CN108716118A - A kind of preparation process of tea polyphenols modification viscose rayon - Google Patents
A kind of preparation process of tea polyphenols modification viscose rayon Download PDFInfo
- Publication number
- CN108716118A CN108716118A CN201810553400.3A CN201810553400A CN108716118A CN 108716118 A CN108716118 A CN 108716118A CN 201810553400 A CN201810553400 A CN 201810553400A CN 108716118 A CN108716118 A CN 108716118A
- Authority
- CN
- China
- Prior art keywords
- viscose rayon
- tea polyphenols
- ratio
- collection
- pure water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
- D06M13/238—Tannins, e.g. gallotannic acids
-
- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/11—Compounds containing epoxy groups or precursors thereof
-
- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
- D06M13/256—Sulfonated compounds esters thereof, e.g. sultones
-
- 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
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
- D06M16/003—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic with enzymes or microorganisms
-
- 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
- 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
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
-
- 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
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/25—Resistance to light or sun, i.e. protection of the textile itself as well as UV shielding materials or treatment compositions therefor; Anti-yellowing treatments
Abstract
A kind of preparation process of tea polyphenols modification viscose rayon, belongs to viscose rayon modification technique field.The present invention is using commercially available tea polyphenols and viscose rayon as raw material, viscose rayon is pre-processed by preparing surfactant, prepare cellulose hydrolyzation viscose rayon, prepare Adsorption of Tea Polyphenols viscose rayon, the step of preparing grafting tea polyphenols viscose rayon just prepares the viscose rayon that tea polyphenols grafting rate is 8~10%.The present invention has carried out cellulose hydrolyzation before preparing grafting tea polyphenols viscose rayon to it so that a degree of degradation occurs for viscose rayon, and activity hydroxy thereon is able to abundant exposure, convenient for improving the grafting rate of tea polyphenols;The method of the present invention uses the bisglycidyl ether with bis-epoxy functional group as cross-linking reaction agent, so that viscose rayon is stably connected with tea polyphenols by chemical covalent bonds, tea polyphenols grafting rate is high, stability enhances, to significantly improve the functions such as the anti-oxidant of product, radioresistance, antibacterial, chelated metal ions.
Description
One, technical field
The invention belongs to viscose rayon modification technique fields, and in particular to a kind of preparation work of tea polyphenols modification viscose rayon
Skill.
Two, background technology
Viscose rayon belongs to regenerated cellulose, be by D-Glucose with β-Isosorbide-5-Nitrae glucosides key connection at high molecular polymer.
Since there are a large amount of hydrophilic hydroxyl groups in cellulosic molecule, cause viscose rayon product that there is good moisture absorption, gas permeability and pro-skin
Performance, it is in addition soft and warming, become the important source material of textile industry.But viscose rayon is wrinkled there is also poor flexibility, easily, is washed
Type and shrink are easily walked afterwards, the defects of shape-retaining ability is poor;Have it is demonstrated experimentally that the certain micro-organisms invested on fiber can utilize cellulose
The moisture flourish of hydroxyl absorption, the enzyme of secretion degradation β-Isosorbide-5-Nitrae glycosidic bond, degraded cellulose at available glucose, this
The structure and intensity for not only destroying fiber also further result in fabric and mildew and spot and then pollute skin;In addition to this, there is pro-skin
The fiber of performance is but difficult to the oxidation for preventing free radical to body, and lacks radioresistance functional group, does not also have suction
The site of attached metal ion, these defects prevent it from meeting the differentiation of modern fabrics, the demand of functionalization and comfort, into
And limit the further expansion of its application field.In order to fully develop the potential function of viscose rayon, viscose rayon is carried out each
Kind study on the modification, the added value for improving viscose rayon and performance have become a general orientation of people's research.
Tea polyphenols are the general names of Polyphenols of Tea.Their basic structure is that 2- connects (or adjacent) phenylol benzo pyrrole
The derivative muttered can be divided into four classes by its chemical constitution:Catechin, flavones and flavonols, leucoanthocyanidin and anthocyan, phenol
Acid and depside.Wherein catechin is its main matter, the 70%~80% of Polyphenols total amount about in tealeaves.Tea polyphenols
Parent nucleus in molecule is 2- phenyl chromones, contains multiple phenolic hydroxyl groups, 2- phenyl chromone rings on the phenyl of the parent nucleus and connection
On electron cloud be uniformly distributed and the phenyl that connects crosses over the delocalized electron cloud of more than 20 atoms, thus phenolic hydroxyl group is made to have antioxygen
Change, the ability of antibacterial and chelating heavy metal ion, the phenyl of 2- phenyl chromone rings and connection is made to have radioresistance, uvioresistant
Performance etc..
The existing technology for preparing functional fiber material and its derivative that tea polyphenols are combined with viscose rayon, such as
Application No. is 201610347050.6 patent, a kind of tea polyphenols cellulose fibre spunlace non-woven cloth and its production work are disclosed
Skill, the tea polyphenols cellulose fibre spunlace non-woven cloth are principal fiber by cellulose fibres such as tencel, viscose rayon and Modals, are added
Sweat antiseptic is led in the tea polyphenol nano grade extraction extract of upper 95% or more purity and moisture absorption, and is manufacturing spunlace non-woven cloth
When be added in web and efficient absorbent is made, leads sweat antibacterial, antiallergy and the product of anti-inflammatory.Although the patent proposes tea polyphenols
The concept of cellulose fibre, but be not tea polyphenols modified fibre truly, it is only object between fiber and tea polyphenols
Reason mixing, is not related to chemically react, therefore the product is in use, tea polyphenols are easy to fall off so that the antibacterial of product resists
The functional stabilizations such as oxidation are not high, also little using the effect obtained in other respects.
In another example application No. is 201611163439.1 patent, a kind of tea polyphenols cellulose fibre and its preparation are disclosed
Method, using silane coupling agent as crosslinking agent, on cellulose by tea polyphenols grafting.The disadvantages of this method is:1. preparing tea
Time needed for polyphenol pretreatment fluid is 8~10 hours, and it is 30~36 hours to maintain the time needed for cross-linking reaction, the reaction time
It is tediously long, it is relatively low for the economic benefit acquired by industrial production;2. crosslinking agent used is silane coupling agent, however silane coupling agent
More it is suitble to the active group of the silicone hydroxyl and organic material surface of connection inorganic material surface, cellulose is macromolecule polysaccharide,
It is carried out being crosslinked unobvious of producing effects with silane coupling agent.3. in addition, silane coupling agent used in the patent is 3- glycidol ethers
Oxygroup propyl-triethoxysilicane, commercially available price are high so that cost increases, and is equally unfavorable for large-scale use and the life of industry
Production.
Three, invention content
The purpose of the present invention is modifying the shortcoming of viscose rayon technique for existing tea polyphenols, a kind of tea polyphenols are provided
Modify the preparation process of viscose rayon.The technique not only makes tea polyphenols with viscose rayon to be covalently keyed and grafting rate significantly carries
High, grafting viscose rayon antibacterial and dyeability enhancing, also maintain the original main mechanical properties of viscose rayon.Moreover,
The technique also has the characteristics that easy to operate, at low cost, easy to utilize, and the grafting tea polyphenols viscose rayon prepared has anti-
The effects that bacterium, anti-oxidant, anti-ultraviolet radiation, it can be applied to the fields such as weaving, clothes, decoration.
The present invention cardinal principle be:Cellulase (β-Isosorbide-5-Nitrae-glucan -4- glucan hydrolases) is degraded cellulose
The general name of glucogenic one group of enzyme, in decomposition of cellulose from biocatalysis, can be by cellulose decomposition at oligosaccharides
Or monosaccharide;Viscose rayon belongs to regenerated cellulose, be by D-Glucose with β-Isosorbide-5-Nitrae glucosides key connection at high molecular polymer,
The reaction condition of control fiber element enzymatic treatment viscose rayon, can bring it about a degree of degradation, to make viscose rayon
More terminal hydroxyl active groups are exposed, to be grafted with tea polyphenols;Bisglycidyl ether crosslinking agent is a kind of double
The hydroxyl crosslinking agent of epoxy-functional has good wetting ability, can also improve the flexibility of cross-linking agent;Through cellulase
Treated viscose rayon and tea polyphenols have abundant free hydroxyl group, can occur under optimum conditions with bisglycidyl ether
Crosslinking.
The object of the present invention is achieved like this:A kind of preparation process of tea polyphenols modification viscose rayon is more with commercially available tea
Phenol and viscose rayon are raw material, pre-process viscose rayon by preparing surfactant, prepare cellulose hydrolyzation viscose rayon,
Prepare Adsorption of Tea Polyphenols viscose rayon, prepare grafting tea polyphenols viscose rayon the step of, just prepare tea polyphenols grafting rate be 8~
10% viscose rayon.Its specific processing step is as follows:
(1) surfactant pretreatment viscose rayon is prepared
Surfactant sodium dodecyl base benzene sulfonic acid sodium salt mass fraction is made first and is 0.5~2% pretreatment fluid, then is pressed
According to the ratio that the ratio between viscose rayon quality and the pretreatment fluid volume are 1: 18~22kg/L, viscose rayon is scattered in added with this
In the reaction kettle of pretreatment fluid, 90~100 DEG C are warming up to, 0.5~1.5h of stirring pretreatment.Tapping after the completion of pretreatment, respectively
It collects pretreated viscose rayon and pre-processes the waste liquid after viscose rayon.The pretreated viscose rayon collected, according to
Viscose rayon quality and the ratio that pure water volume ratio is 1: 8~12kg/L are added pure water and clean 2~4 times.After the completion of cleaning
It is dried at 30~40 DEG C, that is, prepares surfactant pretreatment viscose rayon, it is viscous to prepare cellulose hydrolyzation for lower step
Glue fiber;It to the waste liquid after the pretreatment viscose rayon of collection, is pumped to biochemical treatment station and is handled, discharged after up to standard.
(2) cellulose hydrolyzation viscose rayon is prepared
It is 1: 18 according to surfactant pretreatment the ratio between viscose rayon quality and pure water volume after the completion of (1) step
Surfactant pretreatment viscose rayon is scattered in pure water, is warming up to 40~50 DEG C, adds by the ratio of~22kg/L
Quality accounts for the cellulase of surfactant pretreatment viscose rayon 1~3%, reacts 2~4h after adjusting pH to 5.0~6.0.Instead
Cellulase treated viscose rayon and enzymolysis waste liquid are collected in tapping after answering respectively.After the cellulase processing of collection
Viscose rayon, according to the ratio between viscose rayon quality and pure water volume be 1: 8~12kg/L ratio be added pure water cleaning 2
~4 times.The cellulose hydrolyzation viscose rayon after cleaning and the waste liquid after cleaning cellulose hydrolyzation viscose rayon are collected respectively,
To the waste liquid after the cleaning cellulose hydrolyzation viscose rayon of collection, is merged with the enzymolysis waste liquid of collection, be pumped to biochemistry
Treating stations are handled, and are discharged after up to standard.To the cellulose hydrolyzation viscose rayon after the cleaning of collection, dried at 30~40 DEG C
It is dry, that is, cellulose hydrolyzation viscose rayon is prepared, preparing tea polyphenols for lower step adsorbs viscose rayon.
(3) Adsorption of Tea Polyphenols viscose rayon is prepared
After the completion of (2) step, the aqueous solution that tea polyphenols mass percentage concentration is 0.6~1.2% first is made with pure water,
The body for the aqueous solution that quality according still further to cellulose hydrolyzation viscose rayon is 0.6~1.2% with tea polyphenols mass percentage concentration
The ratio between product is the ratio of 1: 18~22kg/L, cellulose hydrolyzation viscose rayon is scattered in the tea polyphenols aqueous solution, then
With dilute sodium hydroxide regulation system pH to 9~11 1~3h is adsorbed controlled at 80~90 DEG C.Tapping after the completion of to be adsorbed,
The viscose rayon after Adsorption of Tea Polyphenols and the solution after desorption part tea polyphenols are collected respectively, to the Adsorption of Tea Polyphenols of collection
The viscose rayon afterwards, as Adsorption of Tea Polyphenols viscose rayon prepare grafting tea polyphenols viscose rayon for lower step;For collecting
Desorption part tea polyphenols after the solution can be used under preparation after adding tea polyphenols and pure water containing unadsorbed tea polyphenols
Batch Adsorption of Tea Polyphenols viscose rayon.
(4) grafting tea polyphenols viscose rayon is prepared
After the completion of (3) step, according to the body of the quality and pure water of the cellulose hydrolyzation viscose rayon of (3) step addition
The ratio between product is the ratio of 1: 14~18kg/L, and pure water is first added into the reaction kettle equipped with Adsorption of Tea Polyphenols viscose rayon, then
Ethylene glycol bisglycidyl ether or butanediol bisglycidyl ether or hexylene glycol bisglycidyl ether, the second of addition are added thereto
Glycol bisglycidyl ether or the volume of butanediol bisglycidyl ether or hexylene glycol bisglycidyl ether are that tea is added in (3) step
2~4h is reacted in the 0.6~1.2% of polyphenol aqueous solution volume under conditions of temperature is 80~90 DEG C.Tapping after the completion of reaction,
Crosslinking agent treated viscose rayon and waste reaction solution is collected respectively.The crosslinking agent of collection treated viscose rayon, according to viscous
The ratio that the ratio between glue fiber quality and pure water volume are 1: 8~12kg/L is added pure water and cleans 2~4 times.It collects respectively clear
The waste liquid after grafting tea polyphenols viscose rayon and cleaning grafting tea polyphenols viscose rayon after washing is more to the cleaning grafting tea of collection
Waste liquid after phenol viscose rayon is merged with the waste reaction solution of collection, is pumped to biochemical treatment station and is handled, heel row up to standard
It puts.It to the grafting tea polyphenols viscose rayon after the cleaning of collection, moves it into tunnel drier, is 30~40 in temperature
DEG C, transmission speed be 0.1~0.5r/min under conditions of, handle 0.5~1h, that is, prepare grafting tea polyphenols viscose rayon,
Middle tea polyphenols grafting rate is 8~10%.
The present invention is after adopting the above technical scheme, mainly have the following effects:
1, the method for the present invention is using commercially available tea polyphenols and viscose rayon as raw material, low production cost, and production equipment used is equal
For industrial equipment, working condition is easily implemented, easy to operate, is suitble to large-scale production.
2, the method for the present invention uses the bisglycidyl ether with bis-epoxy functional group as cross-linking reaction agent so that viscose glue
Fiber is stably connected with tea polyphenols by chemical covalent bonds, and tea polyphenols grafting rate is high, stability enhancing, to significantly improve production
The functions such as the anti-oxidant of product, radioresistance, antibacterial, chelated metal ions.
3, the present invention has first carried out surfactant to viscose rayon and has located in advance before preparing grafting tea polyphenols viscose rayon
Reason so that the surface group of viscose rayon is activated;Cellulose hydrolyzation then is carried out to it again so that viscose rayon is sent out
Raw a degree of degradation, activity hydroxy thereon are able to abundant exposure, convenient for improving the grafting rate of tea polyphenols.
4, the present invention is typical green production process, easy to utilize, and the grafting tea polyphenols viscose glue being prepared is fine
Dimension product can be widely applied to the fields such as weaving, clothes, decoration.
Four, specific implementation mode
With reference to embodiment, it further illustrates the present invention.
Embodiment 1
A kind of preparation process of tea polyphenols modification viscose rayon, specific processing step are as follows:
(1) surfactant pretreatment viscose rayon is prepared
The pretreatment fluid that surfactant sodium dodecyl base benzene sulfonic acid sodium salt mass fraction is 0.5% is made first, according still further to
The ratio that the ratio between viscose rayon quality and the pretreatment fluid volume are 1: 18kg/L, viscose rayon is scattered in added with the pretreatment
In the reaction kettle of liquid, 90 DEG C are warming up to, stirring pretreatment 0.5h.Tapping after the completion of pretreatment is collected pretreated viscous respectively
Waste liquid after glue fiber and pretreatment viscose rayon.Collect pretreated viscose rayon, according to viscose rayon quality with it is pure
The ratio that water purification volume ratio is 1: 8kg/L is added pure water and cleans 2 times.It is dried at 30 DEG C after the completion of cleaning, that is, prepares table
Face activating agent pre-processes viscose rayon, and cellulose hydrolyzation viscose rayon is prepared for lower step;It is fine to the pretreatment viscose glue of collection
Waste liquid after dimension is pumped to biochemical treatment station and is handled, and is discharged after up to standard.
(2) cellulose hydrolyzation viscose rayon is prepared
It is 1 according to surfactant pretreatment the ratio between viscose rayon quality and pure water volume after the completion of (1) step:
Surfactant pretreatment viscose rayon is scattered in pure water, is warming up to 40 DEG C, adds quality and account for by the ratio of 18kg/L
Surfactant pre-processes the cellulase of viscose rayon 1%, reacts 2h after adjusting pH to 5.0.Tapping after reaction, respectively
Collect cellulase treated viscose rayon and enzymolysis waste liquid.The cellulase of collection treated viscose rayon, according to viscous
The ratio that the ratio between glue fiber quality and pure water volume are 1: 8kg/L is added pure water and cleans 2 times.The fibre after cleaning is collected respectively
Waste liquid after the plain enzyme hydrolysis viscose rayon of dimension and cleaning cellulose hydrolyzation viscose rayon, to the cleaning cellulose hydrolyzation of collection
Waste liquid after viscose rayon is merged with the enzymolysis waste liquid of collection, is pumped to biochemical treatment station and is handled, heel row up to standard
It puts.It to the cellulose hydrolyzation viscose rayon after the cleaning of collection, is dried at 30 DEG C, that is, prepares cellulose hydrolyzation viscose glue
Fiber prepares tea polyphenols for lower step and adsorbs viscose rayon.
(3) Adsorption of Tea Polyphenols viscose rayon is prepared
After the completion of (2) step, first tea polyphenols mass percentage concentration is made with pure water and be 0.6% aqueous solution, then pressed
The ratio between the volume of aqueous solution that quality according to cellulose hydrolyzation viscose rayon is 0.6% with tea polyphenols mass percentage concentration is 1:
Cellulose hydrolyzation viscose rayon is scattered in the tea polyphenols aqueous solution by the ratio of 18kg/L, then with dilute sodium hydroxide tune
Section system pH to 9 adsorbs 1h controlled at 80 DEG C.Tapping after the completion of to be adsorbed, this after collection Adsorption of Tea Polyphenols is viscous respectively
The solution after glue fiber and desorption part tea polyphenols as adsorbs tea to the viscose rayon after the Adsorption of Tea Polyphenols of collection
Polyphenol viscose rayon prepares grafting tea polyphenols viscose rayon for lower step;For after the desorption part tea polyphenols of collection this is molten
Liquid can be used for preparing lower batch Adsorption of Tea Polyphenols viscose rayon containing unadsorbed tea polyphenols after adding tea polyphenols and pure water.
(4) grafting tea polyphenols viscose rayon is prepared
After the completion of (3) step, according to the body of the quality and pure water of the cellulose hydrolyzation viscose rayon of (3) step addition
Pure water is first added into the reaction kettle equipped with Adsorption of Tea Polyphenols viscose rayon in the ratio that the ratio between product is 1: 14kg/L, then to its
The volume of middle addition ethylene glycol bisglycidyl ether, the ethylene glycol bisglycidyl ether of addition is that tea polyphenols water is added in (3) step
The 0.6% of liquor capacity reacts 2h under conditions of temperature is 80 DEG C.Crosslinking agent processing is collected in tapping after the completion of reaction respectively
Viscose rayon afterwards and waste reaction solution.The crosslinking agent of collection treated viscose rayon, according to viscose rayon quality and pure water
The ratio that the ratio between volume is 1: 8kg/L is added pure water and cleans 2 times.Respectively collect cleaning after grafting tea polyphenols viscose rayon and
Waste liquid after cleaning grafting tea polyphenols viscose rayon, to the waste liquid after the cleaning grafting tea polyphenols viscose rayon of collection, with collection
Waste reaction solution merge, be pumped to biochemical treatment station and handled, it is up to standard after discharge.To the grafting tea after the cleaning of collection
Polyphenol viscose rayon, moves it into tunnel drier, under conditions of temperature is 30 DEG C, transmission speed is 0.1r/min,
0.5h is handled, that is, prepares grafting tea polyphenols viscose rayon, wherein tea polyphenols grafting rate is 8~10%.
Embodiment 2
A kind of preparation process of tea polyphenols modification viscose rayon, specific processing step are as follows:
(1) surfactant pretreatment viscose rayon is prepared
The pretreatment fluid that surfactant sodium dodecyl base benzene sulfonic acid sodium salt mass fraction is 1% is made first, according still further to viscous
The ratio that the ratio between glue fiber quality and the pretreatment fluid volume are 1: 20kg/L, viscose rayon is scattered in added with the pretreatment fluid
Reaction kettle in, be warming up to 95 DEG C, stirring pretreatment 1h.It is fine to collect pretreated viscose glue respectively for tapping after the completion of pretreatment
Peacekeeping pre-processes the waste liquid after viscose rayon.The pretreated viscose rayon collected, according to viscose rayon quality and pure water
The ratio that volume ratio is 1: 10kg/L is added pure water and cleans 3 times.It is dried at 35 DEG C after the completion of cleaning, that is, prepares surface work
Property agent pre-process viscose rayon, prepare cellulose hydrolyzation viscose rayon for lower step;After the pretreatment viscose rayon of collection
Waste liquid, be pumped to biochemical treatment station and handled, it is up to standard after discharge.
(2) cellulose hydrolyzation viscose rayon is prepared
It is 1 according to surfactant pretreatment the ratio between viscose rayon quality and pure water volume after the completion of (1) step:
Surfactant pretreatment viscose rayon is scattered in pure water, is warming up to 45 DEG C, adds quality and account for by the ratio of 20kg/L
Surfactant pre-processes the cellulase of viscose rayon 2%, reacts 3h after adjusting pH to 5.5.Tapping after reaction, respectively
Collect cellulase treated viscose rayon and enzymolysis waste liquid.The cellulase of collection treated viscose rayon, according to viscous
The ratio that the ratio between glue fiber quality and pure water volume are 1: 10kg/L is added pure water and cleans 3 times.After collecting cleaning respectively
Waste liquid after cellulose hydrolyzation viscose rayon and cleaning cellulose hydrolyzation viscose rayon, to the cleaning cellulase water of collection
The waste liquid after viscose rayon is solved, is merged with the enzymolysis waste liquid of collection, is pumped to biochemical treatment station and is handled, heel row up to standard
It puts.It to the cellulose hydrolyzation viscose rayon after the cleaning of collection, is dried at 35 DEG C, that is, prepares cellulose hydrolyzation viscose glue
Fiber prepares tea polyphenols for lower step and adsorbs viscose rayon.
(3) Adsorption of Tea Polyphenols viscose rayon is prepared
After the completion of (2) step, first tea polyphenols mass percentage concentration is made with pure water and be 0.9% aqueous solution, then pressed
The ratio between the volume of aqueous solution that quality according to cellulose hydrolyzation viscose rayon is 0.9% with tea polyphenols mass percentage concentration is 1:
Cellulose hydrolyzation viscose rayon is scattered in the tea polyphenols aqueous solution by the ratio of 20kg/L, then with dilute sodium hydroxide tune
Section system pH to 10 adsorbs 2h controlled at 85 DEG C.Being somebody's turn to do after Adsorption of Tea Polyphenols is collected in tapping after the completion of to be adsorbed respectively
The solution after viscose rayon and desorption part tea polyphenols as adsorbs the viscose rayon after the Adsorption of Tea Polyphenols of collection
Tea polyphenols viscose rayon prepares grafting tea polyphenols viscose rayon for lower step;For being somebody's turn to do after the desorption part tea polyphenols of collection
Solution can be used for preparing lower batch Adsorption of Tea Polyphenols viscose rayon containing unadsorbed tea polyphenols after adding tea polyphenols and pure water.
(4) grafting tea polyphenols viscose rayon is prepared
After the completion of (3) step, according to the body of the quality and pure water of the cellulose hydrolyzation viscose rayon of (3) step addition
Pure water is first added into the reaction kettle equipped with Adsorption of Tea Polyphenols viscose rayon in the ratio that the ratio between product is 1: 16kg/L, then to its
The volume of middle addition butanediol bisglycidyl ether, the butanediol bisglycidyl ether of addition is that tea polyphenols water is added in (3) step
The 0.9% of liquor capacity reacts 3h under conditions of temperature is 85 DEG C.Crosslinking agent processing is collected in tapping after the completion of reaction respectively
Viscose rayon afterwards and waste reaction solution.The crosslinking agent of collection treated viscose rayon, according to viscose rayon quality and pure water
The ratio that the ratio between volume is 1: 10kg/L is added pure water and cleans 3 times.The grafting tea polyphenols viscose rayon after cleaning is collected respectively
The waste liquid being grafted with cleaning after tea polyphenols viscose rayon, to the waste liquid after the cleaning grafting tea polyphenols viscose rayon of collection, with receipts
The waste reaction solution of collection merges, and is pumped to biochemical treatment station and is handled, and is discharged after up to standard.To the grafting after the cleaning of collection
Tea polyphenols viscose rayon, moves it into tunnel drier, in the condition that temperature is 35 DEG C, transmission speed is 0.3r/min
Under, 1h is handled, that is, prepares grafting tea polyphenols viscose rayon, wherein tea polyphenols grafting rate is 8~10%.
Embodiment 3
A kind of preparation process of tea polyphenols modification viscose rayon, specific processing step are as follows:
(1) surfactant pretreatment viscose rayon is prepared
The pretreatment fluid that surfactant sodium dodecyl base benzene sulfonic acid sodium salt mass fraction is 2% is made first, according still further to viscous
The ratio that the ratio between glue fiber quality and the pretreatment fluid volume are 1: 22kg/L, viscose rayon is scattered in added with the pretreatment fluid
Reaction kettle in, be warming up to 100 DEG C, stirring pretreatment 1.5h.Pretreated viscose glue is collected in tapping after the completion of pretreatment respectively
Waste liquid after fiber and pretreatment viscose rayon.Collect pretreated viscose rayon, according to viscose rayon quality with it is pure
The ratio that water volume ratio is 1: 12kg/L is added pure water and cleans 4 times.It is dried at 40 DEG C after the completion of cleaning, that is, prepares surface
Activating agent pre-processes viscose rayon, and cellulose hydrolyzation viscose rayon is prepared for lower step;To the pretreatment viscose rayon of collection
Waste liquid afterwards is pumped to biochemical treatment station and is handled, and is discharged after up to standard.
(2) cellulose hydrolyzation viscose rayon is prepared
It is 1 according to surfactant pretreatment the ratio between viscose rayon quality and pure water volume after the completion of (1) step:
Surfactant pretreatment viscose rayon is scattered in pure water, is warming up to 50 DEG C, adds quality and account for by the ratio of 22kg/L
Surfactant pre-processes the cellulase of viscose rayon 3%, reacts 4h after adjusting pH to 6.0.Tapping after reaction, respectively
Collect cellulase treated viscose rayon and enzymolysis waste liquid.The cellulase of collection treated viscose rayon, according to viscous
The ratio that the ratio between glue fiber quality and pure water volume are 1: 12kg/L is added pure water and cleans 4 times.After collecting cleaning respectively
Waste liquid after cellulose hydrolyzation viscose rayon and cleaning cellulose hydrolyzation viscose rayon, to the cleaning cellulase water of collection
The waste liquid after viscose rayon is solved, is merged with the enzymolysis waste liquid of collection, is pumped to biochemical treatment station and is handled, heel row up to standard
It puts.It to the cellulose hydrolyzation viscose rayon after the cleaning of collection, is dried at 40 DEG C, that is, prepares cellulose hydrolyzation viscose glue
Fiber prepares tea polyphenols for lower step and adsorbs viscose rayon.
(3) Adsorption of Tea Polyphenols viscose rayon is prepared
After the completion of (2) step, first tea polyphenols mass percentage concentration is made with pure water and be 1.2% aqueous solution, then pressed
The ratio between the volume of aqueous solution that quality according to cellulose hydrolyzation viscose rayon is 1.2% with tea polyphenols mass percentage concentration is 1:
Cellulose hydrolyzation viscose rayon is scattered in the tea polyphenols aqueous solution by the ratio of 22kg/L, then with dilute sodium hydroxide tune
Section system pH to 11 adsorbs 3h controlled at 90 DEG C.Being somebody's turn to do after Adsorption of Tea Polyphenols is collected in tapping after the completion of to be adsorbed respectively
The solution after viscose rayon and desorption part tea polyphenols as adsorbs the viscose rayon after the Adsorption of Tea Polyphenols of collection
Tea polyphenols viscose rayon prepares grafting tea polyphenols viscose rayon for lower step;For being somebody's turn to do after the desorption part tea polyphenols of collection
Solution can be used for preparing lower batch Adsorption of Tea Polyphenols viscose rayon containing unadsorbed tea polyphenols after adding tea polyphenols and pure water.
(4) grafting tea polyphenols viscose rayon is prepared
After the completion of (3) step, according to the body of the quality and pure water of the cellulose hydrolyzation viscose rayon of (3) step addition
Pure water is first added into the reaction kettle equipped with Adsorption of Tea Polyphenols viscose rayon in the ratio that the ratio between product is 1: 18kg/L, then to its
The volume of middle addition hexylene glycol bisglycidyl ether, the hexylene glycol bisglycidyl ether of addition is that tea polyphenols water is added in (3) step
The 1.2% of liquor capacity, reacts 4h under the conditions of at a temperature of 90 °C.Crosslinking agent processing is collected in tapping after the completion of reaction respectively
Viscose rayon afterwards and waste reaction solution.The crosslinking agent of collection treated viscose rayon, according to viscose rayon quality and pure water
The ratio that the ratio between volume is 1: 12kg/L is added pure water and cleans 4 times.The grafting tea polyphenols viscose rayon after cleaning is collected respectively
The waste liquid being grafted with cleaning after tea polyphenols viscose rayon, to the waste liquid after the cleaning grafting tea polyphenols viscose rayon of collection, with receipts
The waste reaction solution of collection merges, and is pumped to biochemical treatment station and is handled, and is discharged after up to standard.To the grafting after the cleaning of collection
Tea polyphenols viscose rayon, moves it into tunnel drier, in the condition that temperature is 40 DEG C, transmission speed is 0.5r/min
Under, 0.5h is handled, that is, prepares grafting tea polyphenols viscose rayon, wherein tea polyphenols grafting rate is 8~10%.
Claims (1)
1. a kind of preparation process of tea polyphenols modification viscose rayon, it is characterised in that specific processing step is as follows:
(1) surfactant pretreatment viscose rayon is prepared
The pretreatment fluid that surfactant sodium dodecyl base benzene sulfonic acid sodium salt mass fraction is 0.5~2% is made first, according still further to viscous
The ratio between glue fiber quality and the pretreatment fluid volume are the ratio of 1: 18~22kg/L, and viscose rayon is scattered in added with the pre- place
In the reaction kettle for managing liquid, 90~100 DEG C are warming up to, stirring 0.5~1.5h of pretreatment, tapping after the completion of pretreatment is collected respectively
Waste liquid after pretreated viscose rayon and pretreatment viscose rayon, the pretreated viscose rayon of collection, according to viscose glue
Fiber quality and the ratio that pure water volume ratio is 1: 8~12kg/L are added pure water and clean 2~4 times, in 30 after the completion of cleaning
It is dried at~40 DEG C, that is, prepares surfactant pretreatment viscose rayon, it is fine to prepare cellulose hydrolyzation viscose glue for lower step
Dimension;It to the waste liquid after the pretreatment viscose rayon of collection, is pumped to biochemical treatment station and is handled, discharged after up to standard;
(2) cellulose hydrolyzation viscose rayon is prepared
After the completion of (1) step, according to surfactant pre-process the ratio between viscose rayon quality and pure water volume for 1: 18~
Surfactant pretreatment viscose rayon is scattered in pure water, is warming up to 40~50 DEG C, adds matter by the ratio of 22kg/L
Amount accounts for the cellulase of surfactant pretreatment viscose rayon 1~3%, reacts 2~4h, reaction after adjusting pH to 5.0~6.0
After tapping, collect cellulase treated viscose rayon and enzymolysis waste liquid respectively, treated for the cellulase of collection
Viscose rayon, according to the ratio between viscose rayon quality and pure water volume be 1: 8~12kg/L ratio be added pure water cleaning 2~
4 times, the cellulose hydrolyzation viscose rayon after cleaning and the waste liquid after cleaning cellulose hydrolyzation viscose rayon are collected respectively, it is right
Waste liquid after the cleaning cellulose hydrolyzation viscose rayon of collection, merges with the enzymolysis waste liquid of collection, is pumped to biochemical place
Reason station is handled, and is discharged after up to standard, to the cellulose hydrolyzation viscose rayon after the cleaning of collection, is dried at 30~40 DEG C
It is dry, that is, cellulose hydrolyzation viscose rayon is prepared, preparing tea polyphenols for lower step adsorbs viscose rayon;
(3) Adsorption of Tea Polyphenols viscose rayon is prepared
After the completion of (2) step, first tea polyphenols mass percentage concentration is made with pure water and be 0.6~1.2% aqueous solution, then pressed
The volume for the aqueous solution that quality and tea polyphenols mass percentage concentration according to cellulose hydrolyzation viscose rayon are 0.6~1.2% it
Than the ratio for 1: 18~22kg/L, cellulose hydrolyzation viscose rayon is scattered in the tea polyphenols aqueous solution, then with dilute
Sodium hydroxide regulation system pH to 9~11 adsorbs 1~3h, tapping after the completion to be adsorbed, difference controlled at 80~90 DEG C
The viscose rayon after Adsorption of Tea Polyphenols and the solution after desorption part tea polyphenols are collected, after the Adsorption of Tea Polyphenols of collection
The viscose rayon, as Adsorption of Tea Polyphenols viscose rayon prepare grafting tea polyphenols viscose rayon for lower step;For the de- of collection
The solution after attached part tea polyphenols can be used for preparing lower batch containing unadsorbed tea polyphenols after adding tea polyphenols and pure water
Adsorption of Tea Polyphenols viscose rayon;
(4) grafting tea polyphenols viscose rayon is prepared
After the completion of (3) step, according to (3) step be added cellulose hydrolyzation viscose rayon quality and pure water volume it
Than the ratio for 1: 14~18kg/L, be first added pure water into the reaction kettle equipped with Adsorption of Tea Polyphenols viscose rayon, then to its
Middle addition ethylene glycol bisglycidyl ether or butanediol bisglycidyl ether or hexylene glycol bisglycidyl ether, the ethylene glycol of addition
Bisglycidyl ether or the volume of butanediol bisglycidyl ether or hexylene glycol bisglycidyl ether are that tea polyphenols are added in (3) step
2~4h, tapping after the completion of reaction, difference are reacted in the 0.6~1.2% of aqueous solution volume under conditions of temperature is 80~90 DEG C
Collect crosslinking agent treated viscose rayon and waste reaction solution, the crosslinking agent of collection treated viscose rayon, according to viscose glue fibre
It ties up the ratio that the ratio between quality and pure water volume are 1: 8~12kg/L and pure water cleaning 2~4 times is added, after collecting cleaning respectively
Grafting tea polyphenols viscose rayon and cleaning grafting tea polyphenols viscose rayon after waste liquid, it is viscous to the cleaning of collection grafting tea polyphenols
Waste liquid after glue fiber is merged with the waste reaction solution of collection, is pumped to biochemical treatment station and is handled, and is discharged after up to standard,
It to the grafting tea polyphenols viscose rayon after the cleaning of collection, moves it into tunnel drier, is 30~40 DEG C, passes in temperature
Under conditions of dynamic speed is 0.1~0.5r/min, 0.5~1h is handled, that is, prepares grafting tea polyphenols viscose rayon, wherein tea is more
Phenol grafting rate is 8~10%.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810553400.3A CN108716118A (en) | 2018-06-01 | 2018-06-01 | A kind of preparation process of tea polyphenols modification viscose rayon |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810553400.3A CN108716118A (en) | 2018-06-01 | 2018-06-01 | A kind of preparation process of tea polyphenols modification viscose rayon |
Publications (1)
Publication Number | Publication Date |
---|---|
CN108716118A true CN108716118A (en) | 2018-10-30 |
Family
ID=63912630
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810553400.3A Pending CN108716118A (en) | 2018-06-01 | 2018-06-01 | A kind of preparation process of tea polyphenols modification viscose rayon |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108716118A (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110331584A (en) * | 2019-08-21 | 2019-10-15 | 太原理工大学 | Protein/cellulose fibre preparation method based on cellulase activation processing |
CN111809263A (en) * | 2020-07-16 | 2020-10-23 | 宜宾惠美纤维新材料股份有限公司 | Antibacterial and deodorant tea cellulose fiber and preparation method thereof |
CN111995800A (en) * | 2020-09-03 | 2020-11-27 | 蔡营龙 | Preparation method of cellulose-based antibacterial food packaging film |
CN112515154A (en) * | 2020-12-08 | 2021-03-19 | 天津科技大学 | Preparation method of functional salt-reduced hericium erinaceus soy sauce and hericium erinaceus soy sauce |
CN112515110A (en) * | 2020-12-08 | 2021-03-19 | 天津科技大学 | Preparation method of low-tyrosine low-salt flavor soybean paste |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000096433A (en) * | 1998-09-22 | 2000-04-04 | Ito En Ltd | Production of antibacterial fiber |
CN1274026A (en) * | 1999-05-18 | 2000-11-22 | 株式会社伊藤园 | Method of producing antibiotic fiber |
CN104532571A (en) * | 2015-01-19 | 2015-04-22 | 重庆大学 | Preparation process of chitosan oligosaccharide modifying cotton fiber |
CN105648768A (en) * | 2016-04-01 | 2016-06-08 | 南通大学 | Adsorption and antibacterial deodorization treatment method for cotton fabrics by aid of tea polyphenol |
CN106012495A (en) * | 2016-07-05 | 2016-10-12 | 安徽农业大学 | Bast fiber fabric with protective function and preparation method thereof |
CN106521671A (en) * | 2016-12-15 | 2017-03-22 | 宜宾屏山辉瑞油脂有限公司 | Tea polyphenol cellulose fiber and preparation method thereof |
CN106592104A (en) * | 2016-12-15 | 2017-04-26 | 宜宾屏山辉瑞油脂有限公司 | Tea polyphenol cellulose fiber spunlaced non-woven fabrics and production method of the same |
CN107164427A (en) * | 2017-06-15 | 2017-09-15 | 重庆大学 | A kind of method that enzyme process prepares carboxylated viscose rayon |
-
2018
- 2018-06-01 CN CN201810553400.3A patent/CN108716118A/en active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000096433A (en) * | 1998-09-22 | 2000-04-04 | Ito En Ltd | Production of antibacterial fiber |
CN1274026A (en) * | 1999-05-18 | 2000-11-22 | 株式会社伊藤园 | Method of producing antibiotic fiber |
CN104532571A (en) * | 2015-01-19 | 2015-04-22 | 重庆大学 | Preparation process of chitosan oligosaccharide modifying cotton fiber |
CN105648768A (en) * | 2016-04-01 | 2016-06-08 | 南通大学 | Adsorption and antibacterial deodorization treatment method for cotton fabrics by aid of tea polyphenol |
CN106012495A (en) * | 2016-07-05 | 2016-10-12 | 安徽农业大学 | Bast fiber fabric with protective function and preparation method thereof |
CN106521671A (en) * | 2016-12-15 | 2017-03-22 | 宜宾屏山辉瑞油脂有限公司 | Tea polyphenol cellulose fiber and preparation method thereof |
CN106592104A (en) * | 2016-12-15 | 2017-04-26 | 宜宾屏山辉瑞油脂有限公司 | Tea polyphenol cellulose fiber spunlaced non-woven fabrics and production method of the same |
CN107164427A (en) * | 2017-06-15 | 2017-09-15 | 重庆大学 | A kind of method that enzyme process prepares carboxylated viscose rayon |
Non-Patent Citations (1)
Title |
---|
任蓉 等: "新型含茶抗菌纤维的加工技术研究", 《广东茶业》 * |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110331584A (en) * | 2019-08-21 | 2019-10-15 | 太原理工大学 | Protein/cellulose fibre preparation method based on cellulase activation processing |
CN110331584B (en) * | 2019-08-21 | 2021-12-28 | 太原理工大学 | Protein/cellulose fiber preparation method based on cellulase activation treatment |
CN111809263A (en) * | 2020-07-16 | 2020-10-23 | 宜宾惠美纤维新材料股份有限公司 | Antibacterial and deodorant tea cellulose fiber and preparation method thereof |
CN111995800A (en) * | 2020-09-03 | 2020-11-27 | 蔡营龙 | Preparation method of cellulose-based antibacterial food packaging film |
CN112515154A (en) * | 2020-12-08 | 2021-03-19 | 天津科技大学 | Preparation method of functional salt-reduced hericium erinaceus soy sauce and hericium erinaceus soy sauce |
CN112515110A (en) * | 2020-12-08 | 2021-03-19 | 天津科技大学 | Preparation method of low-tyrosine low-salt flavor soybean paste |
CN112515110B (en) * | 2020-12-08 | 2023-01-10 | 天津科技大学 | Preparation method of low-tyrosine low-salt flavor soybean paste |
CN112515154B (en) * | 2020-12-08 | 2023-01-10 | 天津科技大学 | Preparation method of functional salt-reduced hericium erinaceus soy sauce and hericium erinaceus soy sauce |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108716118A (en) | A kind of preparation process of tea polyphenols modification viscose rayon | |
US8092732B2 (en) | Processing method of the natural cellulose fiber with feature for enhancing the capability of antifungi, antibacteria and deodorization | |
EP3284861B1 (en) | Method for preparing salt-resistant and detergent-resistant seaweed fiber | |
JP4431106B2 (en) | Method for producing cellooligosaccharide | |
CN100395384C (en) | Method for fabricating fiber of regenerative bamboo cellulose | |
JP4336562B2 (en) | Method for producing cellulose fiber having antibacterial properties from bamboo pulp produced from bamboo | |
CN105311668A (en) | Bacterial cellulose compound cuprous oxide antimicrobial dressing and preparation method thereof | |
CN106012044A (en) | Degumming technology of natural bamboo fiber | |
CN107699874B (en) | Nano silver-cellulose composite material and preparation method and application thereof | |
CN104532571B (en) | Preparation process of chitosan oligosaccharide modifying cotton fiber | |
CN104372701A (en) | Ultrahigh-viscosity refined cotton production process | |
WO2015165588A1 (en) | Composition comprising cellulose fibres and crosslinking agents, water soluble crosslinked cellulose ethers, and the production thereof | |
CN110373900A (en) | A kind of preparation method of chitosan oligosaccharide grafting viscose rayon | |
JPH0123591B2 (en) | ||
CN110373895B (en) | Preparation method of silver-loaded antibacterial viscose fiber | |
Jiang et al. | Enzymatic preparation of oxidized viscose fibers-based biosorbent modified with ε-polylysine for dyes removal and microbial inactivation | |
CN104606710B (en) | A kind of preparation method of high antibiotic property alginate dressing | |
CN105624920A (en) | Highly-antibacterial novel slightly-soluble nonwoven cloth capable of adsorbing heavy metal particles | |
WO2019100711A1 (en) | Calcium alginate non-woven fabric and preparation method therefor | |
CN111719310A (en) | Preparation method of fiber containing Chinese herbal medicine effective components | |
CN101451131A (en) | Chitin-cotton blended fabric biological enzyme pre-processing technique and used enzyme preparation | |
CN114181425B (en) | Flame-retardant, antibacterial and mildewproof cellulose-based foam material as well as preparation method and application thereof | |
CN103074765B (en) | Method for preparing weak-base ion exchange fibers | |
CN103510180A (en) | Lyocell bamboo fiber and preparation method thereof | |
CN114905806B (en) | Deodorant insole based on antibacterial fibers and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
AD01 | Patent right deemed abandoned |
Effective date of abandoning: 20210910 |
|
AD01 | Patent right deemed abandoned |