, wherein:
fig. 1: example 1 microscopic images of longitudinal section (a) and cross section (B) of a highly elastic polyvinyl alcohol gel fiber, from which it is seen that the microstructure of the fiber material of example 1 exhibits a homogeneous state and exhibits flexibility and high transparency.
Fig. 2: example 2 microscopic images of the longitudinal section (a) and the cross section (B) of the highly elastic polyvinyl alcohol gel fiber, it is understood from the images that the microstructure of the fiber material of example 2 exhibits a homogeneous state and exhibits flexibility and high transparency, and the difference is mainly in the diameter of the fiber as compared with the fiber of example 1.
Fig. 3: mechanical stretching curves of the high-elasticity polyvinyl alcohol gel fibers obtained in examples 1 and 4. It can be seen from the curves that both materials are ductile materials that are capable of greater deformation without fracture when under tension, and that both materials have similar tensile strength and fracture strain, as well as similar toughness, but example 1 has a lower elastic modulus and yield strength than example 4. Wherein a higher modulus of elasticity means a higher stiffness of the material, i.e. a higher stress required per unit strain, the more difficult the material is to be stretched or compressed. The lower the modulus of elasticity, the higher the compliance of the material, i.e., the greater the strain developed under a unit stress, the more easily the material is stretched or compressed. The greater the yield strength, the lower the plastic deformability of the material, i.e. the greater the maximum stress that can be sustained before the yield point is reached, the more difficult the material is to permanently deform. The smaller the yield strength, the higher the plastic deformability of the material, i.e. the smaller the maximum stress that can be sustained before reaching the yield point, the more easily the material is permanently deformed.
Fig. 4: mechanical stretching curves of the high-elasticity polyvinyl alcohol gel fibers obtained in example 1 and comparative example 1. The material of comparative example 1 reached maximum stress when the strain reached about 200%, then dropped rapidly, which indicated that the material was brittle and easily broken after being stretched to some extent, compared to the material of example 1, which reached maximum stress when the strain reached about 1200%, then dropped slowly, which indicated that the material had good toughness, and was able to withstand greater stretching without breaking, and had good deformability.
Fig. 5: the high elastic polyvinyl alcohol gel fiber obtained in example 1 had a drawing cycle curve in which the strain was increased stepwise by 100% (a) and 50 times (B) at 200% strain.
Fig. 6: the high elasticity polyvinyl alcohol gel obtained in example 1 was wound around a finger to give a digitally represented sensing curve.
Fig. 7: the high elasticity polyvinyl alcohol gel fiber obtained in example 1 was knitted, and the sensing curve when the object was landed thereon.
Fig. 8: macroscopic photograph of the high elastic polyvinyl alcohol gel fiber winding obtained in example 1.
Fig. 9: macroscopic photograph of the high elasticity polyvinyl alcohol gel fiber weave obtained in example 1.
Fig. 10: the high-elasticity polyvinyl alcohol gel fiber obtained in example 1 had a light transmission property of 470nm (A), 533nm (B), 635nm (C) for light of different wavelengths; the polyvinyl alcohol gel fiber obtained in comparative example 1 had a light conductivity of 533nm (D).
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The experimental procedures, which do not address the specific conditions in the examples below, are generally carried out under conventional conditions or under conditions recommended by the manufacturer.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The reagents or materials used in the present invention may be purchased in conventional manners, and unless otherwise indicated, they may be used in conventional manners in the art or according to the product specifications. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred methods and materials described herein are presented for illustrative purposes only.
In the present invention, the following methods are used for the relevant tests, unless otherwise specified:
tensile test: tensile testing was performed using a tensile tester (WDS-X) and stretching was performed at 50mm/min until fracture.
Transparency test: the visible light transmittance of the polyvinyl alcohol hydrogel fiber was measured by an ultraviolet-visible light spectrophotometer (UV-vis T9), the test wavelength range was 200-800nm, and the optical transmittance was recorded at 700 nm.
And (3) water loss test: the equilibrium water loss rate of the polyvinyl alcohol hydrogel fiber samples at constant temperature (t=20 ℃, rh=60%) was recorded.
Example 1
Preparing a calcium chloride solution with the concentration of 3mol/L, continuously adding 16wt% of polyvinyl alcohol (Mw=70000), pre-swelling, stirring at a high temperature, uniformly mixing, ultrasonically defoaming, and preparing a gel solution with good fluidity.
Transferring the gel solution to a step injector, injecting liquid nitrogen at a constant speed of 0.5mm/s for rapid freezing and forming, drawing the formed frozen gel fiber in the liquid nitrogen for 2min at a speed of 0.1mm/s, thawing for 5min at room temperature, winding and collecting at a winding speed of 0.1mm/s, and obtaining the high-elasticity polyvinyl alcohol gel fiber with a diameter of 2.5mm. The microstructure of the obtained fiber material is in a homogeneous state and has flexibility and high transparency, the elongation at break is 1200% and the light transmittance is 90% after being measured, the water content is constant after the fiber material is placed for 7 days at room temperature and the water content is lost by 10%, and the freezing resistance temperature reaches-60 ℃. The cross-section microscopic image is shown in fig. 1, the mechanical stretching curve is shown in fig. 3, the stretching cycle curve is shown in fig. 5, the sensing curve is shown in fig. 6 and 7, the macroscopic photograph of the fiber during winding is shown in fig. 8, the macroscopic photograph of the fiber after weaving is shown in fig. 9, and the conductive performance of the fiber to light at different wavelengths is shown in fig. 10.
Example 2
Preparing a calcium chloride solution with the concentration of 3mol/L, continuously adding 16wt% of polyvinyl alcohol (Mw=70000), pre-swelling, stirring at a high temperature, uniformly mixing, ultrasonically defoaming, transferring the obtained gel solution to a step injector, injecting liquid nitrogen at a constant speed of 10mm/s for rapid freeze-forming, drawing the formed frozen gel fiber in the liquid nitrogen for 2min at a speed of 5mm/s, thawing at room temperature for 5min, winding and collecting at a winding speed of 5mm/s, and obtaining the high-elasticity polyvinyl alcohol gel fiber with the diameter of 3.6mm. The microstructure of the resulting fiber, which is shown in fig. 2 as a cross-sectional microscopic image, exhibited a homogeneous state and exhibited flexibility and high transparency, was different from that of example 1 mainly in the diameter of the fiber.
Example 3
Preparing a calcium chloride solution with the concentration of 3mol/L, continuously adding 16wt% of polyvinyl alcohol (Mw=70000), pre-swelling, stirring at high temperature, uniformly mixing, ultrasonically defoaming, transferring the obtained gel solution to a step injector, injecting liquid nitrogen at a constant speed of 0.5mm/s for rapid freeze-forming, drawing the formed frozen gel fiber in the liquid nitrogen at a speed of 0.1mm/s, thawing at room temperature for 5min, winding and collecting, and winding at a speed of 0.1mm/s to obtain the high-elasticity polyvinyl alcohol gel fiber. The properties of the resulting fibers were substantially identical to those of example 1.
Example 4
Preparing a calcium chloride solution with the concentration of 1mol/L, continuously adding 16wt% of polyvinyl alcohol (Mw=70000), pre-swelling, stirring at high temperature, uniformly mixing, ultrasonically defoaming, transferring the obtained gel solution to a step injector, injecting liquid nitrogen at a constant speed of 0.5mm/s for rapid freeze-forming, drawing the formed frozen gel fiber in the liquid nitrogen at a speed of 0.1mm/s, thawing at room temperature for 5min, winding and collecting, and winding at a speed of 0.1mm/s to obtain the high-elasticity polyvinyl alcohol gel fiber. The difference between the obtained fibers and example 1 is mainly that the flexibility, transparency and anti-freezing property are slightly reduced. The elongation at break was measured to be 600% and the light transmittance 65%. The mechanical stretching curve is shown in fig. 3.
Example 5
Preparing a lithium chloride solution with the concentration of 3mol/L, continuously adding 16wt% of polyvinyl alcohol (Mw=70000), pre-swelling, stirring at high temperature, uniformly mixing, ultrasonically defoaming, transferring the obtained gel solution to a step injector, injecting liquid nitrogen at a constant speed of 0.5mm/s for rapid freeze-forming, drawing the formed frozen gel fiber in the liquid nitrogen at a speed of 0.1mm/s, thawing at room temperature for 5min, winding and collecting, and winding at a speed of 0.1mm/s to obtain the high-elasticity polyvinyl alcohol gel fiber. The properties of the resulting fibers were substantially identical to those of example 1.
Example 6
Preparing a calcium chloride solution with the concentration of 3mol/L, continuously adding 10wt% of polyvinyl alcohol (Mw=70000), pre-swelling, stirring at high temperature, uniformly mixing, ultrasonically defoaming, transferring the obtained gel solution to a step injector, injecting liquid nitrogen at a constant speed of 0.5mm/s for rapid freeze-forming, drawing the formed frozen gel fiber in the liquid nitrogen at a speed of 0.1mm/s, thawing at room temperature for 5min, winding and collecting, and winding at a speed of 0.1mm/s to obtain the high-elasticity polyvinyl alcohol gel fiber. The difference between the obtained fibers and example 1 is mainly that the mechanical properties are slightly reduced. Elongation at break was measured to be 370%.
Example 7
Preparing a calcium chloride solution with the concentration of 3mol/L, continuously adding 16wt% of polyvinyl alcohol (Mw=140000), pre-swelling, stirring at a high temperature, uniformly mixing, ultrasonically defoaming, transferring the obtained gel solution to a step injector, injecting liquid nitrogen at a constant speed of 0.5mm/s for rapid freeze-forming, drawing the formed frozen gel fiber in the liquid nitrogen at a speed of 0.1mm/s, thawing at room temperature for 5min, winding and collecting, and winding at a speed of 0.1mm/s to obtain the high-elasticity polyvinyl alcohol gel fiber. Compared with the example 1, the obtained fiber mainly has slightly enhanced mechanical properties, and the elongation at break is 700 percent.
Example 8
Preparing a calcium chloride solution with the concentration of 3mol/L, continuously adding 16wt% of polyvinyl alcohol (Mw=70000), pre-swelling, stirring at high temperature, uniformly mixing, ultrasonically defoaming, transferring the obtained gel solution to a spinneret plate, injecting the gel solution into liquid nitrogen at a constant speed at a propulsion speed of 0.5mm/s for rapid freeze-forming, drawing the formed frozen gel fiber in the liquid nitrogen at a speed of 0.1mm/s, thawing the frozen gel fiber at room temperature for 5min, and collecting the frozen gel fiber in a winding way at a winding speed of 0.1mm/s to obtain the high-elasticity polyvinyl alcohol gel fiber. The properties of the resulting fibers are substantially identical to those of example 1.
Example 9
Preparing a calcium chloride solution with the concentration of 3mol/L, continuously adding 16wt% of polyvinyl alcohol (Mw=70000), pre-swelling, stirring at high temperature, uniformly mixing, ultrasonically defoaming, transferring the obtained gel solution to a step injector, injecting the gel solution into a dry ice environment at a constant speed of 0.5mm/s for rapid freeze molding, drawing the molded frozen gel fiber out at a speed of 0.1mm/s in the dry ice environment for 5min, and collecting the gel fiber after winding at a winding speed of 0.1mm/s to obtain the high-elasticity polyvinyl alcohol gel fiber. The properties of the resulting fibers are substantially identical to those of example 1.
Example 10
Preparing a calcium chloride solution with the concentration of 3mol/L, continuously adding 16wt% of polyvinyl alcohol (Mw=70000), pre-swelling, stirring at high temperature, adding carbon nano tube particles into the solution, uniformly mixing, ultrasonically defoaming, transferring the obtained mixed solution to a step injector, injecting liquid nitrogen into the solution at a uniform speed of 0.5mm/s for rapid freeze-forming, drawing the formed frozen gel fiber in the liquid nitrogen at a speed of 0.1mm/s for 2min, thawing at room temperature for 5min, winding and collecting, and winding at a speed of 0.1mm/s to obtain the high-elasticity polyvinyl alcohol gel functional fiber. The resultant fiber had slightly lower transparency than example 1, but had good overall properties, and in particular, had more excellent conductivity. The light transmittance was measured to be 70%.
Comparative example 1
A polyvinyl alcohol solution (mw=70000) with a concentration of 16wt% was prepared, pre-swollen, stirred at high temperature, uniformly mixed, ultrasonically defoamed, and a gel solution was prepared, and the prepared solution had fluidity, transparency and freezing resistance.
Transferring the gel solution to a step injector, injecting liquid nitrogen at a constant speed at a propulsion speed of 0.5mm/s for rapid freezing and molding, drawing the molded frozen gel fiber in the liquid nitrogen for 2min at a speed of 0.1mm/s, thawing for 5min at room temperature, collecting by winding at a winding speed of 0.1mm/s to obtain gel fiber which is opaque, non-adhesive, poor in ion conductivity, high in fiber brittleness, low in elongation at break, easy to break after stretching, incapable of achieving high elasticity, 260% in elongation at break after measuring, 5% in light transmittance, and constant in water content after a water content loss of 78% after being placed at room temperature for 7 days, wherein a mechanical stretching curve is shown in fig. 4, and a light conduction function is relatively poor at most wavelengths, and a light conduction example at 533nm wavelength is achieved, and a result is shown as D in fig. 10.
Comparative example 2
Preparing a calcium chloride solution with the concentration of 3mol/L, continuously adding 16wt% of polyvinyl alcohol (Mw=70000), pre-swelling, stirring at high temperature, uniformly mixing, ultrasonically defoaming, transferring the obtained mixed solution to a stepping injector, extruding into a culture dish at a uniform speed of 0.5mm/s, putting into a refrigerator with the temperature of minus 20 ℃ for freezing-thawing circulation, wherein the freezing temperature is minus 20 ℃, the freezing time is 12h, thawing at 25 ℃ for 12h, and the number of times of freezing-thawing circulation is 3. After thawing, the hydrogel is obtained.
And drying the obtained hydrogel in a constant temperature and humidity box for 24 hours at a drying temperature of 20 ℃ and a drying humidity of 60%, so as to prepare the hydrogel film. Cutting the hydrogel film into strips with square cross section, pre-stretching the strips for 6 times, and fixing at 1.5mol/L Na concentration 2 SO 4 Soaking in the solution for 3 hours to prepare the polyvinyl alcohol gel fiber.
The fiber diameter of the product is 0.5mm, the water content is 38.8%, the mechanical strength is 8.0MPa, and the product has a special-shaped section (the sheath/core ratio is 62%), but has no adhesiveness and is opaque.
Comparative example 3
Preparing a calcium chloride solution with the concentration of 3mol/L, continuously adding 16wt% of polyvinyl alcohol (Mw=70000), pre-swelling, stirring at a high temperature, uniformly mixing, and ultrasonically defoaming to prepare the gel solution. The gel solution is transferred to a step injector, pushed out at a constant speed of 0.5mm/s and then enters into 1.5mol/L sodium sulfate aqueous solution, and the polyvinyl alcohol gel fiber is obtained, and the fiber is opaque, inelastic and light-guiding.
Further, the polyvinyl alcohol gel fiber is subjected to vacuum freeze drying to obtain the polyvinyl alcohol aerogel fiber, and the fiber is inelastic, opaque, lost in flexibility and not light-guiding.
The foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method of preparing a transparent physical gel fiber, comprising: extruding the polyvinyl alcohol gel precursor liquid into a condensing bath for cold forming, then pulling out and thawing, and winding and collecting; wherein, the polyvinyl alcohol gel precursor liquid contains salt-soluble and antifreeze inorganic salt; the salt-soluble and freeze-resistant inorganic salt is one or more of calcium chloride, magnesium chloride, zinc chloride and lithium chloride; the condensing bath is liquid nitrogen or dry ice.
2. The method according to claim 1, wherein the polyvinyl alcohol gel precursor liquid is a mixed aqueous solution of a salt-soluble, antifreeze inorganic salt and polyvinyl alcohol;
wherein the concentration of the polyvinyl alcohol in the polyvinyl alcohol gel precursor liquid is 10-35 wt%, and the concentration of the salt-soluble and freezing-resistant inorganic salt is 0.5-5 mol/L.
3. The method according to claim 1, wherein the extrusion is performed by a push injection device, and the nozzle of the injection device has an inner diameter of 5 μm to 2500 μm.
4. The method according to claim 1, wherein the extrusion speed is 0.1mm/s to 100mm/s; the pulling-out speed is 0.1 mm/s-100 mm/s; the winding speed is 0.1mm/s to 150mm/s.
5. The method according to claim 1, wherein the time for cold forming in the condensing bath is 0.5 to 15 minutes.
6. The preparation method according to claim 1, wherein thawing is performed at normal temperature for 0.5 to 5 minutes.
7. The production method according to any one of claims 1 to 6, characterized in that the method comprises: preparing a salt-soluble and freezing-resistant inorganic salt aqueous solution, adding polyvinyl alcohol, stirring and uniformly mixing, and then defoaming to obtain a polyvinyl alcohol gel precursor solution; transferring the polyvinyl alcohol gel precursor solution to a propulsion injection device, extruding the polyvinyl alcohol gel precursor solution to a condensing bath at uniform speed for cold forming, drawing out the formed product at uniform speed, thawing, and winding and collecting the thawed product.
8. The production method according to any one of claims 1 to 6, characterized in that the method comprises: functional particles are added into the polyvinyl alcohol gel precursor liquid or are added in the process of preparing the polyvinyl alcohol gel precursor liquid, the defoaming treatment is carried out after the uniform stirring, the mixed solution is transferred to a propulsion injection device and extruded to a condensing bath at uniform speed for cold forming, and the formed product is unfrozen after being pulled out at uniform speed and wound for collection after being unfrozen.
9. Transparent physical gel fiber prepared by the preparation method of any one of claims 1 to 8.
10. Use of the transparent physical gel fiber of claim 9 in the field of flexible sensing materials, fiber core materials.
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