CN112647283A - Modified silk fiber with high moisture-dissipating property and preparation method thereof - Google Patents
Modified silk fiber with high moisture-dissipating property and preparation method thereof Download PDFInfo
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- CN112647283A CN112647283A CN202011507349.6A CN202011507349A CN112647283A CN 112647283 A CN112647283 A CN 112647283A CN 202011507349 A CN202011507349 A CN 202011507349A CN 112647283 A CN112647283 A CN 112647283A
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- 239000000835 fiber Substances 0.000 title claims abstract description 200
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 77
- 229920000431 shape-memory polymer Polymers 0.000 claims abstract description 48
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 18
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 18
- 229920002635 polyurethane Polymers 0.000 claims abstract description 3
- 239000004814 polyurethane Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 73
- 238000003756 stirring Methods 0.000 claims description 64
- 230000000977 initiatory effect Effects 0.000 claims description 32
- 239000002243 precursor Substances 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 21
- 229920002125 Sokalan® Polymers 0.000 claims description 17
- 239000004584 polyacrylic acid Substances 0.000 claims description 17
- 239000003431 cross linking reagent Substances 0.000 claims description 16
- 238000002791 soaking Methods 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- -1 polybutylene adipate Polymers 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 14
- 230000008961 swelling Effects 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 12
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 11
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 229920002101 Chitin Polymers 0.000 claims description 10
- 108010022355 Fibroins Proteins 0.000 claims description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 10
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 10
- 238000007493 shaping process Methods 0.000 claims description 10
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000009960 carding Methods 0.000 claims description 9
- 238000004898 kneading Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 7
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 7
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 7
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 4
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000003100 immobilizing effect Effects 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 238000010521 absorption reaction Methods 0.000 description 21
- 206010042674 Swelling Diseases 0.000 description 11
- 238000007865 diluting Methods 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 230000001012 protector Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000126 substance Substances 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
- 241000205585 Aquilegia canadensis Species 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
- D06M11/155—Halides of elements of Groups 2 or 12 of the Periodic Table
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- D—TEXTILES; PAPER
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/03—Polysaccharides or derivatives thereof
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/15—Proteins or derivatives thereof
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
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- D—TEXTILES; PAPER
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
- D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/507—Polyesters
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
- D06M15/572—Reaction products of isocyanates with polyesters or polyesteramides
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/10—Animal fibres
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- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a modified silk fiber with high moisture-dissipating property, which comprises a silk fiber and a shape memory polymer coated on the surface of the silk fiber, wherein the shape memory polymer contains a hydrophilic material, and the hydrophilic material is coated and fixed on the surface of the silk fiber through the shape memory polymer; the shape memory polymer is shape memory polyurethane or shape memory polycaprolactone; the invention also provides a preparation method of the modified silk fiber with high moisture-dissipating property. The modified silk fiber with high moisture-dissipating performance prepared by the invention can reduce the loss of the hydrophilic material by immobilizing the hydrophilic material on the silk fiber through the shape memory polymer, and meanwhile, the shape memory polymer coated on the surface of the silk fiber can quickly dissipate moisture under the synergistic action of the hydrophilic material.
Description
Technical Field
The invention relates to the technical field of textile materials, in particular to a modified silk fiber with high moisture-dissipating performance and a preparation method thereof.
Background
The silk is a porous protein fiber, is known for skin-friendly and comfortable and has certain health care effect, and although the silk has good moisture absorption and moisture dispersion performance, the silk has a certain distance from high moisture absorption, so that the application of the silk fiber in the moisture absorption field is greatly limited.
Therefore, many researches have been made on improving the moisture absorption performance of silk fibers, for example, chinese patent application No. 201610319815.5 discloses a modified silk fiber with high moisture absorption and retention property and a preparation method thereof, wherein the modified silk fiber with high moisture absorption and retention property is prepared by using fine-fiber silk fibers as a raw material, using low-molecular-weight chitosan, sodium alginate, corn starch and honeysuckle as a high moisture absorption and retention finishing agent, sequentially impregnating the high-moisture absorption and retention finishing agent with a silk fibroin solution, and then performing steam treatment, shaping, water washing and drying steps, wherein the moisture absorption property of the silk fiber prepared by the method can reach more than 25%. The Chinese patent with the application number of 201610317310.5 discloses a preparation method of super-soft and high-moisture-absorption silk fibers, which is characterized in that the silk fibers are boiled to be degummed, and then are soaked in warm water for swelling treatment, the silk fibers are rubbed and rubbed to obtain pretreated silk fibers, and then are soaked in a solution containing nano hydrogel particles, ultrasonic oscillation is carried out, the silk fibers are taken out, spin-drying is carried out to obtain the high-moisture-absorption silk fibers, the high-moisture-absorption silk fibers are added into ice water, heating and stirring are carried out slowly, biological enzyme is added, the silk fibers are taken out after reaction for a period of time, water washing is carried out fully, and the super-soft and high-moisture-absorption silk fibers are obtained by natural drying, and the moisture absorption rate.
Although the moisture absorption performance of the silk is improved by the methods, the substance for improving the moisture absorption performance is coated on the surface of the silk by simple impregnation, and the moisture absorption substance is lost along with the increase of washing, so that the moisture absorption performance of the silk is greatly reduced; in addition, the moisture dispersing property of the silk is not improved, the high moisture absorption performance enables the fibers to absorb moisture quickly, the dryness of a user is kept, if absorbed moisture cannot be dissipated quickly, on one hand, the comfort of the user can be reduced, and on the other hand, the performance of the silk fibers can be influenced due to the fact that the long-time humidity is too large. Therefore, the silk fiber can be widely applied by rapidly dissipating water while absorbing high moisture.
Disclosure of Invention
The invention aims to provide a modified silk fiber with high moisture-dissipating performance, the modified silk fiber can reduce the loss of hydrophilic materials by immobilizing the hydrophilic materials on the silk fiber through shape memory polymers, and meanwhile, the shape memory polymers coated on the surface of the silk fiber and the hydrophilic materials have synergistic effect, so that the silk fiber can rapidly dissipate moisture.
The invention also aims to provide a preparation method of the modified silk fiber with high moisture-dissipating performance.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a modified silk fiber with high hygroscopicity comprises a silk fiber and a shape memory polymer coated on the surface of the silk fiber, wherein the shape memory polymer contains a hydrophilic material, and the hydrophilic material is coated and fixed on the surface of the silk fiber through the shape memory polymer;
the shape memory polymer is shape memory polyurethane or shape memory polycaprolactone.
Furthermore, the hydrophilic material is a mixture of chitin, a polyvinyl alcohol macromonomer and a polyacrylic acid macromonomer, and the mass ratio of the chitin to the polyvinyl alcohol macromonomer to the polyacrylic acid macromonomer is 1 (3-5) to 2.
A preparation method of modified silk fiber with high hygroscopicity comprises the following steps:
(1) silk fiber treatment: degumming silk, adding the degummed silk into a calcium chloride solution for swelling, and kneading and carding the swollen silk fiber to obtain fine-fiber silk fiber;
(2) preparation of a shape memory polymer precursor: putting raw materials of the shape memory polymer, a cross-linking agent and a hydrophilic material into a solvent according to a mass ratio, mixing, and stirring until the raw materials, the cross-linking agent and the hydrophilic material are fully mixed to obtain a required precursor;
(3) dipping the silk fiber obtained in the step (1) in the precursor obtained in the step (2), and stirring until the silk fiber and the precursor are uniformly mixed;
(4) placing the mixture obtained in the step (3) under a vacuum condition, reacting at the temperature of 80-100 ℃, simultaneously using ultraviolet initiation for the first time, stopping ultraviolet initiation after a period of time, adding a hydrophilic material, continuously stirring for 1h, and performing ultraviolet initiation for the second time to obtain the silk fiber coated with the shape memory polymer;
(5) and (4) drying the silk fiber wrapped with the high polymer obtained in the step (4), soaking the silk fiber in silk fibroin aqueous solution, taking out, removing redundant solution on the surface, treating and shaping the silk fiber by using ethanol water vapor, and washing and drying the silk fiber to obtain the modified silk fiber with high moisture-dissipating type.
Further, in the step (2), the shape memory polymer precursor is prepared as follows: vacuumizing and dehydrating the polybutylene adipate under a certain temperature condition, then adding metered 2, 4-toluene diisocyanate into a four-neck flask with a mechanical stirring device, a nitrogen protection device, a thermometer and a dropping funnel, and dropwise adding metered molten polybutylene adipate to obtain a solution A; adding a hydrophilic material into the solution A, quickly stirring and reacting at a certain temperature to obtain a prepolymer, dissolving the prepolymer in DMF to obtain a solution B, adding a certain amount of 1, 6-hexanediol into the solution B, stirring and reacting, and vacuumizing to remove bubbles in the solution to obtain a solution C; and adding a cross-linking agent into the solution C, and uniformly stirring.
Further, the molar ratio of the polybutylene adipate to the 2, 4-toluene diisocyanate to the 1, 6-hexanediol is 1 (2-5) to (1-4), the mass fraction of the hydrophilic material in the solution A is 3-8%, and the mass ratio of the solution C to the cross-linking agent is 3 (0.5-1);
the temperature of vacuumizing is 80-100 ℃; the reaction temperature of the prepolymer is 80-90 ℃; the stirring reaction time is 1-2h, and the stirring speed is 200-.
Further, in the step (2), the shape memory polymer precursor is prepared as follows: weighing a certain proportion of polycaprolactone and a cross-linking agent in dichloromethane, stirring and mixing for 3-5h until the polycaprolactone and the cross-linking agent are completely dissolved to obtain a solution D, adding a hydrophilic material into the solution D, and uniformly mixing;
wherein the stirring speed is 200-400r/min, the purity of the polycaprolactone is more than 98%, the mass fraction of the cross-linking agent is 10-15%, and the mass fraction of the hydrophilic material in the solution D is 3-8%.
Further, the cross-linking agent is any one of polyacrylic acid, benzoyl peroxide and methylene bisacrylamide.
Further, in the step (4), the temperature is 80-100 ℃, the mass fraction of the hydrophilic material is 3-8%, the stirring time is 1-2h, the power of the ultraviolet light is 50-100W, the stirring speed is 200-400r/min, the reaction time of the first ultraviolet initiation is 4-6h, and the reaction time of the second ultraviolet initiation is 6-10 h.
Further, the drying and drying temperature in the step (5) is 50-60 ℃, the dipping time is 30-60min, the volume ratio of ethanol water vapor is 1:1, and the processing time is 10-30 min.
Further, in the step (1), the concentration of the calcium chloride solution is 2-4%, the swelling temperature is 70-80 ℃, and the swelling time is 5-15 min.
Compared with the prior art, the invention has the beneficial effects that:
1. the silk surface is coated with the shape memory polymer with the hydrophilic material, the hydrophilic material adsorbs outside water molecules, and the hydrophilic material generates certain pores in the process of polymerizing the hydrophilic material, so that the adsorbed water molecules can be quickly transferred to the shape memory polymer around the hydrophilic material, the conduction process of the water molecules between the hydrophilic material and the shape polymer is accelerated, and the water absorption performance of the shape memory polymer is improved; and then, the water vapor is rapidly transferred to the surface of the fiber through the micro-planar motion of the molecular chain of the shape memory polymer, and is evaporated through air circulation, so that the water molecules can be rapidly transferred to the shape memory polymer, the process of transferring the water molecules from the outside to the shape memory polymer is shortened, the hydrophilic material and the shape memory polymer act synergistically to accelerate the evaporation rate of the water molecules, the fiber can rapidly absorb and dissipate moisture, the dryness of the fiber is ensured, the modified silk fiber has high moisture dissipation performance, and the evaporation rate can be improved by 200%.
2. In the process of preparing the shape memory polymer, the hydrophilic material is added for many times, the conditions of reaction temperature and ultraviolet initiation are controlled under the vacuum condition, the hydrophilic material is polymerized and wrapped in the shape memory polymer, the hydrophilic material generates certain porosity in the polymerization process, the conduction process of water molecules between the hydrophilic material and the shape polymer is accelerated, and then the shape memory polymer wrapped with the hydrophilic material is wrapped on the surface of the silk fiber, so that the hydrophilic material is wrapped by the polymer instead of being simply soaked and adsorbed on the silk fiber, the loss condition in washing is avoided, and the moisture absorption of the modified silk fiber is more durable.
Detailed Description
In order to better understand the technical content of the invention, specific embodiments are specifically described.
Example 1
In the hydrophilic material in this example, the mass ratio of the chitin, the polyvinyl alcohol macromonomer and the polyacrylic acid macromonomer is 1:3: 2.
(1) Silk fiber treatment: degumming silk, adding into 2% calcium chloride solution, swelling at 70 deg.C for 5min, kneading and carding the swollen silk fiber to obtain fine-fiber silk fiber;
(2) preparing a shape memory polymer precursor: vacuumizing and dehydrating polybutylene adipate (Mn is 3000) at the temperature of 80-100 ℃, then adding metered 2, 4-toluene diisocyanate into a four-neck flask with a mechanical stirrer, a nitrogen gas protector, a thermometer and a dropping funnel, and dropwise adding metered polybutylene adipate which is molten at the temperature of 70 ℃ to obtain a solution A; adding a hydrophilic material into the solution A, quickly stirring and reacting at 80 ℃ for 1-2h to obtain a prepolymer, and dissolving the prepolymer in DMF to obtain a solution B; adding quantitative 1, 6-hexanediol into the obtained solution B, stirring for reaction for 1h, and vacuumizing to remove bubbles in the solution to obtain a solution C; adding polyacrylic acid into the solution C, and uniformly stirring; wherein the stirring speed is 400 r/min; the molar ratio of the polybutylene adipate to the 2, 4-toluene diisocyanate to the 1, 6-hexanediol is 1:2:1, the mass fraction of the hydrophilic material in the solution A is 3%, and the mass ratio of the solution C to the polyacrylic acid is 3: 0.5.
(3) Diluting the precursor obtained in the step (2) to 1000mL by using water, soaking the silk fiber obtained in the step (1) in the diluted precursor, and stirring the silk fiber and the silk fiber until the silk fiber and the silk fiber are completely mixed;
(4) placing the mixture obtained in the step (3) under a vacuum condition, reacting at the temperature of 90 ℃, simultaneously using ultraviolet initiation for 4 hours, stopping the ultraviolet initiation, adding 3% of hydrophilic materials by mass, stirring for 1 hour, performing ultraviolet initiation again for 6 hours, and obtaining silk fibers wrapped with shape memory polymers; wherein the power of the ultraviolet light is 70W, and the stirring speed is 200 r/min;
(5) and (3) drying the silk fiber wrapped with the high polymer obtained in the step (4) at the temperature of 50 ℃, soaking the silk fiber in silk fibroin aqueous solution, taking out the silk fiber after 30min, removing redundant solution on the surface, treating and shaping the silk fiber by using ethanol water vapor with the ratio of 1:1, washing the silk fiber after 10min, and drying the silk fiber at the temperature of 60 ℃ to obtain the modified silk fiber with high moisture-dissipating property.
Example 2
In the hydrophilic material in this example, the mass ratio of the chitin, the polyvinyl alcohol macromonomer and the polyacrylic acid macromonomer is 1:4: 2.
(1) Silk fiber treatment: degumming silk, adding into 4% calcium chloride solution, swelling at 80 deg.C for 15min, kneading and carding the swollen silk fiber to obtain fibril silk fiber;
(2) preparing a shape memory polymer precursor: vacuumizing and dehydrating polybutylene adipate (Mn is 3000) at the temperature of 80-100 ℃, then adding metered 2, 4-toluene diisocyanate into a four-neck flask with a mechanical stirrer, a nitrogen gas protector, a thermometer and a dropping funnel, and dropwise adding metered polybutylene adipate which is molten at the temperature of 70 ℃ to obtain a solution A; adding a hydrophilic material into the solution A, quickly stirring and reacting at 80 ℃ for 1-2h to obtain a prepolymer, and dissolving the prepolymer in DMF to obtain a solution B; adding quantitative 1, 6-hexanediol into the obtained solution B, stirring for reacting for 2h, and vacuumizing to remove bubbles in the solution to obtain a solution C; adding methylene bisacrylamide into the solution C, and uniformly stirring; wherein the stirring speed is 300 r/min; the molar ratio of the polybutylene adipate to the 2, 4-toluene diisocyanate to the 1, 6-hexanediol is 1:3:2, the mass fraction of the hydrophilic material in the solution A is 6%, and the mass ratio of the solution C to the methylene bisacrylamide is 3: 1.
(3) Diluting the precursor obtained in the step (2) to 1000mL by using water, soaking the silk fiber obtained in the step (1) in the diluted precursor, and stirring the silk fiber and the silk fiber until the silk fiber and the silk fiber are completely mixed;
(4) reacting the mixture obtained in the step (3) at the temperature of 90 ℃, simultaneously using ultraviolet initiation for 6 hours, stopping the ultraviolet initiation, adding a hydrophilic material with the mass fraction of 6%, stirring for 1 hour, and performing ultraviolet initiation again for 8 hours to obtain the silk fiber wrapped with the shape memory polymer; wherein the power of the ultraviolet light is 90W, and the stirring speed is 400 r/min;
(5) and (3) drying the silk fiber wrapped with the high polymer obtained in the step (4) at the temperature of 50 ℃, soaking the silk fiber in silk fibroin aqueous solution, taking out the silk fiber after 60min, removing redundant solution on the surface, treating and shaping the silk fiber by using ethanol water vapor with the ratio of 1:1, washing the silk fiber after 20min, and drying the silk fiber at the temperature of 50 ℃ to obtain the modified silk fiber with high moisture-dissipating property.
Example 3
In the hydrophilic material in this example, the mass ratio of the chitin, the polyvinyl alcohol macromonomer and the polyacrylic acid macromonomer is 1:5: 2.
(1) Silk fiber treatment: degumming silk, adding into 3% calcium chloride solution, swelling at 75 deg.C for 10min, kneading and carding the swollen silk fiber to obtain fibril silk fiber;
(2) preparing a shape memory polymer precursor: vacuumizing and dehydrating polybutylene adipate (Mn is 3000) at the temperature of 80-100 ℃, then adding metered 2, 4-toluene diisocyanate into a four-neck flask with a mechanical stirrer, a nitrogen gas protector, a thermometer and a dropping funnel, and dropwise adding metered polybutylene adipate which is molten at the temperature of 70 ℃ to obtain a solution A; adding a hydrophilic material into the solution A; rapidly stirring and reacting at 80 ℃ for 1-2h to obtain a prepolymer, and dissolving the prepolymer in DMF to obtain a solution B; adding quantitative 1, 6-hexanediol into the obtained solution B, stirring for reacting for 2h, and vacuumizing to remove bubbles in the solution to obtain a solution C; adding benzoyl peroxide into the solution C, and uniformly stirring; wherein the stirring speed is 200 r/min; the molar ratio of the polybutylene adipate to the 2, 4-toluene diisocyanate to the 1, 6-hexanediol is 1:5:4, the mass fraction of the hydrophilic material in the solution A is 8%, and the mass ratio of the solution C to the benzoyl peroxide is 3: 1.
(3) Diluting the precursor obtained in the step (2) to 1000mL by using water, soaking the silk fiber obtained in the step (1) in the diluted precursor, and stirring the silk fiber and the silk fiber until the silk fiber and the silk fiber are completely mixed;
(4) reacting the mixture obtained in the step (3) at the temperature of 90 ℃, simultaneously using ultraviolet initiation for 4h, adding 8% of hydrophilic material by mass after stopping the external initiation, stirring for 1h, and performing ultraviolet initiation again for 10h to obtain the silk fiber wrapped with the shape memory polymer; the power of the ultraviolet light is 90W, and the stirring speed is 300 r/min;
(5) and (3) drying the silk fiber wrapped with the high polymer obtained in the step (4) at the temperature of 50 ℃, soaking the silk fiber in silk fibroin aqueous solution for 40min, taking out the silk fiber, removing redundant solution on the surface, treating and shaping the silk fiber by using ethanol water vapor with the ratio of 1:1, washing the silk fiber after 30min, and drying the silk fiber at the temperature of 50 ℃ to obtain the modified silk fiber with high moisture-dissipating property.
Example 4
In the hydrophilic material in this example, the mass ratio of the chitin, the polyvinyl alcohol macromonomer and the polyacrylic acid macromonomer is 1:3: 2.
(1) Silk fiber treatment: degumming silk, adding into 2% calcium chloride solution, swelling at 70 deg.C for 5min, kneading and carding the swollen silk fiber to obtain fine-fiber silk fiber;
(2) preparing a shape memory polymer precursor: weighing polycaprolactone and benzoyl peroxide in a certain proportion in dichloromethane, stirring and mixing for 3 hours until the polycaprolactone and the benzoyl peroxide are completely dissolved to obtain a solution D, adding a hydrophilic material into the solution D, and uniformly mixing; wherein the stirring speed is 300r/min, the purity of the polycaprolactone is more than 98 percent, the mass fraction of the benzoyl peroxide is 10 percent, and the mass fraction of the hydrophilic material in the solution C is 3 percent;
(3) diluting the precursor obtained in the step (2) to 1000mL by using water, soaking the silk fiber obtained in the step (1) in the diluted precursor, and stirring the silk fiber and the silk fiber until the silk fiber and the silk fiber are completely mixed;
(4) reacting the mixture obtained in the step (3) at the temperature of 90 ℃, simultaneously using ultraviolet initiation for 4h, adding 10% of hydrophilic materials by mass after stopping the external initiation, stirring for 1h, and performing ultraviolet initiation again for 10h to obtain the silk fiber wrapped with the shape memory polymer; wherein the power of the ultraviolet light is 70W, and the stirring speed is 300 r/min;
(5) and (3) drying the silk fiber wrapped with the high polymer obtained in the step (4) at the temperature of 60 ℃, soaking the silk fiber in silk fibroin aqueous solution, taking out the silk fiber after 30min, removing redundant solution on the surface, treating and shaping the silk fiber by using ethanol water vapor with the ratio of 1:1, washing the silk fiber after 10min, and drying the silk fiber at the temperature of 50 ℃ to obtain the modified silk fiber with high moisture-dissipating property.
Example 5
In the hydrophilic material in this example, the mass ratio of the chitin, the polyvinyl alcohol macromonomer and the polyacrylic acid macromonomer is 1:3: 2.
(1) Silk fiber treatment: degumming silk, adding into 4% calcium chloride solution, swelling at 80 deg.C for 15min, kneading and carding the swollen silk fiber to obtain fibril silk fiber;
(2) preparing a shape memory polymer precursor: weighing polycaprolactone and methylene bisacrylamide in a certain proportion in dichloromethane, stirring and mixing for 3 hours until the polycaprolactone and the methylene bisacrylamide are completely dissolved to obtain a solution D, adding a hydrophilic material into the solution D, and uniformly mixing; wherein the stirring speed is 400r/min, the purity of the polycaprolactone is more than 98 percent, the mass fraction of the methylene bisacrylamide is 15 percent, and the mass fraction of the hydrophilic material in the solution D is 5 percent;
(3) diluting the precursor obtained in the step (2) to 1000mL by using water, soaking the silk fiber obtained in the step (1) in the diluted precursor, and stirring the silk fiber and the silk fiber until the silk fiber and the silk fiber are completely mixed;
(4) reacting the mixture obtained in the step (3) at the temperature of 90 ℃, simultaneously using ultraviolet initiation for 4h, adding a hydrophilic material with the mass fraction of 5% after stopping the external initiation, stirring for 1h, and performing ultraviolet initiation again for 10h to obtain the silk fiber wrapped with the shape memory polymer; wherein the power of the ultraviolet light is 70W, and the stirring speed is 300 r/min;
(5) and (3) drying the silk fiber wrapped with the high polymer obtained in the step (4) at the temperature of 60 ℃, soaking the silk fiber in silk fibroin aqueous solution, taking out the silk fiber after 60min, removing redundant solution on the surface, treating and shaping the silk fiber by using ethanol water vapor with the ratio of 1:1, washing the silk fiber after 30min, and drying the silk fiber at the temperature of 50 ℃ to obtain the modified silk fiber with high moisture-dissipating property.
Example 6
In the hydrophilic material in this example, the mass ratio of the chitin, the polyvinyl alcohol macromonomer and the polyacrylic acid macromonomer is 1:3: 2.
(1) Silk fiber treatment: degumming silk, adding into 3% calcium chloride solution, swelling at 75 deg.C for 10min, kneading and carding the swollen silk fiber to obtain fibril silk fiber;
(2) preparing a shape memory polymer precursor: weighing polycaprolactone and polyacrylic acid in a certain proportion into dichloromethane, stirring and mixing for 3h until the polycaprolactone and the polyacrylic acid are completely dissolved to obtain a solution D, adding a hydrophilic material into the solution D, and uniformly mixing; wherein the stirring speed is 200r/min, the purity of the polycaprolactone is more than 98 percent, the mass fraction of the polyacrylic acid is 15 percent, and the mass fraction of the hydrophilic material in the solution D is 8 percent;
(3) diluting the precursor obtained in the step (2) to 1000mL by using water, soaking the silk fiber obtained in the step (1) in the diluted precursor, and stirring the silk fiber and the silk fiber until the silk fiber and the silk fiber are completely mixed;
(4) reacting the mixture obtained in the step (3) at the temperature of 90 ℃, simultaneously using ultraviolet initiation for 4h, adding 8% of hydrophilic material by mass after stopping the external initiation, stirring for 1h, and performing ultraviolet initiation again for 10h to obtain the silk fiber wrapped with the shape memory polymer; wherein the power of the ultraviolet light is 70W, and the stirring speed is 300r/min
(5) And (3) drying the silk fiber wrapped with the high polymer obtained in the step (4) at the temperature of 50 ℃, soaking the silk fiber in silk fibroin aqueous solution, taking out the silk fiber after 30min, removing redundant solution on the surface, treating and shaping the silk fiber by using ethanol water vapor with the ratio of 1:1, washing the silk fiber after 20min, and drying the silk fiber at the temperature of 60 ℃ to obtain the modified silk fiber with high moisture-dissipating property.
Comparative example 1
(1) Silk fiber treatment: degumming silk, adding the degummed silk into a calcium chloride solution for swelling, and kneading and carding the swollen silk fiber to obtain fine-fiber silk fiber;
(2) dissolving a hydrophilic material with the mass fraction of 10% in water, diluting the solution to 1000mL with water, soaking the silk fiber obtained in the step (1), and stirring the solution until the silk fiber is completely mixed;
(3) reacting the mixture obtained in the step (2) at the temperature of 90 ℃, simultaneously using ultraviolet initiation for 4 hours, adding a hydrophilic material with the mass fraction of 10% after stopping the external initiation, stirring for 1 hour, and performing ultraviolet initiation again for 6 hours to obtain silk fibers wrapping the hydrophilic material; the power of the ultraviolet light is 70W, and the stirring speed is 300 r/min;
(4) and (3) drying the silk fiber wrapped with the hydrophilic material obtained in the step (3) at the temperature of 50 ℃, soaking the silk fiber in silk fibroin aqueous solution, taking out the silk fiber after 30min, removing redundant solution on the surface, treating and shaping the silk fiber by using ethanol water vapor with the ratio of 1:1, washing the silk fiber after 30min, and drying the silk fiber wrapped with the hydrophilic material at the temperature of 50 ℃ to obtain the modified silk fiber wrapped with the hydrophilic material.
The modified silk fibers obtained in examples 1 to 6 and comparative example 1 were subjected to performance tests, and the results are shown in table 1:
TABLE 1
The modified silk fiber with high hygroscopicity prepared by the invention has high hygroscopicity, and the hydrophilic material immobilized by the shape memory high polymer is more stable and does not greatly lose along with washing time; on the other hand, the hydrophilic material is polymerized with the shape high polymer under certain conditions to generate a large number of pores, so that the conduction process of water molecules between the hydrophilic material and the shape high polymer is accelerated.
Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, the protection scope of the present invention should be determined by the appended claims.
Claims (10)
1. A modified silk fiber with high hygroscopicity is characterized in that: the silk fabric comprises silk fibers and a shape memory polymer coated on the surfaces of the silk fibers, wherein the shape memory polymer contains a hydrophilic material, and the hydrophilic material is coated and fixed on the surfaces of the silk fibers through the shape memory polymer;
the shape memory polymer is shape memory polyurethane or shape memory polycaprolactone.
2. Modified silk fiber with high hygroscopicity according to claim 1, characterized by: the hydrophilic material is a mixture of chitin, polyvinyl alcohol macromonomer and polyacrylic acid macromonomer, and the mass ratio of the chitin to the polyvinyl alcohol macromonomer to the polyacrylic acid macromonomer is 1 (3-5) to 2.
3. A method for preparing modified silk fiber with high moisture-dissipating ability according to any one of claims 1 to 2, comprising the steps of:
(1) silk fiber treatment: degumming silk, adding the degummed silk into a calcium chloride solution for swelling, and kneading and carding the swollen silk fiber to obtain fine-fiber silk fiber;
(2) preparation of a shape memory polymer precursor: putting raw materials of the shape memory polymer, a cross-linking agent and a hydrophilic material into a solvent according to a mass ratio, mixing, and stirring until the raw materials, the cross-linking agent and the hydrophilic material are fully mixed to obtain a required precursor;
(3) dipping the silk fiber obtained in the step (1) in the precursor obtained in the step (2), and stirring until the silk fiber and the precursor are uniformly mixed;
(4) placing the mixture obtained in the step (3) under a vacuum condition, reacting at a certain temperature, simultaneously using ultraviolet initiation for the first time, stopping ultraviolet initiation after reacting for a period of time, adding a hydrophilic material, continuously stirring, and performing ultraviolet initiation for the second time to obtain the silk fiber coated with the shape memory polymer;
(5) and (4) drying the silk fiber wrapped with the high polymer obtained in the step (4), soaking the silk fiber in silk fibroin aqueous solution, taking out, removing redundant solution on the surface, treating and shaping the silk fiber by using ethanol water vapor, and washing and drying the silk fiber to obtain the modified silk fiber with high moisture-dissipating type.
4. The method for preparing modified silk fiber with high hygroscopicity according to claim 3, wherein the method comprises the following steps: in the step (2), the shape memory polymer precursor is prepared as follows: vacuumizing and dehydrating the polybutylene adipate under a certain temperature condition, then adding metered 2, 4-toluene diisocyanate into a four-neck flask with a mechanical stirring device, a nitrogen protection device, a thermometer and a dropping funnel, and dropwise adding metered molten polybutylene adipate to obtain a solution A; adding a hydrophilic material into the solution A, quickly stirring and reacting at a certain temperature to obtain a prepolymer, dissolving the prepolymer in DMF to obtain a solution B, adding a certain amount of 1, 6-hexanediol into the solution B, stirring and reacting, and vacuumizing to remove bubbles in the solution to obtain a solution C; and adding a cross-linking agent into the solution C, and uniformly stirring.
5. The method for preparing modified silk fiber with high hygroscopicity according to claim 4, wherein the method comprises the following steps: the molar ratio of the polybutylene adipate to the 2, 4-toluene diisocyanate to the 1, 6-hexanediol is 1 (2-5) to (1-4), the mass fraction of the hydrophilic material in the solution A is 3-8%, and the mass ratio of the solution C to the cross-linking agent is 3 (0.5-1);
the temperature of vacuumizing is 80-100 ℃; the reaction temperature of the prepolymer is 80-90 ℃; the stirring reaction time is 1-2h, and the stirring speed is 200-.
6. The method for preparing modified silk fiber with high hygroscopicity according to claim 3, wherein the method comprises the following steps: in the step (2), the shape memory polymer precursor is prepared as follows: weighing a certain proportion of polycaprolactone and a cross-linking agent in dichloromethane, stirring and mixing for 3-5h until the polycaprolactone and the cross-linking agent are completely dissolved to obtain a solution D, adding a hydrophilic material into the solution D, and uniformly mixing;
wherein the stirring speed is 200-400r/min, the purity of the polycaprolactone is more than 98%, the mass fraction of the cross-linking agent is 10-15%, and the mass fraction of the hydrophilic material in the solution D is 3-8%.
7. The process for preparing modified silk fiber with high moisture-dissipating ability as claimed in any one of claims 3 to 6, wherein: the cross-linking agent is any one of polyacrylic acid, benzoyl peroxide and methylene bisacrylamide.
8. The method for preparing modified silk fiber with high hygroscopicity according to claim 3, wherein the method comprises the following steps: in the step (4), the temperature is 80-100 ℃, the mass fraction of the hydrophilic material is 3-8%, the stirring time is 1-2h, the power of the ultraviolet light is 50-100W, the stirring speed is 400r/min, the reaction time of the first ultraviolet initiation is 4-6h, and the reaction time of the second ultraviolet initiation is 6-10 h.
9. The method for preparing modified silk fiber with high hygroscopicity according to claim 3, wherein the method comprises the following steps: the drying and drying temperature in the step (5) is 50-60 ℃, the dipping time is 30-60min, the volume ratio of ethanol water vapor is 1:1, and the processing time is 10-30 min.
10. The method for preparing modified silk fiber with high hygroscopicity according to claim 3, wherein the method comprises the following steps: in the step (1), the concentration of the calcium chloride solution is 2-4%, the swelling temperature is 70-80 ℃, and the swelling time is 5-15 min.
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