CN110318120B - Core-shell self-repairing fiber bead type electrostatic spinning material based on pH response and synthesis method and application thereof - Google Patents

Core-shell self-repairing fiber bead type electrostatic spinning material based on pH response and synthesis method and application thereof Download PDF

Info

Publication number
CN110318120B
CN110318120B CN201910279680.8A CN201910279680A CN110318120B CN 110318120 B CN110318120 B CN 110318120B CN 201910279680 A CN201910279680 A CN 201910279680A CN 110318120 B CN110318120 B CN 110318120B
Authority
CN
China
Prior art keywords
shell
core
electrostatic spinning
self
repairing
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.)
Active
Application number
CN201910279680.8A
Other languages
Chinese (zh)
Other versions
CN110318120A (en
Inventor
王巍
陈守刚
窦雯雯
李文
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ocean University of China
Original Assignee
Ocean University of China
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Ocean University of China filed Critical Ocean University of China
Priority to CN201910279680.8A priority Critical patent/CN110318120B/en
Publication of CN110318120A publication Critical patent/CN110318120A/en
Application granted granted Critical
Publication of CN110318120B publication Critical patent/CN110318120B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • 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
    • 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
    • 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
    • D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • 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
    • D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
    • 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
    • D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
    • 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
    • D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Toxicology (AREA)
  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Abstract

The invention provides a core-shell self-repairing fiber beaded electrostatic spinning material based on pH response and a synthesis method and application thereof, belonging to the technical field of polymer chemistry. The shell solution synthesized by the method mainly comprises a polymer shell material, a shell material template agent, a shell material solvent, a cross-linking agent and a catalyst according to the mass ratio of 1: 0.1-2: 5-30: 0.2-5: 0.075-1; the core solution mainly comprises a core material and a core material solvent, and parameters such as a feeding sequence, a heating temperature range, a stirring speed, reaction time and the like are optimized. The electrostatic spinning synthesis process adopts a coaxial spinning mode, and the parameters of voltage, liquid outflow speed, receiver moving speed and the like in the electrostatic spinning process are optimized. The synthesized fiber bead structure can effectively improve the drug loading rate, has pH sensitivity, can realize the pH response self-repairing function of the local area of the coating, and has wide application prospect in the field of self-repairing anticorrosive coatings.

Description

Core-shell self-repairing fiber bead type electrostatic spinning material based on pH response and synthesis method and application thereof
Technical Field
The invention relates to a core-shell self-repairing fiber bead type electrostatic spinning material based on pH response and a synthesis method and application thereof, belonging to the technical field of polymer chemistry.
Background
The anticorrosive coating is the most main anticorrosive means for the surface of steel, and the anticorrosive coating is the most effective, most economic, most common and most easily accepted by engineering designers and users in anticorrosive measures. Environmental protection, energy conservation, resource conservation, high performance and functionalization are the research and development directions, and the coordination of development and environment is the basic requirement of sustainable development. The current self-repairing anticorrosive coating has the characteristics of active repairing function, effective prolonging of the service life of the coating and the like, and is more and more concerned by people.
The method for preparing the nano-fiber by electrostatic spinning is less applied in the field of anticorrosive coatings. The electrostatic spinning material has the characteristics of uniform material, stable structure, enhanced mechanics and the like, can be applied to organic coatings, realizes self-repairing functionalization and realizes the purpose of long-term service of organic coatings. The organic coating is often subjected to the change of pH value of local micro-area environment in the service process to cause the occurrence of failure phenomena such as local cracking, bubbling, peeling and the like. In addition, researches show that the pure linear spinning material has relatively low drug-loading rate and low repair efficiency.
Therefore, the invention discloses an electrostatic spinning material which is sensitive to a pH local region, has a self-repairing function and has high drug loading capacity.
Disclosure of Invention
The technical task of the invention is to provide a core-shell self-repairing fiber beaded type electrostatic spinning material based on pH response and a synthesis method and application thereof aiming at the defects of the prior art, the drug loading rate can be effectively improved by synthesizing the spinning material with the fiber beaded structure, and the pH response self-repairing function of the local area of the coating is realized.
The invention aims to provide a method for synthesizing an electrostatic spinning fiber with the diameter ranging from 80nm to 2000nm and the capability of sensitively responding to the environmental pH. The method is simple and easy to operate, and the obtained fiber has the characteristics of small diameter, large specific surface area, controllable bead structure size on the surface of the fiber and the like.
The technical scheme adopted by the invention for solving the technical problems is as follows:
1. the invention provides a core-shell self-repairing fiber beaded type electrostatic spinning material based on pH response, which comprises a shell structure and a core structure coated in the shell structure,
wherein the shell structure solution is prepared from a shell polymer shell material, a shell material template agent, a shell material solvent, a cross-linking agent and a catalyst according to the mass ratio of 1: 0.1-2: 5-30: 0.2-5: 0.075-1;
The core structure solution is prepared from a core material and a core material solvent according to the mass ratio of 1: 3-10;
and respectively injecting the shell structure solution and the core structure solution into two solution channels of a coaxial electrostatic spinning device, and carrying out electrostatic spinning synthesis to obtain the self-repairing fiber bead type electrostatic spinning material with the core-shell structure.
2. The invention also provides a synthesis method of the core-shell self-repairing fiber beaded type electrostatic spinning material based on pH response, which comprises the following concrete implementation steps:
1) and (3) synthesizing a component A shell solution: mixing a polymer shell material, a shell material template agent, a shell material solvent, a cross-linking agent and a catalyst according to a mass ratio of 1: 0.1-2: 5-30: 0.2-5: 0.075-1, the medicine is added in the order:
1.1) mixing the polymer shell material and the shell material solvent, and stirring for 4-48 hours at the rotating speed of 600-3000rmp within the temperature range of 40-90 ℃;
1.2) adding a shell material template agent, stirring for 1-4 hours at the rotating speed of 600-3000rmp within the temperature range of 50-90 ℃, and respectively adding a cross-linking agent and a catalyst;
1.3) finally stirring for 1-4 hours in a reflux device at the rotating speed of 600-3000rmp within the temperature range of 40-120 ℃;
2) preparation of component B core solution: weighing the core material and the core material solvent according to the mass ratio of 1:3-10, and stirring for 2-4 hours at the rotating speed of 600-;
3) Electrostatic spinning synthesis: fixing tin foil paper or aluminum foil paper on a roller receiver according to a proper size, installing a coaxial needle of an injector of a shell core solution, then switching on a power supply, and carrying out electrostatic spinning synthesis, specifically:
3.1) firstly setting a translation distance, setting the front dead point of the injection device to be zero, setting the capacity of the injector to be 5-50mL, setting the positive voltage to be 15-40KV and the negative voltage to be 2-8KV, setting the injection rate A component to be 0.05-5mm/min, the injection rate B component to be 0.05-5mm/min, the receiving rate to be 1-10 r/min, the translation speed to be 5-50mm/min and the receiving distance to be 5-40 cm;
3.2) the spinning environment needs inert protective gas to fill the preparation cabin;
3.3) spinning for 30min, a shaped spun solid sample can be obtained.
Optionally, in step 1), the polymer shell material is one of polylactic acid, polyethylene terephthalate, polycaprolactone, polyvinyl alcohol, polyvinylidene fluoride, nylon 6, polybutylene terephthalate, chitin, cellulose, methyl cellulose, polyhydroxyalkanoate, polybutylene succinate, polyarylate, polyvinyl acetate, polymethyl methacrylate, and polyaniline, or a mixture of the above polymers.
Optionally, the shell template in the step 1) is pyrrolidine, ethylenediamine, n-butylamine, TiO 2 、Al 2 O 3 、ZrO 2 、Nb 2 O 5 、SnO 2 One or a mixture of several of them.
Optionally, the shell solvent in step 1) is any one or more of methanol, acetone, acetic acid, water, tetrahydrofuran, N-dimethylformamide and N, N-dimethylacetamide.
Optionally, the crosslinking agent in the step 1) is any one or more of dicumyl peroxide, benzoyl peroxide, di-tert-butyl peroxide, dicumyl peroxide and 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide.
Optionally, the catalyst in step 1) is any one or more of stannous octoate, dibutyltin dilaurate, stannous 2-ethyl hexanoate, stannous isooctanoate, bismuth laurate, bismuth neodecanoate and bismuth naphthenate.
Optionally, the core material in the step 2) is any one or more of mercaptobenzothiazole, benzotriazole and sulfonated lignin.
Optionally, the core material solvent in step 2) is any one or more of methyl acetate, ethyl acetate, propyl acetate, cyclohexane, cyclohexanone and toluene cyclohexanone.
Optionally, the inert protective gas in step 3) is any one or more of nitrogen and argon.
3. The invention also provides an application of the core-shell self-repairing fiber beaded type electrostatic spinning material based on pH response, wherein the synthesized electrostatic spinning material and the organic coating are mixed and proportioned according to the mass ratio of 1:1-20, coated on the surface of a substrate, and dried for 48 hours at room temperature to obtain the self-repairing anticorrosive coating.
Optionally, the organic coating is any one of an epoxy resin coating, a polyurethane coating, an alkyd resin coating, and a fluorocarbon coating.
Compared with the prior art, the core-shell self-repairing fiber beaded electrostatic spinning material based on pH response and the synthesis method and the application thereof have the following beneficial effects:
1. the invention provides a synthesis method of a pH response type self-repairing beaded electrostatic spinning material and a preparation method of an electrostatic spinning coating. The synthesized electrostatic spinning has the advantages that the template agent is sensitive to acidic or alkaline environments, the template agent is subjected to chemical reaction in a pH change environment, holes are generated on the surface of a fiber shell material through chemical decomposition or physical swelling, the core material is released, and the purpose of self-repairing is achieved.
2. Experiments show that the fiber bead structure synthesized by the invention can effectively improve the drug loading rate, and compared with the prior art, the drug loading rate of the fiber bead structure is up to 52%.
2. The electrostatic spinning material can be added into organic coating, and the nano structure can form a three-dimensional network structure in the coating, so that the transmission path of corrosive particles is effectively prolonged, and the corrosion resistance of the coating is improved.
Drawings
FIG. 1 is an optical photograph of a synthesized pH-responsive core-shell self-repairing fiber bead block material of example one;
FIG. 2 is a scanning electron micrograph of the example showing the structure of beads of synthetic fibers;
fig. 3 is a graph showing the impedance comparison of the self-healing coating prepared in example one, in an acidic 3.5% sodium chloride solution with a pH of 4.5, after 2 days of scratching;
FIG. 4 is an optical photograph of the pH-responsive core-shell self-repairing fiber bead block material synthesized in example two
FIG. 5 is a scanning electron micrograph of the synthetic fiber bead structure of the second embodiment
Fig. 6 is a graph showing the coating impedance of the self-healing coating prepared in example two compared to a basic 3.5% nacl solution at a pH of 9.8, with a 2 day interval between scratch and scratch.
Detailed Description
The core-shell self-repairing fiber beaded type electrostatic spinning material based on pH response and the synthesis method and application thereof are described in detail below with reference to the accompanying drawings 1 to 6.
The invention relates to a core-shell self-repairing fiber beaded type electrostatic spinning material based on pH response, which comprises a shell structure and a core structure coated in the shell structure,
wherein the shell structure solution is prepared from a shell polymer shell material, a shell material template agent, a shell material solvent, a cross-linking agent and a catalyst according to the mass ratio of 1: 0.1-2: 5-30: 0.2-5: 0.075-1;
The core structure solution is prepared from a core material and a core material solvent according to the mass ratio of 1: 3-10;
and respectively injecting the shell structure solution and the core structure solution into two solution channels of a coaxial electrostatic spinning device, and carrying out electrostatic spinning synthesis to obtain the self-repairing fiber bead type electrostatic spinning material with the core-shell structure.
The invention relates to a synthesis method of a core-shell self-repairing fiber beaded type electrostatic spinning material based on pH response, which comprises the following concrete implementation steps of:
1) and (3) synthesizing a component A shell solution: mixing a polymer shell material, a shell material template agent, a shell material solvent, a cross-linking agent and a catalyst according to a mass ratio of 1: 0.1-2: 5-30: 0.2-5: 0.075-1, the medicine is added in the order:
1.1) mixing the polymer shell material and the shell material solvent, and stirring for 4-48 hours at the rotating speed of 600-3000rmp within the temperature range of 40-90 ℃;
1.2) adding a shell material template agent, stirring for 1-4 hours at the rotating speed of 600-3000rmp within the temperature range of 50-90 ℃, and respectively adding a cross-linking agent and a catalyst;
1.3) finally stirring for 1-4 hours in a reflux device at the rotating speed of 600-3000rmp within the temperature range of 40-120 ℃;
2) preparation of component B core solution: weighing the core material and the core material solvent according to the mass ratio of 1:3-10, and stirring for 2-4 hours at the rotating speed of 600-;
3) Electrostatic spinning synthesis: fixing tin foil paper or aluminum foil paper on a roller receiver according to a proper size, installing a coaxial needle of an injector of a shell core solution, then switching on a power supply, and carrying out electrostatic spinning synthesis, specifically:
3.1) firstly setting a translation distance, setting the front dead point of the injection device to be zero, setting the capacity of the injector to be 5-50mL, setting the positive voltage to be 15-40KV and the negative voltage to be 2-8KV, setting the injection rate A component to be 0.05-5mm/min, the injection rate B component to be 0.05-5mm/min, the receiving rate to be 1-10 r/min, the translation speed to be 5-50mm/min and the receiving distance to be 5-40 cm;
3.2) the spinning environment needs inert protective gas to fill the preparation cabin;
3.3) spinning for 30min, a shaped spun solid sample can be obtained.
The polymer shell material in the step 1) is selected from one of polylactic acid, polyethylene terephthalate, polycaprolactone, polyvinyl alcohol, polyvinylidene fluoride, nylon 6, polybutylene terephthalate, chitin, cellulose, methyl cellulose, polyhydroxyalkanoate, polybutylene succinate, polyarylate, polyvinyl acetate, polymethyl methacrylate and polyaniline, or a mixture of the polymers.
Wherein the shell template in the step 1) is selected from pyrrolidine, ethylenediamine, n-butylamine and TiO 2 、Al 2 O 3 、ZrO 2 、Nb 2 O 5 、SnO 2 One or a mixture of several of them.
Wherein the shell material solvent in the step 1) is selected from any one or more of methanol, acetone, acetic acid, water, tetrahydrofuran, N-dimethylformamide and N, N-dimethylacetamide.
Wherein the cross-linking agent in the step 1) is any one or more selected from dicumyl peroxide, benzoyl peroxide, di-tert-butyl peroxide, dicumyl peroxide and 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide.
Wherein the catalyst in the step 1) is any one or more of stannous octoate, dibutyltin dilaurate, 2-ethyl stannous hexanoate, stannous isooctanoate, bismuth laurate, bismuth neodecanoate and bismuth naphthenate.
Wherein the core material in the step 2) is selected from any one or more of mercaptobenzothiazole, benzotriazole and sulfonated lignin.
Wherein the core material solvent in the step 2) is selected from any one or more of methyl acetate, ethyl acetate, propyl acetate, cyclohexane, cyclohexanone and toluene cyclohexanone.
Wherein the inert protective gas in the step 3) is selected from any one or more of nitrogen and argon.
The synthesized electrostatic spinning material and the organic coating are mixed and proportioned according to the mass ratio of 1:1-20, coated on the surface of a matrix, and dried for 48 hours at room temperature to obtain the self-repairing anticorrosive coating which is applied to the field of matrix anticorrosion.
Wherein the organic coating is selected from any one of epoxy resin coating, polyurethane coating, alkyd resin coating and fluorocarbon coating.
Example one
The invention relates to a core-shell self-repairing fiber beaded type electrostatic spinning material based on pH response, which comprises the following specific steps:
(1) and (3) synthesizing a component A shell solution: 1g of polyethylene terephthalate polymer shell material, 1g of chitin, 0.5g of pyrrolidine, 5g of acetone, 20g of tetrahydrofuran, 1g of dicumyl peroxide and 0.15g of dibutyltin dilaurate are weighed. The medicine is added by mixing 1g of polyethylene terephthalate polymer shell material, 1g of chitin, 5g of acetone and 20g of tetrahydrofuran in sequence, and stirring for 6 hours at the rotating speed of 1000rmp within the temperature range of 45 ℃. Thereafter, 0.5g of pyrrolidine was added and the mixture was stirred at 2000rmp for 1 hour at a temperature in the range of 70 ℃. 1g of dicumyl peroxide and 0.15g of dibutyltin dilaurate were added to the mixture, and the mixture was stirred in a reflux apparatus at a temperature of 80 ℃ at a rpm of 1000rmp for 4 hours.
(2) Preparation of component B core solution: mercaptobenzothiazole 1g and ethyl acetate 10g were weighed and stirred at a temperature range of 60 ℃ at a rotation speed of 3000rmp for 4 hours.
(3) Electrostatic spinning synthesis: the tin foil paper or the aluminum foil paper is fixed on the roller receiver according to a proper size, the coaxial needle of the injector of the shell core solution is installed, then the power supply is switched on, the translation distance is firstly set, the front dead point of the injection device is set to be zero, and the volume of the injector is 10 mL. Positive voltage 18KV and negative voltage 8KV are set. The injection rate of the component A is 0.05mm/min, the component B is 0.1mm/min, the receiving rate is 2 r/min, the translation speed is 7mm/min, and the receiving distance is 6 cm. The spinning environment requires an inert nitrogen blanket gas to fill the preparation chamber. After spinning for 30min, a shaped spun solid sample can be obtained. As shown in fig. 1 and 2.
(4) Preparing a coating: and mixing the synthesized electrostatic spinning sample and the epoxy resin coating according to the mass ratio of 1:10, coating the mixture on the surface of carbon steel, and drying the mixture for 48 hours at room temperature to obtain the self-repairing coating. The self-repairing coating prepared by the method is subjected to impedance comparison in an acidic 3.5% sodium chloride solution with the pH value of 4.5 at an interval of 2 days before and after scratching, and as shown in fig. 3, the coating prepared by the embodiment has better corrosion resistance.
Example two
The invention relates to a core-shell self-repairing fiber beaded type electrostatic spinning material based on pH response, which comprises the following specific steps:
(1) And (3) synthesizing a component A shell solution: mixing polyvinylidene fluoride 0.5g, methyl cellulose 1.5g, polyvinyl acetate 0.5g, and Al 2 O 3 1g、ZrO 2 Weighing 1g, 10g of N, N-dimethylformamide, 10g of methanol, 4g of diisopropylbenzene hydroperoxide and 0.6g of bismuth isooctanoate. The drug is added by mixing 0.5g of polyvinylidene fluoride, 1.5g of methylcellulose, 0.5g of polyvinyl acetate, 10g of N, N-dimethylformamide and 10g of methanol in sequence, and stirring for 48 hours at the rotating speed of 2500rmp within the temperature range of 70 ℃. Then adding Al 2 O 3 1g、ZrO 2 1g, at a temperature in the range of 80 ℃ and at a speed of 2000rmp for 4 hours. Adding 4g of dicumyl peroxide and 0.6g of bismuth isooctanoate respectively into a reflux deviceIn the temperature range of 100 ℃, stirring is carried out for 2 hours at a rotating speed of 2000 rmp.
(2) Preparation of component B core solution: weighing 2g of sulfonated lignin, 6g of cyclohexanone and 2g of toluene cyclohexanone, and stirring at the rotating speed of 2000rmp for 4 hours at the temperature range of 90 ℃.
(3) Electrostatic spinning synthesis: the method comprises the steps of fixing tin foil paper or aluminum foil paper on a roller receiver according to a proper size, installing a coaxial needle of an injector of a shell core solution, then switching on a power supply, firstly setting a translation distance (midpoint setting), setting a front dead point of a pushing injection device to be zero, and using 50mL of the volume of the injector. Positive voltage of 30KV and negative voltage of 2KV are set. The injection rate of the component A is 3mm/min, the component B is 3.5mm/min, the receiving rate is 6 r/min, the translation speed is 30mm/min, and the receiving distance is 15 cm. The spinning environment requires an inert shielding gas to fill the preparation chamber. After spinning for 30min, a shaped spun solid sample can be obtained. As shown in fig. 4 and 5.
(4) Preparing a coating: and (3) mixing the synthesized electrostatic spinning sample and the polyurethane coating according to the mass ratio of 1:20, coating the mixture on the surface of the carbon steel, and drying the mixture for 48 hours at room temperature to obtain the self-repairing coating. The self-repairing coating prepared by the method is subjected to impedance comparison in alkaline 3.5% sodium chloride solution with the pH of 9.8 at an interval of 2 days before and after scratching, and as shown in fig. 6, the coating prepared by the embodiment has better corrosion resistance.
EXAMPLE III
The invention relates to a core-shell self-repairing fiber beaded type electrostatic spinning material based on pH response, which comprises the following specific steps:
(1) and (3) synthesizing a component A shell solution: weighing 0.5g of polycaprolactone, 61.0 g of nylon, 0.5g of cellulose, 0.1g of ethylenediamine, 0.1g of N-butylamine, 5g of N, N-dimethylacetamide, 3g of acetic acid, 2g of water, 0.4g of 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide, 0.15g of bismuth laurate and 0.05g of bismuth neodecanoate. The medicine is added by mixing 0.5g of polycaprolactone, 61.0 g of nylon, 0.5g of cellulose, 5g of N, N-dimethylacetamide, 3g of acetic acid and 2g of water in sequence, and stirring for 24 hours at the rotating speed of 600rmp within the temperature range of 40 ℃. Then, 0.1g of ethylenediamine and 0.1g of n-butylamine were added thereto, and the mixture was stirred at a rotation speed of 600rmp for 3 hours at a temperature of 50 ℃. 0.4g of 2, 5-dimethyl-2, 5-di-tert-butyl-hexane peroxide, 0.15g of bismuth laurate and 0.05g of bismuth neodecanoate were added, and the mixture was stirred in a reflux apparatus at a temperature of 40 ℃ and a rotational speed of 600rmp for 1 hour.
(2) Preparation of component B core solution: 2.5g of benzotriazole, 5g of propyl acetate and 2.5g of cyclohexane were weighed and stirred at a rotation speed of 600rmp for 2 hours at a temperature range of 40 ℃.
(3) Electrostatic spinning synthesis: the tin foil paper or the aluminum foil paper is fixed on the roller receiver according to a proper size, the coaxial needle of the injector of the shell core solution is installed, then the power is switched on, the translation distance (midpoint setting) is firstly set, the front dead point of the injection device is set to be zero, and the volume of the injector is 5 mL. The positive voltage is set to be 15KV, and the negative voltage is set to be 6 KV. The injection rate of the component A is 2mm/min, the component B is 0.0.5mm/min, the receiving rate is 1 r/min, the translation speed is 5mm/min, and the receiving distance is 5 cm. The spinning environment requires an inert shielding gas to fill the preparation chamber. After spinning for 30min, a shaped spun solid sample can be obtained.
(4) Preparing a coating: and (3) mixing the synthesized electrostatic spinning sample with the alkyd resin coating according to the mass ratio of 1:20, coating the mixture on the surface of carbon steel, and drying the mixture for 48 hours at room temperature to obtain the self-repairing coating. The self-repairing coating prepared by the method is subjected to impedance comparison in alkaline 3.5% sodium chloride solution with the pH value of 4.7 at an interval of 2 days before and after scratching, and the coating prepared by the embodiment has better corrosion resistance.
Example four
The invention relates to a core-shell self-repairing fiber beaded type electrostatic spinning material based on pH response, which comprises the following specific steps:
(1) synthesizing component A shell solution: mixing polybutylene terephthalate 0.5g, polyhydroxyalkanoate 0.5g, and Nb 2 O 5 0.5g、SnO 2 0.5g、TiO 2 Weighing 1g, 10g of N, N-dimethylformamide, 10g of acetone, 10g of methanol, 1g of benzoyl peroxide, 2g of di-tert-butyl peroxide, 2g of diisopropylbenzene hydroperoxide, 0.5g of 2-ethyl stannous hexanoate and 0.5g of stannous isooctanoate. The adding sequence of the medicine is respectively 0.5g of polybutylene terephthalate, 0.5g of polyhydroxyalkanoate and N10g of N-dimethylformamide, 10g of acetone and 10g of methanol are mixed and stirred at a rotational speed of 3000rmp for 4 hours at a temperature of 90 ℃. Then adding Nb 2 O 5 0.5g、SnO 2 0.5g、TiO 2 1g, at a temperature in the range of 90 ℃ and at a speed of 3000rmp for 3 hours. 1g of benzoyl peroxide, 2g of di-tert-butyl peroxide, 2g of diisopropylbenzene hydroperoxide, 0.5g of 2-ethyl stannous hexanoate and 0.5g of stannous isooctanoate are respectively added, and the mixture is stirred in a reflux device at the temperature of 120 ℃ for 3 hours at the rotating speed of 3000 rmp.
(2) Preparation of component B core solution: weighing 1g of mercaptobenzothiazole, 1g of benzotriazole, 4g of methyl acetate and 4g of ethyl acetate, and stirring for 4 hours at the rotating speed of 2000rmp within the temperature range of 90 ℃.
(3) Electrostatic spinning synthesis: the method comprises the steps of fixing tin-foil paper or aluminum-foil paper on a roller receiver according to a proper size, installing a coaxial needle of an injector of a shell core solution, then switching on a power supply, firstly setting a translation distance (midpoint setting), setting a front dead point of a pushing injection device to be zero, and using 25mL of the volume of the injector. The positive voltage is set to be 40KV, and the negative voltage is set to be 5 KV. The injection rate of the component A is 5mm/min, the component B is 5mm/min, the receiving rate is 10 revolutions/min, the translation speed is 50mm/min, and the receiving distance is 40 cm. The spinning environment requires an inert shielding gas to fill the preparation chamber. After spinning for 30min, a shaped spun solid sample can be obtained.
(4) Preparing a coating: and (3) mixing the synthesized electrostatic spinning sample and the fluorocarbon coating according to the mass ratio of 1:20, coating the mixture on the surface of the carbon steel, and drying the mixture for 48 hours at room temperature to obtain the self-repairing coating. The self-repairing coating prepared by the method is subjected to impedance comparison in alkaline 3.5% sodium chloride solution with the pH of 9.8 at an interval of 2 days before and after scratching, and the coating prepared by the embodiment has better corrosion resistance.
EXAMPLE five
The invention relates to a core-shell self-repairing fiber beaded type electrostatic spinning material based on pH response, which comprises the following specific steps:
(1) And (3) synthesizing a component A shell solution: 0.5g of polyvinyl alcohol, 1.0g of poly (butylene succinate) and Al 2 O 3 2g of N, N dimethyl10g of formamide, 20g of methanol, 3g of di-tert-butyl peroxide and 0.6g of bismuth naphthenate. The medicine is added by firstly mixing 0.5g of polyvinyl alcohol, 1.0g of poly butylene succinate, 10g of N, N-dimethylformamide and 20g of methanol in sequence, and stirring for 36 hours at the rotating speed of 2500rmp within the temperature range of 75 ℃. Then adding Al 2 O 3 2g, stirred at 2000rmp for 3 hours at a temperature in the range of 70 ℃. 3g of di-tert-butyl peroxide and 0.6g of bismuth naphthenate are respectively added, and the mixture is stirred for 2 hours in a reflux device at the rotating speed of 2500rmp within the temperature range of 90 ℃.
(2) Preparation of component B core solution: 1g of benzotriazole, 4g of methyl acetate and 2g of ethyl acetate were weighed and stirred at a rotation speed of 2000rmp for 3 hours at a temperature range of 85 ℃.
(3) Electrostatic spinning synthesis: the method comprises the steps of fixing tin foil paper or aluminum foil paper on a roller receiver according to a proper size, installing a coaxial needle of an injector of a shell core solution, then switching on a power supply, firstly setting a translation distance (midpoint setting), setting a front dead point of a pushing injection device to be zero, and using 40mL of the volume of the injector. The positive voltage is set to be 25KV, and the negative voltage is set to be 5 KV. The injection rate of the component A is 4mm/min, the component B is 3.5mm/min, the receiving rate is 5 revolutions/min, the translation speed is 35mm/min, and the receiving distance is 20 cm. The spinning environment requires an inert shielding gas to fill the preparation chamber. After spinning for 30min, a shaped spun solid sample can be obtained.
(4) Preparing a coating: and mixing the synthesized electrostatic spinning sample and the polyurethane coating according to the mass ratio of 1:20, coating the mixture on the surface of carbon steel, and drying the mixture for 48 hours at room temperature to obtain the self-repairing coating. The self-repairing coating prepared by the method is subjected to impedance comparison in an alkaline 3.5% sodium chloride solution with the pH value of 9.8 at an interval of 2 days before and after scratching, and the coating prepared by the embodiment has better corrosion resistance.
While the preferred embodiments of the present application have been described, additional variations and modifications of these embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all alterations and modifications as fall within the scope of the application.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present application without departing from the spirit and scope of the application. Thus, if such modifications and variations of the present application fall within the scope of the claims of the present application and their equivalents, the present application is intended to include such modifications and variations as well.
In addition to the technical features described in the specification, the technology is known to those skilled in the art.

Claims (10)

1. A core-shell self-repairing fiber beaded type electrostatic spinning material based on pH response is characterized by comprising a shell structure and a core structure coated in the shell structure,
Wherein the shell structure solution is prepared from a shell polymer shell material, a shell material template agent, a shell material solvent, a cross-linking agent and a catalyst according to a mass ratio of 1: 0.1-2: 5-30: 0.2-5: 0.075-1;
the core structure solution is prepared from a core material and a core material solvent according to the mass ratio of 1: 3-10;
respectively injecting the shell structure solution and the core structure solution into two solution channels of a coaxial electrostatic spinning device, and carrying out electrostatic spinning synthesis to obtain a self-repairing fiber bead type electrostatic spinning material with a core-shell structure;
the method comprises the following concrete steps:
1) and (3) synthesizing a component A shell solution: mixing a polymer shell material, a shell material template agent, a shell material solvent, a cross-linking agent and a catalyst according to a mass ratio of 1: 0.1-2: 5-30: 0.2-5: 0.075-1, the medicine is added in the order:
1.1) mixing the polymer shell material and the shell material solvent, and stirring for 4-48 hours at the rotating speed of 600-3000rmp within the temperature range of 40-90 ℃;
1.2) adding a shell material template agent, stirring for 1-4 hours at the rotating speed of 600-3000rmp within the temperature range of 50-90 ℃, and respectively adding a cross-linking agent and a catalyst;
1.3) finally stirring for 1-4 hours in a reflux device at the rotating speed of 600-3000rmp within the temperature range of 40-120 ℃;
2) Preparation of component B core solution: weighing the core material and the core material solvent according to the mass ratio of 1:3-10, and stirring for 2-4 hours at the rotating speed of 600-;
3) electrostatic spinning synthesis: fixing tin foil paper or aluminum foil paper on a roller receiver according to a proper size, installing a coaxial needle of an injector of a shell core solution, then switching on a power supply, and carrying out electrostatic spinning synthesis, specifically:
3.1) firstly setting a translation distance, setting the front dead point of the injection device to be zero, setting the capacity of the injector to be 5-50mL, setting the positive voltage to be 15-40KV and the negative voltage to be 2-8KV, setting the injection rate A component to be 0.05-5mm/min, the injection rate B component to be 0.05-5mm/min, the receiving rate to be 1-10 r/min, the translation speed to be 5-50mm/min and the receiving distance to be 5-40 cm;
3.2) the spinning environment needs inert protective gas to fill the preparation cabin;
3.3) spinning for 30min to obtain a molded spinning solid sample;
and mixing the synthesized electrostatic spinning material and the organic coating according to the mass ratio of 1:1-20, coating the mixture on the surface of a substrate, and drying the substrate for 48 hours at room temperature to obtain the self-repairing anticorrosive coating.
2. A synthesis method of a core-shell self-repairing fiber beaded type electrostatic spinning material based on pH response is characterized in that the method is based on the core-shell self-repairing fiber beaded type electrostatic spinning material of claim 1, and the specific implementation steps are as follows:
1) And (3) synthesizing a component A shell solution: mixing a polymer shell material, a shell material template agent, a shell material solvent, a cross-linking agent and a catalyst according to a mass ratio of 1: 0.1-2: 5-30: 0.2-5: 0.075-1, the medicine is added in the order:
1.1) mixing the polymer shell material and the shell material solvent, and stirring for 4-48 hours at the rotating speed of 600-3000rmp within the temperature range of 40-90 ℃;
1.2) then adding a shell material template agent, stirring for 1-4 hours at the rotating speed of 600-3000rmp within the temperature range of 50-90 ℃, and respectively adding a cross-linking agent and a catalyst;
1.3) finally stirring for 1-4 hours in a reflux device at the rotating speed of 600-3000rmp within the temperature range of 40-120 ℃;
2) preparing a component B core solution: weighing the core material and the core material solvent according to the mass ratio of 1:3-10, and stirring for 2-4 hours at the rotating speed of 600-;
3) electrostatic spinning synthesis: fixing tin foil paper or aluminum foil paper on a roller receiver according to a proper size, installing a coaxial needle of an injector of a shell core solution, then switching on a power supply, and carrying out electrostatic spinning synthesis, specifically:
3.1) firstly setting a translation distance, setting the front dead point of the injection device to be zero, setting the capacity of the injector to be 5-50mL, setting the positive voltage to be 15-40KV and the negative voltage to be 2-8KV, setting the injection rate A component to be 0.05-5mm/min, the injection rate B component to be 0.05-5mm/min, the receiving rate to be 1-10 r/min, the translation speed to be 5-50mm/min and the receiving distance to be 5-40 cm;
3.2) the spinning environment needs inert protective gas to fill the preparation cabin;
3.3) spinning for 30min, a shaped spun solid sample can be obtained.
3. The method for synthesizing the core-shell self-repairing fiber beaded electrospinning material based on the pH response of claim 2, wherein in the step 1), the polymer shell material is one of polylactic acid, polyethylene terephthalate, polycaprolactone, polyvinyl alcohol, polyvinylidene fluoride, nylon 6, polybutylene terephthalate, chitin, cellulose, methyl cellulose, polyhydroxyalkanoate, polybutylene succinate, polyarylate, polyvinyl acetate, polymethyl methacrylate, and polyaniline, or a mixture of the above polymers.
4. The synthesis method of the core-shell self-repairing fiber beaded type electrostatic spinning material based on the pH response according to claim 2 or 3, wherein the shell template agent in the step 1) is pyrrolidine, ethylenediamine, n-butylamine, TiO 2 、Al 2 O 3 、ZrO 2 、Nb 2 O 5 、SnO 2 One or a mixture of several of them.
5. The synthesis method of the core-shell self-repairing fiber beaded electrospinning material based on the pH response according to claim 2 or 3, wherein the shell solvent in step 1) is any one or more of methanol, acetone, acetic acid, water, tetrahydrofuran, N-dimethylformamide, and N, N-dimethylacetamide.
6. The method for synthesizing the core-shell self-repairing fiber beaded electrospinning material based on the pH response according to claim 2 or 3, wherein the cross-linking agent in the step 1) is any one or more of dicumyl peroxide, benzoyl peroxide, di-tert-butyl peroxide, dicumyl hydroperoxide, and 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide; the catalyst in the step 1) is any one or more of stannous octoate, dibutyltin dilaurate, 2-ethyl stannous hexanoate, stannous isooctanoate, bismuth laurate, bismuth neodecanoate and bismuth naphthenate.
7. The method for synthesizing the core-shell self-repairing fiber beaded type electrostatic spinning material based on the pH response according to claim 2 or 3, wherein the core material in the step 2) is any one or more of mercaptobenzothiazole, benzotriazole and sulfonated lignin; in the step 2), the core material solvent is any one or more of methyl acetate, ethyl acetate, propyl acetate, cyclohexane, cyclohexanone and toluene cyclohexanone.
8. The synthesis method of the core-shell self-repairing fiber beaded electrospinning material based on the pH response according to claim 2 or 3, wherein the inert protective gas in the step 3) is any one or more of nitrogen and argon.
9. An application of a core-shell self-repairing fiber beaded electrostatic spinning material based on pH response is characterized in that the electrostatic spinning material synthesized in the claim 1 and an organic coating are mixed and proportioned according to a mass ratio of 1:1-20, coated on the surface of a substrate, and dried for 48 hours at room temperature to obtain a self-repairing anticorrosive coating.
10. The application of the core-shell self-repairing fiber bead-type electrospinning material based on the pH response of claim 9, wherein the organic coating is any one of an epoxy resin coating, a polyurethane coating, an alkyd resin coating, and a fluorocarbon coating.
CN201910279680.8A 2019-04-09 2019-04-09 Core-shell self-repairing fiber bead type electrostatic spinning material based on pH response and synthesis method and application thereof Active CN110318120B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910279680.8A CN110318120B (en) 2019-04-09 2019-04-09 Core-shell self-repairing fiber bead type electrostatic spinning material based on pH response and synthesis method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910279680.8A CN110318120B (en) 2019-04-09 2019-04-09 Core-shell self-repairing fiber bead type electrostatic spinning material based on pH response and synthesis method and application thereof

Publications (2)

Publication Number Publication Date
CN110318120A CN110318120A (en) 2019-10-11
CN110318120B true CN110318120B (en) 2022-07-29

Family

ID=68112849

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910279680.8A Active CN110318120B (en) 2019-04-09 2019-04-09 Core-shell self-repairing fiber bead type electrostatic spinning material based on pH response and synthesis method and application thereof

Country Status (1)

Country Link
CN (1) CN110318120B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111592820A (en) * 2020-06-10 2020-08-28 青岛鸿澜防水科技有限责任公司 Self-repairing waterborne polyurethane coating and preparation method thereof
CN113072862B (en) * 2021-04-28 2022-08-19 山东冠通交通设施有限公司 Anti-cracking self-repairing epoxy floor coating and preparation process thereof
CN113930859B (en) * 2021-10-29 2022-11-22 中国海洋大学 Multifunctional core-shell self-repairing electrostatic spinning material and synthesis method and application thereof
CN113897691A (en) * 2021-11-16 2022-01-07 上海理工大学 Preparation method of bead nanofiber with composite structure
CN114702866B (en) * 2022-03-01 2022-12-02 江苏凯乐迪新材料科技有限公司 Water-based anticorrosive paint

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106048757A (en) * 2016-06-20 2016-10-26 中原工学院 Method for preparing phase-changing fiber having core-shell beaded structure
CN107474615A (en) * 2017-09-06 2017-12-15 中国科学院过程工程研究所 A kind of anti-corrosion self-healing coatings
CN107829164A (en) * 2017-10-27 2018-03-23 上海理工大学 A kind of selfreparing nanofiber and its preparation method and application
CN107823692A (en) * 2017-11-30 2018-03-23 广州市众为生物技术有限公司 A kind of wound dressing composite nano-fiber membrane and preparation method thereof
CN109371451A (en) * 2018-10-10 2019-02-22 中国船舶重工集团公司第七二五研究所 A kind of Metal Substrate self-repairing plating coat and its preparation method and application

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106048757A (en) * 2016-06-20 2016-10-26 中原工学院 Method for preparing phase-changing fiber having core-shell beaded structure
CN107474615A (en) * 2017-09-06 2017-12-15 中国科学院过程工程研究所 A kind of anti-corrosion self-healing coatings
CN107829164A (en) * 2017-10-27 2018-03-23 上海理工大学 A kind of selfreparing nanofiber and its preparation method and application
CN107823692A (en) * 2017-11-30 2018-03-23 广州市众为生物技术有限公司 A kind of wound dressing composite nano-fiber membrane and preparation method thereof
CN109371451A (en) * 2018-10-10 2019-02-22 中国船舶重工集团公司第七二五研究所 A kind of Metal Substrate self-repairing plating coat and its preparation method and application

Also Published As

Publication number Publication date
CN110318120A (en) 2019-10-11

Similar Documents

Publication Publication Date Title
CN110318120B (en) Core-shell self-repairing fiber bead type electrostatic spinning material based on pH response and synthesis method and application thereof
WO2012015254A2 (en) Production method for a transparent conductive film and a transparent conductive film produced thereby
CN1880526A (en) Ultra-hydrophobic conductive macromolecular nano fiber and method for preparing same and use thereof
CN109927356B (en) Heat-insulating anti-radiation laminated glass film and production process thereof
CN108997894A (en) A kind of conductive coating
CN105332136A (en) Conductive micro-nanometer fiber stranded wire based on solvent-free electrospinning and preparing method thereof
CN102432815B (en) Waterborne polyurethane resin and preparation method
CN102167876B (en) Butyl acrylate-styrene-acrylonitrile copolymer/titanium dioxide composite film and preparation method thereof
CN1468910A (en) Conducting polymer on needle shape substrate
CN114618760B (en) Photo-thermal response nanofiber self-repairing coating and preparation method thereof
KR20000010221A (en) Conductive polymer hard coating film with good transparency and conductivity
Das et al. Bioaugmented polyaniline decorated polylactic acid nanofiber electrode by electrospinning technique for real wastewater‐fed MFC application
CN112778850A (en) Weather-resistant transparent coating
CN113979991A (en) UV conductive prepolymer and preparation method thereof, and transparent conductive UV curing coating and preparation method thereof
CN109254369B (en) Anti-electric-mark corrosion self-supporting optical cable
CN109626520B (en) Production process of high-efficiency electrocatalytic oxidation electrode
CN109943895B (en) Preparation method of polyvinyl alcohol nanofiber
CN111440390A (en) Thermoelectric polymer film and preparation method thereof
CN111019173B (en) Preparation method of degradable polylactic acid-glycolic acid composite material
CN112812725A (en) Full-biodegradable pressure-sensitive adhesive and preparation method thereof
CN113241211B (en) Preparation method of organic film
CN114628082B (en) Environment-aging-resistant conductive silver paste and preparation method thereof
CN216433124U (en) Overload protection type intelligent gas meter
CN218921757U (en) Antistatic breathable protective clothing
CN103333289A (en) RVImX and VAc based copolymer gel electrolyte 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
GR01 Patent grant
GR01 Patent grant