CN110016731A - A kind of quantum titanium fibrous material - Google Patents
A kind of quantum titanium fibrous material Download PDFInfo
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- CN110016731A CN110016731A CN201910364913.4A CN201910364913A CN110016731A CN 110016731 A CN110016731 A CN 110016731A CN 201910364913 A CN201910364913 A CN 201910364913A CN 110016731 A CN110016731 A CN 110016731A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/106—Radiation shielding agents, e.g. absorbing, reflecting agents
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
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Abstract
The invention discloses a kind of quantum titanium fibrous materials, the quantum titanium fibrous material is by quantum dot, the hybrid material of natural silk and polymer material is prepared by spining technology, the present invention is other than the performance of the soft comfortable with silk fiber, also there is excellent gas permeability, antibiotic property, antiultraviolet, antistatic property and durability and healthcare function, the UPF for the fabric being woven into is far longer than 30, T(UVA) it is far smaller than 5%, and antibiotic rate has reached 90% or more, solve the problems, such as that current silk fabric has a single function and durability is poor, for textile fabric, meet demand of the people to multiple laundry.
Description
Technical field
The present invention relates to complex fiber material fields, and in particular to a kind of quantum titanium fibrous material and preparation method thereof.
Background technique
With the improvement of living standards, requirement of the people to clothing be not only satisfied with it is comfortable and easy to wear, and wish clothing have
Functional property, such as there is perspiration removing moisture absorption, ventilative, antiultraviolet, anti-microbial property, health properties, functionality of the people to clothing
It is required that it is higher and higher, and it is concerned the research of clothing textile material.
Silk is light and elongated, and fabric sheen is good, comfortable and easy to wear, and feel is smooth plentiful, and moisture absorption is ventilative, referred to as fiber emperor
Afterwards, it is widely used in weaving various high-grade silks and satins and knitwear, but silk is a kind of natural azelon, mainly includes fibroin
And silk gum, the silk after degumming under the factors such as long-term light, heat, biology, surface topography, aggregate structure, divide by mechanical property
The structures such as protonatomic mass and performance can change, and the stiffness, antibody Monoclonal ability and wrinkle resistance of silk fabric is caused to decline,
The small-molecule substance that silk decomposes the yellow generated simultaneously can make silk fabric yellowing, so influence silk fabric aesthetics and
Durability.
It generallys use at present and final finishing processing is carried out to improve the performance of silk fabric to silk fabric, but to molded
Fabric carries out the preparation process that final finishing not only increases silk fabric, and final finishing process is using some chemistry examinations mostly
Agent arranges post-finishing agent in web surface physically or chemically to act on attachment, can there is finishing agent in the long-term use process
The problem of falling off, and the purpose being permanently modified to silk is not achieved.
Fiber is set to have the function of that certain antibacterial, antiultraviolet, antistatic etc. have using quantum-dot modified fiber at present
Certain Research foundation, but mostly use quantum dot is supported on fiber surface in a manner of physically or chemically greatly, existing for ask
Topic is: first is that the quantum dot utilization rate easy to reunite for reducing quantum dot in fiber surface；Second is that can be deposited in subsequent fabrication processes
The problem of quantum dot falls off, and cause the waste of quantum dot；Third is that can only to assign fibrous material single for single quantum dot
It is functional.Therefore composite quantum dot is added in fibrous material in situ and quantum dot existing stability in the fibre can be improved,
It can make fiber that there is multifunctionality, and in the prior art by synthesis application in quantum dot in situ addition fibrous material in textile clothes
Quantum dot fibrous material have not been reported.
Based on this, the present invention is to prepare a kind of multi-functional amount using quantum dot as filler using silk fiber as matrix
Sub- titanium fiber is manufactured silk fabric using it as fabric and inherently solves the problems, such as that silk fabric has and assign silkworm
Silk face fabric is multi-functional, and then obtains comfortable and easy to wear, multi-functional clothing.
Summary of the invention
In view of the deficiencies of the prior art, the object of the present invention is to provide one kind to have antiultraviolet, antibacterial, antistatic, saturating
The quantum titanium fibrous material of gas performance, the fibrous material and skin have good compatibility, while having the work of health care
With can directly be contacted with human skin, and antiultraviolet, anti-microbial property will not be cut down during working process, solve mesh
Preceding silk fiber has a single function and the problem of durability difference, meets demand of the people to multiple laundry.
The technical solution that the present invention solves above-mentioned technical problem is:
A kind of quantum titanium fibrous material, the material are by the hybrid material of quantum dot, natural silk and polymer material
It is prepared by spining technology, wherein the quantum dot is graphene/titanium dioxide composite quantum dot, graphene/bis-
Titanium oxide composite quantum dot includes: sulphur, nitrogen co-doped graphene/titanium dioxide composite quantum dot, sulphur, nitrogen co-doped titanium dioxide
Titanium/graphene composite quantum dot, sulphur, nitrogen co-doped graphene/sulphur, nitrogen co-doped titanium dioxide composite quantum dot, described is poly-
Close object material to be made of the raw material of following parts by weight: 22-42 parts of polyethyleneimines, 15-28 parts of alginic acids and 3-8 parts are bright
Glue；
The preparation method of the quantum titanium fibrous material, comprising the following steps:
(1) graphene/titanium dioxide composite quantum dot preparation:
Butyl titanate and glacial acetic acid are dissolved in deionized water, it is molten to be thoroughly mixed acquisition TiO 2 precursor
Citric acid, thioacetic acid and cysteine is added in liquid thereto, is protected from light in a kettle and is stirred to react 6-24h for 130-180 DEG C,
Ethyl alcohol is added, centrifuge separation obtains graphene/titanium dioxide composite quantum dot；
(2) it disperses the graphene in step (1)/titanium dioxide composite quantum dot in deionized water, is added thereto
Dispersing agent obtains graphene/titanium dioxide composite quantum dot dispersion liquid with the power ultrasonic disperse 1-3h of 1000-2000W, to
With；
(3) alginic acid of the parts by weight, gelatin are dissolved in deionized water, limestone powder is added thereto, stirred
Reaction 2-3h is mixed, the polyethyleneimine of the parts by weight is then added thereto, ultrasonic disperse is blended to form polymer solution
A, for use；
(4) by after silk raw material NaOH aqueous solution degumming process, the alkaline solution of natural silk is obtained, is added thereto
Polymer solution A in step (3), is stirred to react, until mixed solution is in neutrality, graphite in step (2) is then added thereto
Alkene/titanium dioxide composite quantum dot dispersion liquid, ultrasonic disperse is uniform, spinning solution is obtained, by spinning solution in 35~40 DEG C of items
Wet spinning is carried out under part, resulting as-spun fibre is immersed in 5wt% ionic calcium soln and is aged after 1~3 times of post-tensioning
24-48h, then through 60~120 DEG C of heat treatments to get quantum titanium fiber.
Preferably, the graphene/titanium dioxide composite quantum dot and the weight ratio of polymer material, natural silk are
1∶4-20∶25-27。
Preferably, the molar ratio of butyl titanate, glacial acetic acid and deionized water described in step (1) is 1: 0.5-1: 3-5.
Preferably, citric acid, thioacetic acid described in step (1), the molar ratio of cysteine are 1: 1-6: 1-6.
Preferably, the weight ratio of butyl titanate and citric acid described in step (1) is 9: 7.
Preferably, dispersing agent described in step (2) be sodium lignin sulfonate, potassium lignosulfonate, Disodium sulfosuccinate,
Succinate potassium sulfonate；Dispersing agent and graphene/titanium dioxide composite quantum dot weight ratio is 1: 1.
Preferably, the weight ratio of limestone powder and alginic acid described in step (3) is 1-10: 1, the limestone powder
Partial size be 300-400 mesh；
Preferably, silk raw material described in step (4) is that useless silk, light defective cocoon, silk offcut and discarded silk product etc. are useless
One or more of gurry.
Preferably, the mass percentage concentration of NaOH solution described in step (4) is 0.5%-1%.
Preferably, the mass percentage concentration of the alkaline solution of natural silk described in step (4) is 18%-24%.
The principle of the invention:
The present invention is using natural silk and polymer composites as matrix, and quantum dot uses spinning skill as filler
The multi-functional quantum titanium fiber that art obtains.The mixture of alginic acid and gelatin is reacted to the titanium dioxide generated with lime stone first
Carbon makes composite material have porosity, the carbon dioxide reaction then filled in addition polymerization aziridine and duct, and is supported on hole
The inside of road structure, while the amino on polyethyleneimine surface and alginic acid or the reaction of the carboxyl of gelatin surface remaining, and reach
The purpose for supporting pore structure, is further compounded to form the compound with porous structure, the quantum being then added with natural silk
Point, which is filled in the cellular structure of composite materials, obtains the evenly dispersed porous quantum titanium fibrous material of quantum dot, compound
Porous structure provides sufficient attachment point for the quantum dot that the later period is added, and the attachment of quantum dot further supports pore structure.
Raw material of the present invention:
Alginic acid: alginic acid is a kind of natural polysaccharide, is mainly derived from seaweed products, as a kind of bioabsorbable polymer material
Have the function of nontoxic, and is widely used, and alginate solution can be with bivalent cation (such as: Ca2+) form crosslinking
The gel of reticular structure.
Gelatin: gelatin be it is a kind of by animal collagen boil bioabsorbable polymer material, have it is cheap and easy to get, nontoxic,
The features such as low swellability, contains a large amount of hydroxyl in gelatin molecule structure, makes it have the water imbibition of reinforcement, and it is rich in carboxylic
Base, amino isoreactivity group can react to form complicated reticular structure with a variety of high molecular materials, in the present invention gelatin
Presence increase the compatibility of natural silk Yu other high molecular materials, and reacting to each other between promoting fibrous material raw material twines
Knot, improves the mechanical property of fiber.
Polyethyleneimine: polyethyleneimine reactivity with higher, the amino energy and carbon dioxide reaction on surface,
Therefore the carbon dioxide in polyethyleneimine meeting oriented attachment duct, is filled in its macromolecular chain in pore structure, supported hole knot
Structure.In addition, polyethyleneimine can also be reacted with various fibers for fibre modification, compound fiber is more with polyethyleneimine
Easily printing and dyeing, polyethyleneimine play the role of printing and dyeing assistant；Polyethyleneimine can occur anti-with groups such as the hydroxyls of fiber surface
Simultaneously cross-linked polymeric is answered, makes that still there is certain wet strength after fibrous absorbent, so that fabric lining is absorbed sweat and still keep later admittedly
Some shapes.
Lime stone: the present invention has both sides effect using lime stone: first is that utilizing its carbonate and boiomacromolecule
The carboxyl on surface reflects to form carbon dioxide, is filled in high molecular material and manufactures porous structure, the size of the partial size of lime stone
Determine the size of pore structure, the limestone powder of uniform particle diameter is evenly dispersed in high molecular material, obtain it is evenly dispersed and
The almost the same porous structure of pore structure, evenly dispersed attachment point is provided for quantum dot, and avoids the group of later period quantum dot
It is poly-, cause the spinning head that high speed spinning is blocked in later period spinning process, and spinning is caused to fail, second is that its calcium ion tentatively with sea
The carboxyl on alginic acid surface forms weak crosslinking, forms the gel with certain fluidity, enhances the mechanical strength of macromolecular chain, be conducive to
Subsequent spinning process.
Natural silk: natural silk is a kind of fibroin that silk is formed after degumming, and fibroin is in alkaline solution
In linear structure, amino acid composition has various polarity group, relies primarily on hydrogen bond, various salt type bonds between protein macromolecule
Etc. interlinking.In subsequent Blending Processes, silk fibroin is intertwine with each other with polyethyleneimine and alginic acid macromolecule,
A degree of crosslinking is generated, after a large amount of linked polymer coils are formed, in fibroin and high molecular polymer mixture
Linear macromolecule reticular structure is formd in system, ensure that the intensity of subsequent fiber.Subsequent fiber is solidifying during the spinning process
Further keep fiber more stable with calcium ion crosslinking in bath and there is higher intensity.
Graphene: graphene is a kind of sheet two dimension material of honeycomb structure being made of single layer sp2 hydbridized carbon atoms
Material, is added into fibrous material, has lamella humidification, and fiber is made to have high-intensitive, high tenacity.Graphene has simultaneously
Excellent conduction and heating conduction plays excellent conduction electrons access in fibrous inside, and then fiber is made to have certain resist
Electrostatic interaction；When the effect of extraneous ultraviolet light, the conduction electrons access of graphene itself can conduct free electron, in fiber
The free electron that addition graphene generates fiber by ultraviolet light diffuses to fiber everywhere, and avoids the mistake of free radical electronics
Concentration is crossed, makes the reduced performance of fiber, achievees the purpose that uvioresistant performance；Graphene quantum dot has antibacterial action, inhibits thin
Bacterium growth, while graphene quantum dot also has the function of emitting far infrared, and play certain health-care effect.
Titanium dioxide: titanium dioxide TiO2There is extraordinary bactericidal effect under the conditions of natural light irradiation, utilize TiO2It receives
Microbial cell is killed in rice material light catalysis effect, and there are two types of different biochemical reaction processes: one is light to excite TiO2Nanometer material
Material is directly contacted with cell, that is, other anabolic actions of light induced electron, hole directly with cell wall, cell membrane or cell；
Another method is exactly light excitation TiO2Nano material does not act on directly with cell, that is, light induced electron either photohole
React to each other with the water either oxygen that is dissolved in water, generate active oxygen, for example, hydroxyl radical free radical and superoxide radical from
Son etc. passes through they and cell wall, cell membrane or intracellular substance generation biochemical reaction.Nano-TiO2Addition on the one hand
Synergic remove is played with direct bactericidal effect and graphene, kills the bacterium bred on fabric lining surface, it is another
Aspect, TiO2With certain self-cleaning function, the strain pollution fabric lining in air is prevented, and clothing is avoided to store for a long time
In journey due to dampness Signs of Mould generation.
The beneficial effects of the present invention are:
Compared with existing silk fiber material, quantum titanium fibrous material of the present invention not only maintains the softness of silk fiber
Comfort property also has multifunctionality, including gas permeability, antibiotic property, antiultraviolet, antistatic and durability and health care function
Can, the UPF for the fabric being woven into is far longer than 30, T (UVA) and is far smaller than 5%, and antibiotic rate has reached 90% or more.
The present invention is met green non-pollution, is repeated to hold to waste and old resource using pollution-free waste and old silk fiber production
The continuous requirement utilized, realizes the resource utilization to waste and old silk, avoids the waste of resource, has better realistic meaning.
The present invention prepares a kind of quantum titanium fiber by the way of In-situ reaction, which has porosity, improves
The gas permeability of textile fabric, and quantum dot is filled in the pore structure of fibrous material, on the one hand avoid fibrous material
Pore structure reduces the mechanical strength of fibrous material, on the other hand avoids the reunion of quantum dot, avoids subsequent spinning
Quantum dot blocks high speed spinning mouth in journey, also avoids fiber quantum dot in subsequent process and reunites again and reduce
The utilization rate of quantum dot.And quantum dot is the inside for being present in fibrous material in form in situ, in the long-term use process
It will not fall off, antibacterial uvioresistant performance is permanently effective, improves the durability of material.
Quantum dot of the invention is the graphene/titanium dioxide composite quantum obtained by the way of one-step method In-situ reaction
Point, graphene, titanium dioxide have synergistic effect in terms of antiultraviolet and antibacterial action, improve antibacterial, the UV resistance of material
Linearly energy, and graphene and titanium dioxide are mutually interspersed between mutual particle, avoid mutual mutual reunion, and use
Nitrogen, sulphur mix up titanium dioxide altogether and graphene plays the role of both sides: first is that improving quantum dot in high molecular material
Dispersibility avoids reuniting；On the other hand the hetero-junctions for changing titanium dioxide and graphene, changes its light, electrical property, widens its suction
Optical range, and further increase the ability of fibrous material antiultraviolet and improve the resistance to visible light ability of material and improve clothing
Wear the service life.
Quantum titanium fiber of the present invention has certain ability and ultraviolet resistance and water-resistant capacity, avoids the long-term dress of clothing
Discoloration (is such as turned to be yellow), with certain wet strength when meeting a small amount of water, is guaranteed the stiffness of clothing, is worn clothing for a long time
It is beautiful.
Quantum titanium fiber of the present invention also has medical care effect, and graphene has transmitting far infrared in quantum titanium fiber
Ability, far infrared have the ability for promoting blood circulation and strengthening body metabolism, improving immunity of organism.
Specific embodiment
Further to illustrate technological means and its effect adopted by the present invention, carried out below in conjunction with specific embodiment detailed
Thin description.
Embodiment 1
A kind of quantum titanium fibrous material, the material are by the hybrid material of quantum dot, natural silk and polymer material
It is prepared by spining technology, wherein the quantum dot is graphene/titanium dioxide composite quantum dot, graphene/bis-
Titanium oxide composite quantum dot includes: sulphur, nitrogen co-doped graphene/titanium dioxide composite quantum dot, sulphur, nitrogen co-doped titanium dioxide
Titanium/graphene composite quantum dot, sulphur, nitrogen co-doped graphene/sulphur, nitrogen co-doped titanium dioxide composite quantum dot, described is poly-
It closes object material to be made of the raw material of following parts by weight: 22 parts of polyethyleneimines, 15 parts of alginic acids and 3 parts of gelatin；Specific system
Preparation Method is as follows:
(1) graphene/titanium dioxide composite quantum dot preparation:
0.05mol glacial acetic acid is added to the butyl titanate of 0.1mol, then adds in 5.4g deionized water, sufficiently stirs
It mixes mixing and obtains TiO 2 precursor solution, sequentially add half Guang of 14.9g citric acid, 7.1g thioacetic acid and 9.4g thereto
Propylhomoserin is protected from light and is stirred to react for 24 hours for 130 DEG C in a kettle, cooling, ethyl alcohol is then added, centrifuge separation obtains graphene/dioxy
Change titanium composite quantum dot；
(2) it disperses the graphene in step (1)/titanium dioxide composite quantum dot in deionized water, is added thereto
Graphene/titanium dioxide is obtained with the power ultrasonic disperse 3h of 1000W with the sodium lignin sulfonate of the quality such as composite quantum dot
Composite quantum dot dispersion liquid, for use；
(3) alginic acid of the parts by weight, gelatin are dissolved in deionized water, are added thereto and the quality such as alginic acid
300-400 mesh limestone powder, be stirred to react 2h, the polyethyleneimine of the parts by weight be then added thereto, surpass
Sound dispersion, which is blended, forms polymer solution A, for use；
(4) by after silk offcut 1wt%NaOH aqueous solution degumming process, acquisition mass percentage concentration is 18wt% silkworm
The polymer solution A in step (3) is added thereto, is stirred to react for the alkaline solution of silk fibroin, until mixed solution is in neutrality,
Graphene/titanium dioxide composite quantum dot dispersion liquid in step (2) is then added thereto, ultrasonic disperse is uniform, obtains spinning
Spinning solution is carried out wet spinning by solution under the conditions of 35 DEG C, and resulting as-spun fibre immerses after 1~3 times of post-tensioning
It is aged for 24 hours in 5wt% ionic calcium soln, then through 60 DEG C of heat treatments to get quantum titanium fiber.
Further, the weight ratio of the graphene/titanium dioxide composite quantum dot and polymer material, natural silk
It is 1: 4: 25.
Embodiment 2
A kind of quantum titanium fibrous material, the material are by the hybrid material of quantum dot, natural silk and polymer material
It is prepared by spining technology, wherein the quantum dot is graphene/titanium dioxide composite quantum dot, graphene/bis-
Titanium oxide composite quantum dot includes: sulphur, nitrogen co-doped graphene/titanium dioxide composite quantum dot, sulphur, nitrogen co-doped titanium dioxide
Titanium/graphene composite quantum dot, sulphur, nitrogen co-doped graphene/sulphur, nitrogen co-doped titanium dioxide composite quantum dot, described is poly-
It closes object material to be made of the raw material of following parts by weight: 32 parts of polyethyleneimines, 21.5 parts of alginic acids and 5.5 parts of gelatin；Tool
Preparation are as follows:
(1) graphene/titanium dioxide composite quantum dot preparation:
0.075mol glacial acetic acid is added into 0.1mol butyl titanate, is then added in 7.2g deionized water, sufficiently stirs
It mixes mixing and obtains TiO 2 precursor solution, sequentially add 14.9g citric acid, 24.85g thioacetic acid and 32.9g thereto
Cysteine is protected from light in a kettle and is stirred to react 15h for 155 DEG C, cooling, and ethyl alcohol is added, and centrifuge separation obtains graphene/dioxy
Change titanium composite quantum dot；
(2) it disperses the graphene in step (1)/titanium dioxide composite quantum dot in deionized water, is added thereto
Graphene/titanium dioxide is obtained with the power ultrasonic disperse 2h of 1500W with the Disodium sulfosuccinate of the quality such as composite quantum dot
Titanium composite quantum dot dispersion liquid, for use；
(3) alginic acid of the parts by weight, gelatin are dissolved in deionized water, 300-400 mesh lime is added thereto
Stone powder is stirred to react 2.5h, is then added the polyethyleneimine of the parts by weight thereto, ultrasonic disperse be blended to be formed it is poly-
Polymer solution A, for use, wherein the weight ratio of limestone powder and alginic acid is 5.5: 1；
(4) after silk offcut 0.75wt%NaOH aqueous solution degumming process, will obtain mass percentage concentration is
The polymer solution A in step (3) is added thereto, is stirred to react, until mixed solution for the alkaline solution of 21wt% natural silk
It is in neutrality, graphene/titanium dioxide composite quantum dot dispersion liquid in step (2) is then added thereto, ultrasonic disperse is uniform, obtains
Spinning solution, spinning solution is subjected to wet spinning under the conditions of 38 DEG C, resulting as-spun fibre is through 1~3 times of post-tensioning
Afterwards, it immerses in 5wt% ionic calcium soln and is aged 36h, then through 90 DEG C of heat treatments to get quantum titanium fiber.
Further, the weight ratio of the graphene/titanium dioxide composite quantum dot and polymer material, natural silk
It is 1: 12: 26.
Embodiment 3
A kind of quantum titanium fibrous material, the material are by the hybrid material of quantum dot, natural silk and polymer material
It is prepared by spining technology, wherein the quantum dot is graphene/titanium dioxide composite quantum dot, graphene/bis-
Titanium oxide composite quantum dot includes: sulphur, nitrogen co-doped graphene/titanium dioxide composite quantum dot, sulphur, nitrogen co-doped titanium dioxide
Titanium/graphene composite quantum dot, sulphur, nitrogen co-doped graphene/sulphur, nitrogen co-doped titanium dioxide composite quantum dot, described is poly-
It closes object material to be made of the raw material of following parts by weight: 42 parts of polyethyleneimines, 28 parts of alginic acids and 8 parts of gelatin；It is specifically made
It is standby that steps are as follows:
(1) graphene/titanium dioxide composite quantum dot preparation:
0.1mol glacial acetic acid is added into 0.1mol butyl titanate, is then added in 9.0g deionized water, is sufficiently stirred
Mixing obtains TiO 2 precursor solution, sequentially adds half Guang of 14.9g citric acid, 42.6g thioacetic acid and 56.4g thereto
Propylhomoserin is protected from light in a kettle and is stirred to react 6h for 180 DEG C, cooling, and ethyl alcohol is added, and centrifuge separation obtains graphene/titanium dioxide
Composite quantum dot；
(2) it disperses the graphene in step (1)/titanium dioxide composite quantum dot in deionized water, is added thereto
Graphene/titanium dioxide is obtained with the power ultrasonic disperse 1h of 2000W with the sodium lignin sulfonate of the quality such as composite quantum dot
Composite quantum dot dispersion liquid, for use；
(3) alginic acid of the parts by weight, gelatin are dissolved in deionized water, the stone of 300-400 mesh is added thereto
Lime stone powder is stirred to react 3h, is then added the polyethyleneimine of the parts by weight thereto, ultrasonic disperse be blended to be formed it is poly-
Polymer solution A, for use, wherein the weight ratio of limestone powder and alginic acid is 10: 1；
(4) alkalinity for after silk raw material 1wt%NaOH aqueous solution degumming process, obtaining 24wt% natural silk is molten
The polymer solution A in step (3) is added thereto, is stirred to react, until mixed solution is in neutrality, is then added thereto for liquid
Graphene/titanium dioxide composite quantum dot dispersion liquid in step (2), ultrasonic disperse is uniform, spinning solution is obtained, by spinning solution
Wet spinning is carried out under the conditions of 40 DEG C, resulting as-spun fibre immerses 5wt% ionic calcium soln after 1~3 times of post-tensioning
Middle ageing 48h, then through 120 DEG C of heat treatments to get quantum titanium fiber.
Further, the weight ratio of the graphene/titanium dioxide composite quantum dot and polymer material, natural silk
It is 1: 20: 27.
Comparative example 1
Comparative example 1 is substantially the same manner as Example 3, the difference is that being not added with graphene/titanium dioxide composite quantum dot.
Comparative example 2
Comparative example 2 is substantially the same manner as Example 3, the difference is that graphene/titanium dioxide composite quantum dot equivalent
Graphene quantum dot replace.
There is the blocked phenomenon of the spinning head of high speed spinning during the spinning process.
Comparative example 3
Comparative example 3 is substantially the same manner as Example 3, the difference is that graphene/titanium dioxide composite quantum dot equivalent
Nano-titanium dioxide powder replace.
There is the blocked phenomenon of the spinning head of high speed spinning during the spinning process.
Comparative example 4
Comparative example 4 is substantially the same manner as Example 3, the difference is that being not added with limestone powder.
There is the blocked phenomenon of the spinning head of high speed spinning during the spinning process.
Comparative example 5
Comparative example 5 is substantially the same manner as Example 3, the difference is that the alginic acid of polyethyleneimine equivalent replaces.
Comparative example 6
Comparative example 6 is substantially the same manner as Example 3, the difference is that the alginic acid of gelatin equivalent replaces.
Comparative example 7
Comparative example 7 is substantially the same manner as Example 3, the difference is that polymer material all uses the natural silk generation of equivalent
It replaces.
Silk solution-polymerized SBR can not form, and illustrate that individual natural silk lacks polymer material as attachment, no
Textile fabric can be formed.
Performance test
The Mechanics Performance Testing of quantum titanium fibrous material:
Performance test is carried out to the fibrous material of silk, embodiment 1-3 and comparative example 1-6 preparation respectively, as a result such as table 1
It is shown.
The mechanical experimental results of 1. silk of table, embodiment 1-3 and comparative example 1-7 resulting materials
As shown in table 1, the mechanical property for the quantum titanium fibrous material that embodiment 1-3 is obtained is better than silk, illustrates this hair
The quantum titanium fiber of bright preparation can be used for textile fabric field.And the mechanical property for the fibrous material that comparative example 1-7 is prepared
Lower than the embodiment of the present invention 3 obtain quantum titanium fiber, comparative example 1 is substantially the same manner as Example 3, be only not added with graphene/
Titanium dioxide composite quantum dot, mechanical property are lower than embodiment 3, are that be uniformly filled in fibrous material due to composite quantum dot more
Support and reinforcing are played the role of to fiber in the inside of pore structure, are conducive to the raising of the mechanical property of fiber；Comparative example 2 and 3
It is substantially the same manner as Example 3, the difference is that graphene/titanium dioxide composite quantum dot with graphene quantum dot and is received respectively
Rice titanium dioxide replaces, and it is due to undoped individual graphene quantum dot or nanometer two that mechanical property, which is lower than embodiment 3,
Bad dispersibility of the titanium oxide powder in fibrous material, and the mechanical property of fiber is influenced, while the mechanical property of comparative example 2 is slightly
It is weaker than comparative example 3, illustrates the good dispersion of graphene quantum dot in the fibre compared with nano-titanium dioxide powder, and it is enhancing
Advantage is had more in terms of the mechanical property of fiber；Comparative example 4 is substantially the same manner as Example 3, the difference is that being not added with lime stone
Powder, mechanical property are poor compared with embodiment 3, are on the one hand since lacking for lime stone makes to be formed uniform hole knot in fiber
Structure, and composite quantum dot has lacked attachment point in the fibre, and composite quantum dot is caused to reunite in the material seriously does not make it not only not
The intensity that can increase fiber also adds the breaking point in fiber, and causes difficulty in spinning；On the other hand be due to lack calcium from
Son lacks calcium ion crosslinking body in fibrous inside in spinning solution forming process as crosslinking agent, and the fiber for obtaining the later period
Mechanical property it is poor；Comparative example 5 is substantially the same manner as Example 3, the difference is that, polyethyleneimine equivalent therein
Alginic acid replaces, and 5 poor mechanical property of comparative example is due to lacking polyethyleneimine in the porous structure for the fiber that early period is formed
The supporting role of amine easily causes the fracture of fiber at pore structure, and the mechanical property of polyethyleneimine is better than alginic acid, is mentioning
It plays an important role in terms of high microsteping mechanical property；Comparative example 6 is substantially the same manner as Example 3, the difference is that, it is therein bright
The alginic acid of glue equivalent replaces, 6 poor mechanical property of comparative example, is since gelatin and natural silk belong to protein, gelatin
Presence, increase the compatibility of polyethyleneimine and alginic acid and natural silk, making fibrous inside, there is no layering is existing
As be cross-linked with each other entanglement between high molecular material, is conducive to the mechanical property for improving fiber.
In conclusion can illustrate there is chemiluminescence in the present invention between each raw material, suitable raw material proportioning makes this hair
Bright quantum titanium fiber has good mechanical property, meets the requirement of textile fiber material.
Antiultraviolet, anti-microbial property test:
Silk, embodiment 1-3 and comparative example 1-6 acquisition fibrous material are made into after fabric and carry out following performance test, knot
Fruit such as table 2.
Antiultraviolet test: GB/T18830-2009 " evaluation of properties of textile " according to national standards uses textile fabric
The UV protection factor UPF and ultraviolet ray transmissivity T of SPF analyzer test blended fabric；As the UPF > 30 of fabric,
When T (UVA) < 5%, which belongs to antiultraviolet product.
Antibacterial test: GB/20944.3-2008 " the evaluation third portion of antibacterial textile performance: oscillation according to national standards
Method " method tested, the anti-microbial property of sample is evaluated by bacteriostasis rate, calculation formula are as follows: XS=(A-B)/A, formula
In: XS is bacteriostasis rate (%)；A is average colony number before being vibrated by test agent；B is average colony number after being vibrated by test agent, such as
Average colony number after fruit oscillation is greater than the average colony number before oscillation, and bacteriostasis rate is calculated by 0.
The fibrous material antiultraviolet and anti-microbial property test result that 2. silk of table, embodiment 1-3 and comparative example 1-6 are obtained
As shown in table 2, the fabric ultraviolet resistance that the quantum titanium fiber that 1-3 of the embodiment of the present invention is prepared is made into is surveyed
Test result shows that UPF value is far longer than 30, T (UVA) less than 5%, to Escherichia coli, Candida albicans, Staphylococcus aureus
The antibiotic rate of bacterium has reached 90% or more, and silk fiber fabric UPF value, less than 30, T (UVA) transmitance is far longer than 5%,
Illustrate that quantum titanium fiber of the invention has excellent antiultraviolet and anti-microbial property.
The embodiment of the present invention 3 obtains the fabric ultraviolet resistance that is made into of quantum titanium fiber and anti-microbial property is better than pair
The fibrous material of ratio 1-6；
Comparative example 1 compared with Example 3, is not added with composite quantum dot in comparative example 1, UPF < 30, T (UVA) > 5%,
Antibiotic rate is 0, illustrates that it does not have the performance of antiultraviolet and antibacterial；Respectively with graphene quantum dot and receiving in comparative example 2 and 3
Rice titanium dioxide powder replaces composite quantum dot, and UPF < 30, T (UVA) > 5% illustrates that it does not have the property of antiultraviolet
Can, antibiotic rate illustrates that the antibiotic property of fiber prepared by comparative example 2 and comparative example 3 is poor also below embodiment 3；Comparative example 2 and right
Ratio 3 is with the comparison of embodiment 3 the result shows that the antiultraviolet that the composite quantum dot in the present invention plays the role of in the fibre
Effect is better than individual graphene quantum dot or nano-titanium dioxide powder.
Compared with Example 3, comparative example 4-6 is to be not added with limestone powder, polyethyleneimine use etc. respectively to comparative example 4-6
The alginic acid of amount replaces, the alginic acid of gelatin equivalent replaces, and UPF value is all larger than 30, T (UVA) and is respectively less than 5%, illustrates it
With certain ultraviolet resistance, but the effect of antiultraviolet is less than embodiment 3, also low to the antibiotic rate of three kinds of bacteriums
In embodiment 3, illustrate that its antibiotic property is also poorer than embodiment 3；By being compared above it is found that having between each raw material of the invention certain
Synergistic effect, promote fiber that there is excellent structure and be conducive to the attachment of quantum dot, and then it is excellent to show fibrous material
Different antiultraviolet and anti-microbial property.
The performance test results of quantum titanium fibrous material of the invention show: raw material properly matches between quantum titanium fibrous material
Than ensure that the excellent structural behaviour of fibrous material, and its functional performance is further improved, there is excellent antiultraviolet
And antibiotic property.
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, this field is common
Other modifications or equivalent replacement that technical staff makes technical solution of the present invention, without departing from technical solution of the present invention
Spirit and scope, be intended to be within the scope of the claims of the invention.
Claims (10)
1. a kind of quantum titanium fibrous material, which is to lead to the hybrid material of quantum dot, natural silk and polymer material
It crosses spining technology to prepare, wherein the quantum dot is graphene/titanium dioxide composite quantum dot, the graphene/dioxy
Changing titanium composite quantum dot includes: sulphur, nitrogen co-doped graphene/titanium dioxide composite quantum dot, and sulphur, nitrogen co-doped titanium dioxide/
Graphene composite quantum dot, sulphur, nitrogen co-doped graphene/sulphur, nitrogen co-doped titanium dioxide composite quantum dot, the polymer
Material is made of the raw material of following parts by weight: 22-42 parts of polyethyleneimines, 15-28 parts of alginic acids and 3-8 parts of gelatin；
The preparation method of the quantum titanium fibrous material, comprising the following steps:
(1) graphene/titanium dioxide composite quantum dot preparation:
Butyl titanate and glacial acetic acid are dissolved in deionized water, is thoroughly mixed and obtains TiO 2 precursor solution,
Citric acid, thioacetic acid and cysteine are added thereto, is protected from light in a kettle and is stirred to react 6-24 h for 130-180 DEG C, add
Enter ethyl alcohol, centrifuge separation obtains graphene/titanium dioxide composite quantum dot；
(2) it disperses the graphene in step (1)/titanium dioxide composite quantum dot in deionized water, dispersion is added thereto
Agent obtains graphene/titanium dioxide composite quantum dot dispersion liquid, for use with the power ultrasonic disperse 1-3 h of 1000-2000W；
(3) alginic acid of the parts by weight, gelatin are dissolved in deionized water, limestone powder is added thereto, stirring is anti-
2-3 h to be answered, the polyethyleneimine of the parts by weight is then added thereto, ultrasonic disperse is blended to form polymer solution A, to
With；
(4) by after silk raw material NaOH aqueous solution degumming process, the alkaline solution of natural silk is obtained, step is added thereto
(3) the polymer solution A in, is stirred to react, until mixed solution is in neutrality, graphene/bis- in step (2) are then added thereto
Titanium oxide composite quantum dot dispersion liquid, ultrasonic disperse is uniform, obtain spinning solution, by spinning solution under the conditions of 35~40 DEG C into
Row wet spinning, resulting as-spun fibre immerse after 1~3 times of post-tensioning and are aged 24-48 h in 5wt% ionic calcium soln,
Again through 60~120 DEG C of heat treatments to get quantum titanium fiber.
2. quantum titanium fibrous material as described in claim 1, which is characterized in that the graphene/titanium dioxide compound quantity
Son point and the weight ratio of polymer material, natural silk are 1: 4-20: 25-27.
3. quantum titanium fibrous material as described in claim 1, which is characterized in that butyl titanate described in step (1), ice vinegar
The molar ratio of acid and deionized water is 1: 0.5-1: 3-5.
4. quantum titanium fibrous material as described in claim 1, which is characterized in that citric acid described in step (1), sulfydryl second
Sour, cysteine molar ratio is 1: 1-6: 1-6.
5. quantum titanium fibrous material as described in claim 1, which is characterized in that butyl titanate and lemon described in step (1)
The weight ratio of lemon acid is 9: 7.
6. quantum titanium fibrous material as described in claim 1, which is characterized in that dispersing agent described in step (2) is lignin
Sodium sulfonate, potassium lignosulfonate, Disodium sulfosuccinate, Disodium sulfosuccinate potassium；The dispersing agent and graphene/dioxy
The weight ratio for changing titanium composite quantum dot is 1: 1.
7. quantum titanium fibrous material as described in claim 1, which is characterized in that limestone powder described in step (3) and sea
The weight ratio of alginic acid is 1-10: 1, and the partial size of the limestone powder is 300-400 mesh.
8. quantum titanium fibrous material as described in claim 1, which is characterized in that silk raw material described in step (4) is useless silkworm
One or more of wastes such as silk, light defective cocoon, silk offcut and discarded silk product.
9. quantum titanium fibrous material as described in claim 1, which is characterized in that the matter of NaOH aqueous solution described in step (4)
Amount percentage concentration is 0.5%-1%.
10. quantum titanium fibrous material as described in claim 1, which is characterized in that the alkalinity of natural silk described in step (4)
The mass percentage concentration of solution is 18%-24%.
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| CN111575858A (en) * | 2020-05-23 | 2020-08-25 | 石洛豪 | Quantum fiber fabric with functional effect |
| CN112778583A (en) * | 2021-01-11 | 2021-05-11 | 无锡万斯家居科技股份有限公司 | Latex pillow containing graphene quantum dots and preparation method thereof |
| CN118685876A (en) * | 2024-08-27 | 2024-09-24 | 天津包钢稀土研究院有限责任公司 | A rare earth functional material for antibacterial spinning and rare earth antibacterial fabric |
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