CN105297289B - A kind of fibroin albumen energy-saving and temperature-regulating fiber membrane preparation method - Google Patents
A kind of fibroin albumen energy-saving and temperature-regulating fiber membrane preparation method Download PDFInfo
- Publication number
- CN105297289B CN105297289B CN201510888419.XA CN201510888419A CN105297289B CN 105297289 B CN105297289 B CN 105297289B CN 201510888419 A CN201510888419 A CN 201510888419A CN 105297289 B CN105297289 B CN 105297289B
- Authority
- CN
- China
- Prior art keywords
- silk fibroin
- regenerated silk
- aqueous solution
- energy storage
- fiber membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 108010022355 Fibroins Proteins 0.000 title claims abstract description 93
- 239000000835 fiber Substances 0.000 title claims abstract description 50
- 239000012528 membrane Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000003094 microcapsule Substances 0.000 claims abstract description 41
- 238000004146 energy storage Methods 0.000 claims abstract description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000725 suspension Substances 0.000 claims abstract description 24
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000012071 phase Substances 0.000 claims abstract description 22
- 230000008859 change Effects 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 239000000839 emulsion Substances 0.000 claims abstract description 10
- 239000012074 organic phase Substances 0.000 claims abstract description 7
- 238000002844 melting Methods 0.000 claims abstract description 3
- 230000008018 melting Effects 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 26
- 238000009987 spinning Methods 0.000 claims description 23
- 230000033228 biological regulation Effects 0.000 claims description 20
- 239000002736 nonionic surfactant Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 239000003945 anionic surfactant Substances 0.000 claims description 6
- 230000001804 emulsifying effect Effects 0.000 claims description 6
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000012782 phase change material Substances 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 5
- 239000003995 emulsifying agent Substances 0.000 claims description 5
- 241000255789 Bombyx mori Species 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000007710 freezing Methods 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
- 238000005338 heat storage Methods 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 230000008439 repair process Effects 0.000 claims description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 125000005354 acylalkyl group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- -1 alkyl phenol Chemical compound 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 230000008876 conformational transition Effects 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 230000001939 inductive effect Effects 0.000 claims description 2
- 229920000136 polysorbate Polymers 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Chemical group 0.000 claims description 2
- 108090000623 proteins and genes Proteins 0.000 claims description 2
- 102000004169 proteins and genes Human genes 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 230000003068 static effect Effects 0.000 claims description 2
- 230000001954 sterilising effect Effects 0.000 claims description 2
- 238000004659 sterilization and disinfection Methods 0.000 claims description 2
- 238000010257 thawing Methods 0.000 claims description 2
- 239000001993 wax Substances 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims 1
- 239000000194 fatty acid Substances 0.000 claims 1
- 229930195729 fatty acid Natural products 0.000 claims 1
- 150000004665 fatty acids Chemical class 0.000 claims 1
- 239000011257 shell material Substances 0.000 claims 1
- 238000004945 emulsification Methods 0.000 abstract description 4
- 238000002347 injection Methods 0.000 abstract description 4
- 239000007924 injection Substances 0.000 abstract description 4
- 230000006698 induction Effects 0.000 abstract description 2
- 230000007423 decrease Effects 0.000 abstract 1
- 230000009466 transformation Effects 0.000 abstract 1
- 239000002131 composite material Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 6
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 6
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 239000011162 core material Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- 230000029663 wound healing Effects 0.000 description 3
- 229920001661 Chitosan Polymers 0.000 description 2
- 206010048038 Wound infection Diseases 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000012510 hollow fiber Substances 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000035900 sweating Effects 0.000 description 2
- 230000017423 tissue regeneration Effects 0.000 description 2
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 206010072170 Skin wound Diseases 0.000 description 1
- 206010052428 Wound Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 235000021120 animal protein Nutrition 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 229940124350 antibacterial drug Drugs 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 229920002674 hyaluronan Polymers 0.000 description 1
- 229960003160 hyaluronic acid Drugs 0.000 description 1
- 230000005847 immunogenicity Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000037314 wound repair Effects 0.000 description 1
Landscapes
- Artificial Filaments (AREA)
- Materials For Medical Uses (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
A kind of fibroin albumen energy-saving and temperature-regulating fiber membrane preparation method, comprises the following steps：Prepare the regenerated silk fibroin water solution A and B of two kinds of concentration of 2~6wt% and 10~20wt%；Mass ratio according to organic phase change material and regenerated silk fibroin is 1:1.2~2:1 weighs organic phase change material, and 10~30min of solution A emulsification is added after melting and obtains emulsion；Volume ratio according to ethanol and solution A is 3:20~7:20 measure ethanol, add the emulsion, and then stirring, induction fibroin occurred conformation transformation first freezes, thaws again, obtain the suspension that microcapsules of storing energy through phase change is suspended phase, water is dispersed phase；The suspension is added into solution B, stirred, is concentrated into 25~35wt%, injection electrostatic spinning apparatus and carries out electrostatic spinning, obtain fibroin albumen energy-saving and temperature-regulating tunica fibrosa.The problem of which solving intensity decreases and the low energy storage efficiency that energy-saving and temperature-regulating fiber made from prior art is present.
Description
Technical Field
The invention belongs to the field of energy storage and temperature regulation fibers, and particularly relates to a preparation method of a biodegradable and biocompatible regenerated silk fibroin energy storage and temperature regulation nanofiber membrane.
Background
The energy storage and temperature regulation fiber is an intelligent fiber capable of automatically regulating the temperature by compounding a phase change energy storage material and the fiber. The phase-change material contained in the fiber material utilizes the absorption and release of heat generated in the phase-change process to cope with the change of the environmental temperature, thereby achieving the balance and adjustment effect of the fiber on the temperature of a local microenvironment. Therefore, the energy storage temperature regulating fiber as a novel material has wide application prospect in the fields of clothing fabrics, buildings, aerospace and the like, and gradually occupies a place in the field of medical textiles and even in the field of wound repair.
The preparation method of the energy storage and temperature regulation fiber at present mainly comprises a hollow fiber filling method, a surface coating method, a blending spinning method, a microcapsule composite spinning method, a skin-core composite spinning method, a chemical grafting method and the like. However, these methods have limitations, such as the thick fibers prepared by the hollow fiber filling method, special production process and difficult industrialization; the skin-core spinning has high requirement on the sealing property of a skin layer polymer so as to avoid the loss of the phase change material from the fiber; the fiber prepared by the blending spinning method has the problems of easy loss of the phase-change material, poor fiber forming property of the fiber, poor energy storage property of the fiber and the like; the chemical grafting preparation process is relatively complicated, and the grafting efficiency is not high. Compared with the processes, the microcapsule composite spinning technology is mature and widely applied. However, the microcapsule technology has strict requirements on equipment, technology and process, and has high cost and high product price. Moreover, because the problem of interfacial strength exists between the microcapsules and the fiber base material, the strength of the fiber obtained by microcapsule composite spinning is obviously reduced, and the energy storage efficiency is not high.
The regenerated silk fibroin is a natural protein obtained from silkworm cocoons, has excellent performances such as good biocompatibility and degradability, good air and moisture permeability, low immunogenicity, electrostatic spinning performance and the like, and has unique superiority in various fields such as medical dressings, tissue engineering, drug-loaded sustained-release microcapsules, films and the like. The phase change energy storage microcapsule prepared by taking the regenerated fibroin as the wall material not only keeps the excellent performance of the fibroin, but also can play a role in temperature regulation and control. Therefore, the regenerative fibroin phase change microcapsule is applied to biomedical materials such as skin wound dressing, tissue engineering and the like, and can provide proper temperature conditions for the repair and regeneration of skin, thereby being beneficial to the healing of the wound and the regeneration of tissues. In the patent application of the invention of china with application number 200510025903.6, the physical adsorption technique of the eastern virginia et al is adopted to prepare the phase-change microcapsule by using animal proteins such as gelatin and fibroin as wall materials, which is suitable for mixing, compounding, coating or pouring of flexible textile materials. However, the method inevitably causes the problems of residual toxic solvent or metal ions, leakage of the phase-change material, and the like. Senem et al also report a phase-change microcapsule prepared by complex coacervation method and using fibroin and chitosan as capsule wall material and n-eicosane as core material (Colloid Polymer Science 2009, 287, 1455; Journal of applied Polymer Science 2011, 121, 1885), but the obtained microcapsule has poor appearance and energy storage efficiency, and the silk fibroin subjected to crosslinking treatment has unsatisfactory compactness.
Disclosure of Invention
The invention aims to provide a preparation method of a silk fibroin energy storage and temperature regulation fiber membrane, which aims to solve the problems of strength reduction and low energy storage efficiency of energy storage and temperature regulation fibers prepared by the existing microcapsule composite spinning technology.
The conception of the invention is as follows: aiming at the defects of low strength and low energy storage efficiency of the energy storage and temperature regulation fiber prepared by the existing microcapsule composite spinning technology, a wall material with excellent microcapsule encapsulation performance is selected and simultaneously used as a microcapsule wall material and a fiber base material, the composite fiber is obtained by the microcapsule composite spinning technology, and the interface bonding strength of two phases is improved so as to improve the fiber strength and the energy storage density. At present, no public research report in the aspect is found. The preparation process of the phase change energy storage microcapsule taking the regenerated silk fibroin as the wall material integrates the preparation of oil-in-water type emulsion and the self-assembly of silk fibroin, and finally the obtained microcapsule suspension takes water as a disperse phase. And directly blending the suspension with the silk fibroin aqueous solution to prepare spinning solution for electrostatic spinning. The method also avoids the problem of uneven dispersion of the microcapsule in the common microcapsule composite spinning technology, and the interaction of the microcapsule wall material and the silk fibroin in the solution also makes the method have great feasibility.
The specific technical scheme of the invention is as follows:
a preparation method of a silk fibroin energy storage and temperature regulation fiber membrane is characterized by comprising the following steps:
preparing regenerated silk fibroin aqueous solutions A and B with two concentrations of 2-6 wt% and 10-20 wt%;
weighing the organic phase change material according to the mass ratio of the organic phase change material to the regenerated silk fibroin of 1: 1.2-2: 1, adding a regenerated silk fibroin aqueous solution A after melting, and emulsifying at the rotating speed of 1000-12000 rpm for 10-30 min under the action of an emulsifier to obtain an emulsion;
measuring ethanol according to the volume ratio of the ethanol to the regenerated silk fibroin aqueous solution A of 3: 20-7: 20, adding the emulsion, stirring, inducing the silk fibroin to generate conformational transition, freezing, and then thawing to obtain milky suspension with the phase change energy storage microcapsule as a suspension phase and water as a dispersion phase;
and adding the suspension into a regenerated silk fibroin aqueous solution B, uniformly stirring, concentrating to 25-35 wt%, and injecting into an electrostatic spinning device for electrostatic spinning to obtain the silk fibroin energy-storage temperature-regulating fiber membrane.
In the above method for preparing the silk fibroin energy storage temperature-regulating fiber membrane, one preferable preparation method of the regenerated silk fibroin aqueous solutions a and B is as follows: boiling silkworm cocoon with 0.5 wt% Na2CO3Decocting the water solution with slow fire for 30min, repeating the above steps, and cleaning to obtain silk fibroin; dissolving the obtained silk fibroin in 9Mol/L LiBr aqueous solution for 2h at 40 ℃ to obtain regenerated silk fibroin aqueous solution; and dialyzing the obtained regenerated silk fibroin aqueous solution in deionized water for 3 days, and concentrating to obtain regenerated silk fibroin aqueous solutions A and B with corresponding concentrations.
In the preparation method of the silk fibroin energy storage temperature regulation fiber membrane, the organic phase change material is preferably C12-30Of phase-change waxes or C8-18And esters thereof.
In the preparation method of the silk fibroin energy storage temperature regulation fiber membrane, the emulsifier is preferably the compound of a nonionic surfactant and an anionic surfactant, and the nonionic surfactant has the molecular formula of R (OCH2CH2)nOH, Tween and/or span nonionic surfactant, wherein R is selected from C8-18The alkyl phenol, the alkyl and the acyl alkyl, n is 3-20; the anionic surfactant is composed ofHas a sub-formula of RSO3M, wherein R is C8-18And M is sodium, potassium or ammonium. The method for compounding the anionic surfactant and the nonionic surfactant as the emulsifier in the preparation process of the regenerated silk fibroin energy-storage temperature-regulating microcapsule improves the emulsification efficiency of the regenerated silk fibroin to the phase-change material, effectively utilizes the crosslinking effect of the anionic surfactant to regenerated silk fibroin molecules and improves the mechanical strength of the regenerated silk fibroin microcapsule.
In the preparation method of the silk fibroin energy storage temperature-regulating fiber membrane, the spinning solution of electrostatic spinning is obtained by blending silk fibroin phase change energy storage microcapsule suspension and regenerated silk fibroin aqueous solution. The problems of difficult microcapsule dispersion, silk fibroin denaturation and the like caused by adding the microcapsule powder are avoided.
In the above method for preparing the silk fibroin energy storage temperature-regulating fiber membrane, the electrostatic spinning parameters are preferably as follows: the static voltage is 20-40 kV, the acceptance distance is 15-25 cm, and the spinning advancing speed is 0.3-1.2 mL/h.
In the above method for preparing the silk fibroin energy-storage temperature-regulating fiber membrane, preferably, the regenerated silk fibroin aqueous solution a and/or B further comprises a skin repair component and/or a sterilization component. The corresponding drug-loaded fiber membrane can be prepared, can be applied to the fields of wound healing, tissue regeneration and the like, prevents overhigh local temperature, prevents wound infection caused by sweating, and promotes wound healing and skin tissue regeneration. The skin repairing component can be hyaluronic acid or other existing skin repairing components, and the antibacterial component can be chitosan or other anti-inflammatory antibacterial drugs.
The invention has the following beneficial effects:
the invention adopts ethanol induction and freezing technology to induce and regenerate silk fibroin to change from water-soluble random/alpha-helical conformation to water-insoluble beta-folded conformation, so as to promote microcapsules to separate out water phase for molding and generate suspension liquid taking silk fibroin phase change energy storage microcapsules as suspension phase; when the suspension of the microcapsule is added into regenerated silk fibroin aqueous solution, the problem of uneven dispersion of the microcapsule in the common microcapsule composite spinning technology is avoided, and meanwhile, the regenerated silk fibroin in the microcapsule wall material can adsorb silk fibroin molecules in the regenerated silk fibroin aqueous solution and acts with the silk fibroin molecules, so that the interface bonding strength of the microcapsule and a fiber base material is improved when the fiber is formed, and the reduction of the mechanical strength of the fiber is avoided. Meanwhile, the preparation method has low cost, simple operation, no toxicity and no pollution. The prepared fiber membrane has good mechanical property and excellent temperature regulation performance, has good biocompatibility, can be applied to medical textiles such as medical dressings and the like, prevents local overhigh temperature, prevents wound infection caused by sweating, and promotes wound healing.
Detailed Description
The present invention is further illustrated by the following specific examples.
These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. After reading the teaching of the present invention, the skilled in the art can make various changes or modifications to the invention, and these equivalents also fall within the scope of the claims appended to the present application.
Example 1:
(1) boiling silkworm cocoon with 0.5 wt% Na2CO3Decocting the water solution with slow fire for 30min, repeating the above steps, and cleaning to obtain silk fibroin; dissolving the obtained silk fibroin in 9Mol/L LiBr aqueous solution for 2h at 40 ℃ to obtain regenerated silk fibroin aqueous solution; and dialyzing the obtained regenerated silk fibroin aqueous solution in deionized water for 3 days, and concentrating to obtain a regenerated silk fibroin aqueous solution A with the mass concentration of 3.3 wt% and a regenerated silk fibroin aqueous solution B with the mass concentration of 10.2 wt%.
(2) 0.83g of span-80, 0.05g of n-dodecanol and 0.18g of sodium dodecyl sulfate are weighed and added into 200g of regenerated silk fibroin aqueous solution A, and the mixture is stirred uniformly; adding 6.5g of molten phase-change paraffin into the water bath environment at 40 ℃, emulsifying the mixture for 30min at a stirring speed of 1000rpm, and continuously dripping 0.18g of sodium dodecyl sulfate into the mixture during the emulsification process; then measuring 30ml of ethanol, adding the ethanol into the prepared emulsion, and stirring for 3min at the rotating speed of 300 rpm; then the obtained solution is frozen at-25 ℃ for 24 hours and unfrozen to obtain microcapsule suspension; and concentrating the suspension to 120g, adding the concentrated suspension into 60g of regenerated silk fibroin aqueous solution B, uniformly stirring, and continuously concentrating until the concentration reaches 35.4 wt% to obtain the spinning solution.
(3) Transferring the spinning solution into a syringe, taking an aluminum foil as a receiving device, and carrying out electrostatic spinning in a normal-temperature environment, wherein the electrostatic spinning conditions are as follows: the voltage is 25kV, the push speed of an injection pump is 0.7ml/h, the receiving distance is 16cm, the regenerated silk fibroin energy storage temperature regulation electrostatic spinning fiber membrane is obtained, the fiber diameter is 3-7 mu m, the phase change temperature is 29-40 ℃, and the heat storage enthalpy value is 35J/g.
Example 2:
(1) preparing regenerated silk fibroin aqueous solution A with the mass concentration of 3.2 wt% and regenerated silk fibroin aqueous solution B with the mass concentration of 10.1 wt%.
(2) 0.83g of span-80, 0.05g of n-dodecanol and 0.18g of sodium dodecyl sulfate are weighed and added into 200g of regenerated silk fibroin aqueous solution A, and the mixture is stirred uniformly; adding 6.4g of molten phase-change paraffin into the water bath environment at 40 ℃, emulsifying the mixture for 30min at a homogenization speed of 5000rpm, and continuously dripping 0.18g of sodium dodecyl sulfate into the mixture during the emulsification process; then measuring 30ml of ethanol, adding the ethanol into the prepared emulsion, and stirring for 3min at the rotating speed of 300 rpm; then the obtained solution is frozen at-25 ℃ for 24 hours and unfrozen to obtain microcapsule suspension; and concentrating the suspension to 120g, adding the concentrated suspension into 60g of regenerated silk fibroin aqueous solution B, uniformly stirring, and continuously concentrating until the concentration reaches 34.7 wt% to obtain the spinning solution.
(3) Transferring the spinning solution into a syringe, taking an aluminum foil as a receiving device, and carrying out electrostatic spinning in a normal-temperature environment, wherein the electrostatic spinning conditions are as follows: the voltage is 35kV, the push rate of an injection pump is 0.7ml/h, the receiving distance is 16cm, the regenerated silk fibroin energy storage temperature regulation electrostatic spinning fiber membrane is obtained, the fiber diameter is 2-5 mu m, the phase change temperature is 20-31 ℃, and the heat storage enthalpy value is 30J/g.
Example 3:
(1) preparing regenerated silk fibroin aqueous solution A with the mass concentration of 3.1 wt% and regenerated silk fibroin aqueous solution B with the mass concentration of 10.5 wt%.
(2) Weighing 1.1g of span-80, 0.1g of n-dodecanol and 0.36g of sodium dodecyl sulfate, adding into 200g of regenerated silk fibroin aqueous solution A, and stirring uniformly; adding 12.4g of melted n-octadecane into the mixture in a water bath environment at the temperature of 40 ℃, emulsifying the mixture for 10min at a homogenization speed of 12000rpm, and continuously dripping 0.36g of sodium dodecyl sulfate into the mixture in the emulsifying process; then measuring 30ml of ethanol, adding the ethanol into the prepared emulsion, and stirring for 3min at the rotating speed of 300 rpm; then, freezing the obtained solution at-25 ℃ for 24h, and unfreezing to obtain microcapsule suspension; and concentrating the suspension to 120g, adding the concentrated suspension into 60g of regenerated silk fibroin aqueous solution B, uniformly stirring, and continuously concentrating until the concentration reaches 33.5 wt% to obtain the spinning solution.
(3) Transferring the spinning solution into a syringe, taking an aluminum foil as a receiving device, and carrying out electrostatic spinning in a normal-temperature environment, wherein the electrostatic spinning conditions are as follows: the voltage is 35kV, the push rate of an injection pump is 0.7ml/h, the receiving distance is 16cm, the regenerated silk fibroin energy storage temperature regulation electrostatic spinning fiber membrane is obtained, the fiber diameter is 1-3 mu m, the phase change temperature is 15-23 ℃, and the heat storage enthalpy value is 63J/g.
Claims (4)
1. A preparation method of a silk fibroin energy storage temperature regulation fiber membrane is characterized in that regenerated silk fibroin is used as a shell material of a heat storage temperature regulation microcapsule and simultaneously used as a base material of electrostatic spinning fiber, and the preparation method comprises the following steps:
preparing regenerated silk fibroin aqueous solutions A and B with two concentrations of 2-6 wt% and 10-20 wt%, wherein the specific preparation method comprises the following steps: boiling silkworm cocoon with 0.5 wt% Na2CO3Decocting the water solution with slow fire for 30min, and cleaning with deionized water; the degumming process is carried out twice, and finally the silk is obtained by cleaningA vegetarian protein; dissolving the obtained silk fibroin in 9Mol/L LiBr aqueous solution for 2h at 40 ℃ to obtain regenerated silk fibroin aqueous solution; dialyzing the obtained regenerated silk fibroin aqueous solution in deionized water for 3 days, and concentrating to obtain regenerated silk fibroin aqueous solutions A and B with corresponding concentrations;
weighing the organic phase change material according to the mass ratio of the organic phase change material to the regenerated silk fibroin of 1: 1.2-2: 1, adding a regenerated silk fibroin aqueous solution A after melting, and emulsifying at the rotating speed of 5000-12000 rpm for 10-30 min under the action of an emulsifier to obtain an emulsion;
measuring ethanol according to the volume ratio of the ethanol to the regenerated silk fibroin aqueous solution A of 3: 20-7: 20, adding the emulsion, stirring, inducing the silk fibroin to generate conformational transition, freezing, and then thawing to obtain milky suspension with the phase change energy storage microcapsule as a suspension phase and water as a dispersion phase;
adding the suspension into a regenerated silk fibroin aqueous solution B, uniformly stirring, concentrating to 25-35 wt%, injecting into an electrostatic spinning device, and performing electrostatic spinning to obtain a silk fibroin energy storage and temperature regulation fiber membrane; wherein,
the emulsifier is a compound of a nonionic surfactant and an anionic surfactant, and the molecular formula of the nonionic surfactant is R (OCH2CH2)nOH, Tween and/or span nonionic surfactant, wherein R is selected from C8-18The alkyl phenol, the alkyl and the acyl alkyl, n is 3-20; the anionic surfactant is RSO3M, wherein R is C8-18M is sodium, potassium or ammonium;
the microcapsule blending silk fibroin spinning solution for electrostatic spinning is added in a mode that unfrozen suspension is directly blended with a regenerated silk fibroin aqueous solution B.
2. The method for preparing the silk fibroin energy storage temperature regulation fiber membrane of claim 1, characterized in that: the organic phase-change material is C12-30Of phase-change waxes or C8-18Of (2)Fatty acids and esters thereof.
3. The preparation method of the silk fibroin energy storage temperature regulating fiber membrane as claimed in claim 1, wherein electrostatic spinning parameters are as follows: the static voltage is 20-40 kV, the receiving distance is 15-25 cm, and the spinning advancing speed is 0.3-1.2 mL/h.
4. The method for preparing the silk fibroin energy storage temperature regulation fiber membrane of claim 1, characterized in that: the regenerated silk fibroin aqueous solution A and/or B also comprises a skin repair component and/or a sterilization component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510888419.XA CN105297289B (en) | 2015-12-07 | 2015-12-07 | A kind of fibroin albumen energy-saving and temperature-regulating fiber membrane preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510888419.XA CN105297289B (en) | 2015-12-07 | 2015-12-07 | A kind of fibroin albumen energy-saving and temperature-regulating fiber membrane preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105297289A CN105297289A (en) | 2016-02-03 |
| CN105297289B true CN105297289B (en) | 2017-10-31 |
Family
ID=55195070
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510888419.XA Expired - Fee Related CN105297289B (en) | 2015-12-07 | 2015-12-07 | A kind of fibroin albumen energy-saving and temperature-regulating fiber membrane preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105297289B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105802587B (en) * | 2016-05-24 | 2019-02-26 | 清华大学深圳研究生院 | Wall material is TiO2Microcapsules of storing energy through phase change and preparation method thereof |
| CN106592228B (en) * | 2016-10-25 | 2019-03-01 | 林飘飘 | A kind of children's silk quilt of temperature and humidity control and preparation method thereof |
| CN106567193B (en) * | 2016-11-11 | 2019-06-28 | 上海理工大学 | A method of increasing electrospinning protein nano tunica fibrosa surface area |
| CN109251732A (en) * | 2018-09-17 | 2019-01-22 | 南通和清纺织科技有限公司 | A kind of preparation method of graphene microcapsules fiber |
| CN112553733A (en) * | 2020-11-30 | 2021-03-26 | 闽江学院 | Method for preparing energy-storage temperature-regulating blended multifunctional yarn by utilizing electrostatic spinning process |
| CN112482034B (en) * | 2020-12-07 | 2023-01-06 | 吴江市腾旭纺织厂 | Preparation method of silk fibroin/cellulose temperature-sensitive fabric |
| CN116497474B (en) * | 2023-05-16 | 2023-12-22 | 宁波远成服饰有限公司 | Antistatic fabric and preparation method thereof |
| CN117777859B (en) * | 2023-12-28 | 2025-09-09 | 江南大学 | Silk-based photonic crystal structure color coating solution and application thereof |
| CN118166440A (en) * | 2024-01-15 | 2024-06-11 | 成都纺织高等专科学校 | Intelligent temperature-regulating silk fiber and preparation method thereof |
| CN119877288B (en) * | 2025-03-31 | 2025-06-17 | 宁波博洋家纺集团有限公司 | Tencel small jacquard home textile fabric and preparation method thereof |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63309580A (en) * | 1987-06-12 | 1988-12-16 | Nok Corp | Production of heat storage material capsule |
| CA2423123A1 (en) * | 2000-09-21 | 2002-03-28 | Outlast Technologies, Inc. | Multi-component fibers having reversible thermal properties |
| US6855422B2 (en) * | 2000-09-21 | 2005-02-15 | Monte C. Magill | Multi-component fibers having enhanced reversible thermal properties and methods of manufacturing thereof |
| CN100362075C (en) * | 2005-05-18 | 2008-01-16 | 东华大学 | Phase-change energy storage microcapsules coated with animal protein, preparation method and use thereof |
| WO2011041395A2 (en) * | 2009-09-29 | 2011-04-07 | Trustees Of Tufts College | Silk nanospheres and microspheres and methods of making same |
| CN104389039A (en) * | 2014-11-06 | 2015-03-04 | 龙达（江西）差别化化学纤维有限公司 | Method for producing temperature-regulating viscose fibers |
| CN104893187A (en) * | 2015-04-09 | 2015-09-09 | 同济大学 | High energy storage density and efficiency polymer composite film and preparation method thereof |
| CN104947320B (en) * | 2015-05-28 | 2017-11-14 | 清华大学深圳研究生院 | A kind of bio-medical energy-saving and temperature-regulating tunica fibrosa and preparation method thereof |
| CN104927777B (en) * | 2015-06-02 | 2018-04-24 | 清华大学深圳研究生院 | Microcapsules of storing energy through phase change preparation method and application |
-
2015
- 2015-12-07 CN CN201510888419.XA patent/CN105297289B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN105297289A (en) | 2016-02-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105297289B (en) | A kind of fibroin albumen energy-saving and temperature-regulating fiber membrane preparation method | |
| CN102008756B (en) | Preparation method of nano-fibrous silk fibroin-based porous scaffold | |
| CN102787382A (en) | Method for preparing natural material inorganic nanoparticle composite nano-fiber through electrostatic spinning | |
| CN107952112A (en) | A kind of nerve trachea of the function of directional guide containing silk fibroin nano-fiber and preparation method thereof | |
| CN103341209A (en) | Silk fibroin nanofiber membrane and preparation method thereof | |
| CN106729982A (en) | A kind of preparation method of silk fibroin nanosphere | |
| CN102817105A (en) | Preparation method of core-shell structured synthetic polymer-natural polymer composite fiber | |
| CN103418021B (en) | In-situ-crossly-linked electrospun fibrous membrane dressing made from collangen I and preparation method of in-situ crosslinking electrospun fibrous membrane dressing | |
| CN107898533B (en) | Artificial drug-loaded coaxial regenerated vascular stent and its composite process preparation method | |
| CN103467756A (en) | Method for preparing chitosan/hydroxyapatite composite microspheres | |
| CN108641100A (en) | A kind of preparation method of high ionic conductivity nano-cellulose/polyvinyl alcohol hydrogel film | |
| CN105126175B (en) | A kind of electrospinning fiber can be loaded with periodontal tissue regeneration material and preparation method thereof | |
| CN108192731B (en) | Sweet orange essence-silk fibroin microcapsule and preparation method thereof | |
| CN111588907A (en) | Preparation method of multifunctional heterostructure microfiber | |
| CN108159502A (en) | Aurantiin microballoon fibroin albumen/hydroxyapatite compound rest and preparation method thereof | |
| CN105879113A (en) | Method for preparing three-dimensional cell scaffolds on basis of silk fibroins | |
| CN103436992B (en) | Method for preparing nano drug-carrying capsule-loaded alginate fibers | |
| CN106729981A (en) | A kind of silk fibroin nano-fiber and its preparation method and application | |
| CN107661540B (en) | A method for preparing high-strength hydroxyapatite-chitosan-silica hybrid scaffolds by 3D printing | |
| CN109183173B (en) | Silk fibroin hollow fiber containing wormwood microcapsule and preparation method thereof | |
| CN101352585B (en) | Preparation method of nano-hydroxyapatite/chitosan scaffold with oriented particle arrangement | |
| CN107670111B (en) | Highly oriented composite fiber membrane and preparation method and application thereof | |
| CN103266474A (en) | Method for preparing polyaspartic acid nano hydrogel felt | |
| CN113801345A (en) | High molecular weight soluble silk fibroin powder and preparation method thereof | |
| CN117327646A (en) | Three-dimensional bionic orientation gel scaffold and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Luo Jie Inventor after: Song Guolin Inventor after: Tang Guoyi Inventor after: Zhao Liang Inventor after: Chen Yaogang Inventor after: Tang Miao Inventor after: Yang Yanyan Inventor after: Liu Yuan Inventor after: Chen Lijie Inventor before: Luo Jie Inventor before: Song Guolin Inventor before: Tang Guoyi Inventor before: Zhao Liang Inventor before: Yang Yanyang Inventor before: Liu Yuan Inventor before: Chen Lijie |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171031 Termination date: 20201207 |