CN110964300A - Biodegradable composite material with antibacterial property and preparation method thereof - Google Patents
Biodegradable composite material with antibacterial property and preparation method thereof Download PDFInfo
- Publication number
- CN110964300A CN110964300A CN201811140276.4A CN201811140276A CN110964300A CN 110964300 A CN110964300 A CN 110964300A CN 201811140276 A CN201811140276 A CN 201811140276A CN 110964300 A CN110964300 A CN 110964300A
- Authority
- CN
- China
- Prior art keywords
- parts
- modified
- fiber
- bactericide
- composite material
- 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.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- 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
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/008—Treatment with radioactive elements or with neutrons, alpha, beta or gamma rays
-
- 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
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic System
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/18—Spheres
-
- 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
-
- 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
Abstract
The invention discloses a biodegradable composite material with antibacterial performance and a preparation method thereof, wherein the composite material comprises, by weight, 40-50 parts of polylactic acid, 10-20 parts of polyamide, 15-20 parts of modified composite fiber, 10-15 parts of modified plasticizer, 3-5 parts of poly epsilon-caprolactone, 2-6 parts of silane coupling agent, 3-5 parts of bactericide microspheres, 3-5 parts of polyethylene wax and 10-20 parts of white carbon black. The invention utilizes the modified composite fiber and the modified plasticizer to increase the mechanical property of the material, and improves the bending strength and the tensile strength of the material.
Description
Technical Field
The invention relates to a composite material, in particular to a biodegradable composite material with antibacterial performance and a preparation method thereof.
Background
In the case recycling process, case wastes are generally classified and processed in recycling due to various materials for case manufacturing, such as artificial leather, cloth, plastics, metal pull rods and the like, but the plastics used in the case are plastics which are integrally formed and cannot be directly used, and in order to increase the recycling rate of the plastics used in the case, thermoplastic plastics are used, but the following problems exist when the thermoplastic plastics are recycled: during use, creep and stress relaxation can occur; secondly, the overall mechanical effect of the thermoplastic is poor. In order to solve the above problems, fibers or other substances are usually added into the plastic matrix to modify the plastic matrix, so as to increase the strength of the plastic.
At present, when the thermoplastic plastic is reused in waste products, useful original chemical substances need to be pyrolyzed and recycled, the recycled plastic can be mixed with or without fillers, plasticizers, stabilizers, coloring agents and the like to prepare a molded product again, but the recycling of many plastic products is difficult due to surface treatment, and in the recycling process of the thermoplastic plastic, carcinogenic substances are possibly generated in poor-quality or poorly-worked products due to the problems of raw material use, and the durability of boxes is reduced and the boxes are easy to damage.
Biodegradable plastics have been produced at the same time, and the annual production of biodegradable plastics has been increased, but the biodegradable plastics have the following problems: first, compatibility between the additive and the matrix material; and the mechanical property of the biodegradable plastic.
However, the biodegradable material has poor antibacterial performance due to the use of natural raw materials, and the biodegradable material cannot meet the requirements because the biodegradable material has a short service life in a high-humidity environment.
Disclosure of Invention
The purpose of the invention is as follows: the invention provides a preparation method of a biodegradable composite material, and the biological material prepared by the method has good water resistance and excellent mechanical property. The invention also aims to provide the application of the composite material prepared by the preparation method in case products.
The technical scheme is as follows: the invention relates to a biodegradable composite material with antibacterial property, which comprises, by weight, 40-50 parts of polylactic acid, 10-20 parts of polyamide, 15-20 parts of modified composite fiber, 10-15 parts of modified plasticizer, 3-5 parts of poly epsilon-caprolactone, 2-6 parts of silane coupling agent, 3-5 parts of bactericide microspheres, 3-5 parts of polyethylene wax and 10-20 parts of white carbon black;
the modified fiber is prepared by the following method: mixing bamboo fibers, flax fibers, hemp fibers and cotton fibers according to a mass ratio of 2-3:1:0.3-1:0.5-1, adding the mixture into a 5-10% sodium hydroxide aqueous solution, soaking the mixture at the temperature of 90-95 ℃ for 2-3h, then carrying out ultrasonic treatment on the solution for 20-30min, washing and drying the composite fibers after ultrasonic treatment, dispersing the dried composite fibers in dimethylformamide, adding epoxy chloropropane, carrying out esterification at the temperature of 110-120 ℃, wherein the reaction time is 6-8h, after the reaction is finished, purifying reactants to obtain modified composite fibers, and carrying out irradiation treatment on the obtained reactants in an air atmosphere to obtain the modified composite fibers;
the modified plasticizer is prepared by the following method: mixing starch, chitosan, carboxymethyl cellulose, hemicellulose and hyaluronic acid according to the mass ratio of 2-5:1-2:0.5-1:0.2-0.5:1-2 to obtain a mixture A, dispersing the obtained mixture A in dimethylformamide, adding fatty acid ester, reacting at the temperature of 60-80 ℃ for 4-5 hours, and after the reaction is finished, purifying reactants to obtain a modified plasticizer;
the bactericide microsphere is prepared by the following method: adding bactericide into the solution containing 2-3% of chitosan to prepare microspheres, and freeze-drying to obtain the bactericide microspheres.
It is further noted that:
in the invention, polylactic acid is selected as a substrate material, and the polylactic acid is biodegradable and has higher mechanical strength.
The invention solves the defects of short service time and poor strength durability of polylactic acid by utilizing the compatibility of polylactic acid and polyamide and the characteristics of toughness, wear resistance, high temperature resistance and excellent impact resistance of polyamide.
According to the invention, the natural fiber is added to increase the toughness and tensile resistance of the substrate material, but the natural fiber usually has hydrophilic property, and the substrate material has hydrophobic property, so that the natural fiber needs to be subjected to surface treatment, the property of the material is improved through the surface treatment, the adhesion between the fiber and the plasticizer can be effectively improved, and the sensitivity to moisture is reduced.
In addition, the natural fiber is modified to serve as an additive, the natural fiber has poor thermoplasticity and cannot bear the processing temperature of more than 200 ℃, the natural fiber is subjected to graft modification, the oxidation resistance and the water resistance of the natural fiber are improved, and the insolubility of the natural fiber is changed.
In the invention, the addition of the coupling agent can improve the compatibility of the inorganic filler and a system, increase the crosslinking degree of different substances in a reaction system and improve the mechanical property of the material.
In the step (1) and the step (2), the reactant purification can adopt a common reactant purification method in the prior art, and can adopt reactant purification methods such as filtration, centrifugation, dialysis, alcohol precipitation, reduced pressure distillation and the like according to the property of a reaction system.
Preferably, the method adopts an alcohol precipitation mode, industrial grade ethanol with 2-3 times volume of the reaction system is added, and the obtained reactant is washed and dried.
The invention adopts natural materials as the matrix material, and needs to add the bactericide, but when the bactericide is used, the sterilization duration and the compatibility with the matrix material in the processing process need to be improved.
The biodegradable composite material with antibacterial property, which is prepared by the invention, is applied to case products, so that the defect that the plastic used in the existing case products cannot be recycled or cannot be effectively utilized during recycling is overcome.
The polyethylene wax is used as a lubricant, so that the wear resistance and the tearing strength are improved, and the solvent resistance of the polyamide is improved.
The addition of the inorganic particles can improve the wear resistance of the composite material, so that the composite material has excellent wear resistance.
Preferably, the fatty acid ester is a fatty acid methyl ester; the mass-volume ratio of the mixture A to the fatty acid ester is 1:1-5 mg/ml.
Preferably, the fatty acid methyl ester is a mixture of methyl stearate, methyl oleate and methyl laurate in a volume ratio of 2-3:0.5-1: 1-2.
Preferably, the irradiation treatment is with Co60Is used as irradiation light source, and the irradiation dose rate is 3-4 kGy. H-1The irradiation time is 2-3 h.
Preferably, the output power of the ultrasonic treatment is 200-300W.
Preferably, the mass-to-volume ratio of the composite fiber to the epichlorohydrin is 1:10-15 mg/ml.
Preferably, the bactericide microspheres are prepared by the following method: adding polyhexamethylene guanidine bactericide into a solution containing 2-3% of chitosan, carrying out ultrasonic treatment for 20-30min under the condition of 25KW power, and after the ultrasonic treatment is finished, carrying out freeze drying on the mixed solution to obtain bactericide microspheres.
Preferably, the volume ratio of the chitosan solution to the polyhexamethylene guanidine bactericide is 100: 1-2.
The preparation method of the biodegradable composite material with antibacterial performance comprises the following steps:
(1) preparing modified composite fiber: mixing bamboo fiber, flax fiber, hemp fiber and cotton fiber according to the mass ratio of 2-3:1:0.3-1:0.5-1, adding 5-10% of sodium hydroxide aqueous solution to soak for 2-3h at the temperature of 90-95 ℃, then carrying out ultrasonic treatment on the solution for 20-30min, washing and drying the composite fiber after ultrasonic treatment, dispersing the dried composite fiber in dimethylformamide, adding epoxy chloropropane, carrying out esterification at the temperature of 110-120 ℃, wherein the reaction time is 6-8h, after the reaction is finished, purifying reactants to obtain modified composite fiber, and carrying out Co-based modification on the obtained reactants in an air atmosphere60Is used as irradiation light source, and the irradiation dose rate is 3-4 kGy. H-1Irradiating for 2-3h to obtain modified composite fiber;
in the invention, in order to reduce the reaction time of natural fiber modification, ultrasonic treatment is carried out to change the surface appearance of the fiber, and compared with the reaction without ultrasonic treatment, the reaction time can be shortened.
In the invention, the irradiation treatment initiates active groups on the surface of the fiber to enhance the interface bonding force.
(2) Preparation of modified plasticizer: mixing starch, chitosan, carboxymethyl cellulose, hemicellulose and hyaluronic acid according to the mass ratio of 2-5:1-2:0.5-1:0.2-0.5:1-2 to obtain a mixture A, dispersing the obtained mixture A in dimethylformamide, adding fatty acid ester, reacting at the temperature of 60-80 ℃ for 4-5 hours, and after the reaction is finished, purifying reactants to obtain a modified plasticizer;
(3) preparation of the bactericide microspheres: adding polyhexamethylene guanidine bactericide into a solution containing 2-3% of chitosan, carrying out ultrasonic treatment for 20-30min under the condition of 25KW power, and after the ultrasonic treatment is finished, carrying out freeze drying on the obtained mixed solution to obtain bactericide microspheres;
(4) according to parts by weight, melting 40-50 parts of polylactic acid, 10-20 parts of polyamide, 15-20 parts of modified composite fiber obtained in the step (1), 10-15 parts of modified plasticizer obtained in the step (2), 3-5 parts of poly epsilon-caprolactone, 2-6 parts of silane coupling agent, 3-5 parts of bactericide microspheres, 3-5 parts of polyethylene wax and 10-20 parts of white carbon black at the temperature of 180-200 ℃, then adding 10-20 parts of polyamide into an internal mixer, melting at the temperature of 260-280 ℃, and mixing for 20-30min to obtain the biodegradable composite material with antibacterial property.
In the present invention, "%" represents mass% unless otherwise specified.
Has the advantages that: (1) according to the invention, polylactic acid is selected as a substrate material, so that the composite material has higher mechanical strength; (2) the invention solves the defects of short use time and poor strength durability of polylactic acid by utilizing the compatibility of polylactic acid and polyamide and the characteristics of toughness, wear resistance, high temperature resistance and excellent impact resistance of polyamide; (3) the modified natural fiber is added to improve the toughness and tensile resistance of the substrate material, so that the adhesion between the fiber and the plasticizer can be effectively improved, and the sensitivity to moisture is reduced; (4) in the invention, the compatibility of the inorganic filler and a system can be improved by adding the coupling agent, and the mechanical property of the material is also improved; (5) the antibacterial agent is added in the invention, so that the service cycle of the composite material is prolonged.
Detailed Description
Firstly, the source of raw materials
The polylactic acid is 4032D, the grade is extrusion grade, the melting temperature is 160 ℃, and the manufacturer is American NatureWorks;
the polyamide is 101F and is from DuPont;
poly-epsilon-caprolactone with model of PCL-20 and intrinsic viscosity range of 1.75-2.25dl/g, available from Shandong gain Biotech Co., Ltd;
the silane coupling agent is KH 560;
flax fiber: the density was 1.45 g.cm-3The tensile strength is 850 MPa;
hemp fiber: the density was 1.48 g.cm-3The tensile strength is 680 MPa;
the average length of the cotton fiber is 1-4mm, and the average diameter is 2-10 μm;
the specification of the bamboo fiber is 1.5D 38 mm;
the polyethylene wax has a relative molecular weight of 1900-;
the calcium carbonate is from Qingyuan high peak powder company;
starch: is corn starch with density of 1.5g cm-3From the Dongyang auxiliary agent plant in Li, Wu Jiang City;
the effective content of chitosan is more than 99%, and the chitosan is from Kaschin-Beta-Shibata Biotech limited;
carboxymethyl cellulose: the effective content is more than 99%, and the density is 1.0g cm-3Chemical technology, ltd, dennay sunny day;
the hemicellulose is xylan, the content of effective substances is more than 95 percent, and the relative molecular weight is 200-;
the content of effective substances of hyaluronic acid is more than 99 percent, the CAS number is 3514685, and the hyaluronic acid is from Huaxing bioengineering Co., Ltd in the Hunan century;
the polyhexamethylene guanidine bactericide is from Shanghai Germany and chemical industry Co.Ltd;
the remaining materials were obtained commercially.
Secondly, material preparation
2.1 preparation of modified conjugate fibers
Sample 1: mixing bamboo fiber, flax fiber, hemp fiber and cotton fiber at a mass ratio of 2:1:0.3:0.5, pretreating with a cutting machine to make the average length of the mixed fiber be 0.5-1mm, adding 5% sodium hydroxide aqueous solution into the composite fiber, soaking at 90 deg.C for 2 hr, and ultrasonic cleaning with ultrasonic cleaning machineSetting the sound power to be 250W, carrying out ultrasonic treatment for 30min, washing the composite fiber to be neutral, drying, dispersing the dried composite fiber in dimethylformamide, wherein the material-liquid ratio of the composite fiber to the dimethylformamide is 1:10mg/ml, adding epoxy chloropropane, the mass-volume ratio of the composite fiber to the epoxy chloropropane is 1:10mg/ml, carrying out esterification at the temperature of 120 ℃, the reaction time is 6h, after the reaction is finished, purifying the reactant, carrying out air atmosphere treatment on the obtained reactant by adopting Co60The irradiation dose rate is 3 kGy.H for the irradiation light source-1And the irradiation time is 2 hours, so as to obtain the modified composite fiber.
Sample 2: mixing bamboo fiber, flax fiber, hemp fiber and cotton fiber according to a mass ratio of 3:1:1:1, pretreating by using a cutting machine to enable the average length of the mixed fiber to be 0.5-1mm, adding 10% sodium hydroxide aqueous solution into composite fiber, soaking for 3h at a temperature of 95 ℃, setting the ultrasonic power of an ultrasonic cleaning machine to be 250W, carrying out ultrasonic treatment for 30min, washing the composite fiber to be neutral, drying, dispersing the dried composite fiber into dimethylformamide, adding epichlorohydrin into the composite fiber and the dimethylformamide at a material-to-liquid ratio of 1:10mg/ml, carrying out esterification at a temperature of 120 ℃ for 8h, carrying out reactant purification after the reaction is finished, purifying the obtained reactant in an air atmosphere, by using Co60The irradiation dose rate is 4 kGy.H for the irradiation light source-1And the irradiation time is 3h, thus obtaining the modified composite fiber.
Sample 3: mixing bamboo fiber, flax fiber, hemp fiber and cotton fiber according to the mass ratio of 2.5:1:0.5:1, pretreating by using a cutting machine to ensure that the average length of the mixed fiber is 0.5-1mm, adding 10% sodium hydroxide aqueous solution into the composite fiber, soaking for 3h at the temperature of 95 ℃, setting the ultrasonic power of an ultrasonic cleaning machine to be 250W, carrying out ultrasonic treatment for 30min, washing the composite fiber to be neutral, drying, dispersing the dried composite fiber in dimethylformamide, adding epoxy chloropropane, and adding the composite fiber and dimethylformamide at the feed-liquid ratio of 1:10mg/mlThe mass volume ratio of vitamin to epichlorohydrin is 1:12mg/ml, the esterification is carried out at the temperature of 120 ℃, the reaction time is 8h, the purification of reactants is carried out after the reaction is finished, the obtained reactants are carried out in the air atmosphere by adopting Co60The irradiation dose rate is 4 kGy.H for the irradiation light source-1And the irradiation time is 3h, thus obtaining the modified composite fiber.
Sample 1: mixing bamboo fiber, flax fiber, hemp fiber and cotton fiber at a mass ratio of 2.5:1:0.5:1, pretreating with a cutting machine, enabling the average length of the mixed fiber to be 0.5-1mm, adding 10% sodium hydroxide aqueous solution into the composite fiber, soaking for 3h at the temperature of 95 ℃, setting the ultrasonic power of an ultrasonic cleaning machine to be 250W, carrying out ultrasonic treatment for 30min, washing the composite fiber to be neutral, drying, dispersing the dried composite fiber into dimethylformamide, wherein the material-liquid ratio of the composite fiber to the dimethylformamide is 1:10mg/ml, adding epoxy chloropropane, and the mass-volume ratio of the composite fiber to the epoxy chloropropane is 1:12mg/ml, and (3) carrying out esterification at the temperature of 120 ℃, wherein the reaction time is 8h, and after the reaction is finished, purifying reactants to obtain the modified composite fiber.
2.2 preparation of the modifying plasticizer
Sample 4: mixing methyl stearate, methyl oleate and methyl laurate according to the volume ratio of 2:0.5:1 to obtain fatty acid ester; mixing starch, chitosan, carboxymethyl cellulose, hemicellulose and hyaluronic acid according to a mass ratio of 2:1:0.5:0.2:1 to obtain a mixture A; dispersing the mixture A in dimethylformamide, wherein the feed-liquid ratio of the mixture A to the dimethylformamide is 1:10mg/ml, adding fatty acid ester into a reaction system, the mass-volume ratio of the mixture A to the fatty acid ester is 1:1mg/ml, reacting for 4 hours at the temperature of 60 ℃, and purifying reactants after the reaction is finished to obtain the modified plasticizer.
Sample 5: mixing methyl stearate, methyl oleate and methyl laurate in a volume ratio of 3:1:2 to obtain fatty acid ester; mixing starch, chitosan, carboxymethyl cellulose, hemicellulose and hyaluronic acid according to a mass ratio of 5:2:1:0.5:2 to obtain a mixture A; dispersing the mixture A in dimethylformamide, wherein the feed-liquid ratio of the mixture A to the dimethylformamide is 1:10mg/ml, adding fatty acid ester into a reaction system, the mass-volume ratio of the mixture A to the fatty acid ester is 1:5mg/ml, reacting for 5 hours at the temperature of 70 ℃, and purifying reactants after the reaction is finished to obtain the modified plasticizer.
Sample 6: mixing methyl stearate, methyl oleate and methyl laurate according to the volume ratio of 2.5:0.6:1.5 to obtain fatty acid ester; mixing starch, chitosan, carboxymethyl cellulose, hemicellulose and hyaluronic acid according to a mass ratio of 3:1.5:1:0.3:1.5 to obtain a mixture A; dispersing the mixture A in dimethylformamide, wherein the feed-liquid ratio of the mixture A to the dimethylformamide is 1:10mg/ml, adding fatty acid ester into a reaction system, wherein the mass-volume ratio of the mixture A to the fatty acid ester is 1:3mg/ml, reacting at 70 ℃ for 5 hours, and after the reaction is finished, purifying reactants to obtain the modified plasticizer.
Sample 2: mixing starch, chitosan, carboxymethyl cellulose, hemicellulose and hyaluronic acid according to a mass ratio of 3:1.5:1:0.3:1.5 to obtain a mixture A; dispersing the mixture A in dimethylformamide, wherein the feed-liquid ratio of the mixture A to the dimethylformamide is 1:10mg/ml, adding stearic ester into a reaction system, the mass-volume ratio of the mixture A to the stearic ester is 1:3mg/ml, reacting at the temperature of 70 ℃ for 5 hours, and after the reaction is finished, purifying reactants to obtain the modified plasticizer.
Sample 3: mixing starch, chitosan, carboxymethyl cellulose, hemicellulose and hyaluronic acid according to the mass ratio of 3:1.5:1:0.3:1.5 to obtain a sample 3.
2.3 preparation of Fungicide microspheres
Sample 7: adding polyhexamethylene guanidine bactericide with two percent of the volume of the chitosan solution into the solution containing 2 percent of chitosan, carrying out ultrasonic treatment for 25min under the condition of 25KW power, and after the ultrasonic treatment is finished, carrying out freeze drying on the obtained mixed solution to obtain the bactericide microspheres.
Determination of microspheres of sample 7 Fungicide, D50The particle size was 2.35. mu.m.
2.4 preparation of the composite Material
A DS 32-IA twin-screw host machine was used to perform the composite samples.
Example 1: adding 40 parts of polylactic acid, 15 parts of modified composite fiber prepared by the sample 1, 10 parts of modified plasticizer prepared by the sample 4, 3 parts of poly-epsilon-caprolactone, 2 parts of silane coupling agent, 3 parts of bactericide microspheres prepared by the sample 7, 3 parts of polyethylene wax and 10 parts of white carbon black into an internal mixer, melting at 190 ℃, then adding 10 parts of polyamide, and further mixing for 20min at 260 ℃ to obtain the biodegradable composite material.
Example 2: adding 50 parts of polylactic acid, 20 parts of modified composite fiber prepared by the sample 2, 15 parts of modified plasticizer prepared by the sample 5, 5 parts of poly-epsilon-caprolactone, 6 parts of silane coupling agent, 5 parts of bactericide microsphere prepared by the sample 7, 5 parts of polyethylene wax and 20 parts of white carbon black into an internal mixer, melting at 200 ℃, then adding 20 parts of polyamide, and further mixing for 30min at 280 ℃ to obtain the biodegradable composite material.
Example 3: adding 45 parts of polylactic acid, 18 parts of modified composite fiber prepared by the sample 3, 12 parts of modified plasticizer prepared by the sample 6, 4 parts of poly-epsilon-caprolactone, 5 parts of silane coupling agent, 4 parts of bactericide microspheres prepared by the sample 7, 4 parts of polyethylene wax and 15 parts of white carbon black into an internal mixer, melting at 190 ℃, then adding 15 parts of polyamide, and further mixing for 25min at 270 ℃ to obtain the biodegradable composite material.
Example 4: adding 40 parts of polylactic acid, 15 parts of modified composite fiber prepared by the sample 1, 10 parts of modified plasticizer prepared by the sample 5, 3 parts of poly-epsilon-caprolactone, 2 parts of silane coupling agent, 3 parts of bactericide microspheres prepared by the sample 7, 3 parts of polyethylene wax and 10 parts of white carbon black into an internal mixer, melting at 190 ℃, then adding 10 parts of polyamide, and further mixing for 20min at 260 ℃ to obtain the biodegradable composite material.
Example 5: adding 50 parts of polylactic acid, 20 parts of modified composite fiber prepared by the sample 2, 15 parts of modified plasticizer prepared by the sample 6, 5 parts of poly-epsilon-caprolactone, 6 parts of silane coupling agent, 5 parts of bactericide microspheres prepared by the sample 7, 5 parts of polyethylene wax and 20 parts of white carbon black into an internal mixer, melting at 200 ℃, then adding 20 parts of polyamide, and further mixing for 30min at 280 ℃ to obtain the biodegradable composite material.
Example 6: adding 45 parts of polylactic acid, 18 parts of modified composite fiber prepared by the sample 3, 12 parts of modified plasticizer prepared by the sample 4, 4 parts of poly-epsilon-caprolactone, 5 parts of silane coupling agent, 4 parts of bactericide microspheres prepared by the sample 7, 4 parts of polyethylene wax and 15 parts of white carbon black into an internal mixer, melting at 190 ℃, then adding 15 parts of polyamide, and further mixing for 25min at 270 ℃ to obtain the biodegradable composite material.
Comparative example 1: adding 45 parts of polylactic acid, 18 parts of modified composite fiber prepared by a sample 1, 12 parts of modified plasticizer prepared by a sample 2, 4 parts of poly-epsilon-caprolactone, 5 parts of silane coupling agent, 4 parts of bactericide microspheres prepared by a sample 7, 4 parts of polyethylene wax and 15 parts of white carbon black into an internal mixer, melting at 190 ℃, then adding 15 parts of polyamide, and further mixing for 25min at 270 ℃ to obtain the biodegradable composite material.
Comparative example 2: adding 45 parts of polylactic acid, 18 parts of modified composite fiber prepared by a sample 3, 12 parts of modified plasticizer prepared by a sample 2, 4 parts of poly-epsilon-caprolactone, 5 parts of silane coupling agent, 5 parts of bactericide microspheres prepared by a sample 7, 4 parts of polyethylene wax and 15 parts of white carbon black into an internal mixer, melting at 190 ℃, then adding 15 parts of polyamide, and further mixing for 25min at 270 ℃ to obtain the biodegradable composite material.
Comparative example 3: adding 45 parts of polylactic acid, 18 parts of modified composite fiber prepared by a sample 1, 12 parts of modified plasticizer prepared by a sample 3, 4 parts of poly-epsilon-caprolactone, 5 parts of silane coupling agent, 4 parts of bactericide microspheres prepared by a sample 7, 4 parts of polyethylene wax and 15 parts of white carbon black into an internal mixer, melting at 190 ℃, then adding 15 parts of polyamide, and further mixing for 25min at 270 ℃ to obtain the biodegradable composite material.
Comparative example 4: adding 45 parts of polylactic acid, 18 parts of modified composite fiber prepared by the sample 3, 12 parts of modified plasticizer prepared by the sample 6, 5 parts of silane coupling agent, 3 parts of bactericide microspheres prepared by the sample 7, 4 parts of polyethylene wax and 15 parts of white carbon black into an internal mixer, melting at 190 ℃, then adding 15 parts of polyamide, and further mixing for 25min at 270 ℃ to obtain the biodegradable composite material.
Third, performance test
3.1 mechanical Property test
The mechanical properties of the prepared samples of examples 1 to 6 and comparative examples 1 to 4 were measured, and the measurement results are shown in Table 1.
TABLE 1 mechanical Property test results for different samples
From the results in table 1, it can be seen that the use of the modified composite fiber and the modified plasticizer in the present invention increases the mechanical properties of the material, thereby improving both the bending strength and the tensile strength of the material.
3.2 test of comprehensive Properties
And (3) testing the high-temperature resistance and waterproof performance: the test method comprises the following steps: after the temperature is 45 ℃ and the relative humidity is 95 percent for 300 hours, whether the sample is corroded or not is observed.
And (3) wear resistance test: and (3) wearing the test sample by using a wearing machine, placing the test sample on a rotating turntable with a constant rotating speed of 60rpm, pressing a grinding wheel with a certain weight on the test sample, and finishing the test when the number of turns of the turntable reaches 1000. And then weighing the mass of the worn sample fragments to represent the wear resistance index of the material, and representing the wear resistance of the material by using the wear amount.
Low-temperature impact resistance: the material is placed at minus 40 ℃ for 2h, 1kg of iron ball falls down to impact the sample from the height of 1m, and the area with the radius of 6mm taking the impact point as the center of a circle has no cracking, delamination, peeling or other damage phenomena.
TABLE 2 results of comprehensive Property measurements of different samples
| Sample (I) | High temperature resistantWater performance | Amount of wear (mg/1000 ring) | Low temperature impact resistance |
| Example 1 | No erosion | 0.02 | Without change |
| Example 2 | No erosion | 0.02 | Without change |
| Example 3 | No erosion | 0.02 | Without change |
| Example 4 | No erosion | 0.03 | Without change |
| Example 5 | No erosion | 0.04 | Without change |
| Example 6 | No erosion | 0.03 | Without change |
| Comparative example 1 | Surface water swelling | 1.79 | Fine cracks |
| Comparative example 2 | Surface water swelling | 1.86 | Fine cracks |
| Comparative example 3 | Surface water swelling | 1.90 | Fine cracks |
| Comparative example 4 | No erosion | 1.37 | Fine cracks |
The results in table 2 show that the modified plasticizer of the present invention can increase the waterproof performance of the sample, mainly because the high hydroxyl content in the polymeric polysaccharide and the fiber is high, and the hydrophobic modification is required, so that the waterproof performance of the sample can be greatly improved in addition to changing the mechanical properties of the composite sample. From the results of comparative example 4, it can be seen that blending of PCL of the present invention with a modifying plasticizer gives a sample with good water resistance.
As can be seen from the wear resistance of Table 2, the wear resistance of the composite material of the present invention is significantly improved by the addition of the modified conjugate fiber and the modified plasticizer.
It can be seen from the impact resistance of table 2 that the modified composite fiber and modified plasticizer of the present invention increase the uniformity of the composite material, through esterification modification, the hydroxyl groups on the surface of the fiber or polysaccharide are replaced, thereby avoiding decomposition at lower temperature, improving thermoplasticity, and the esterification modification effectively transfers the interfacial stress, thereby changing the compatibility of the fiber and thermoplastic polymer interface. In addition, the sample prepared by the invention is added with the bactericide, so that the performance reduction caused by microorganisms can be prevented, and the prepared product has longer shelf life.
Claims (9)
1. A biodegradable composite material with antibacterial performance is characterized by comprising, by weight, 40-50 parts of polylactic acid, 10-20 parts of polyamide, 15-20 parts of modified composite fiber, 10-15 parts of modified plasticizer, 3-5 parts of poly epsilon-caprolactone, 2-6 parts of silane coupling agent, 3-5 parts of bactericide microspheres, 3-5 parts of polyethylene wax and 10-20 parts of white carbon black;
the modified fiber is prepared by the following method: mixing bamboo fibers, flax fibers, hemp fibers and cotton fibers according to a mass ratio of 2-3:1:0.3-1:0.5-1, adding the mixture into a 5-10% sodium hydroxide aqueous solution, soaking the mixture at the temperature of 90-95 ℃ for 2-3h, then carrying out ultrasonic treatment on the solution for 20-30min, washing and drying the composite fibers after ultrasonic treatment, dispersing the dried composite fibers in dimethylformamide, adding epoxy chloropropane, carrying out esterification at the temperature of 110-120 ℃, wherein the reaction time is 6-8h, after the reaction is finished, purifying reactants to obtain modified composite fibers, and carrying out irradiation treatment on the obtained reactants in an air atmosphere to obtain the modified composite fibers;
the modified plasticizer is prepared by the following method: mixing starch, chitosan, carboxymethyl cellulose, hemicellulose and hyaluronic acid according to the mass ratio of 2-5:1-2:0.5-1:0.2-0.5:1-2 to obtain a mixture A, dispersing the obtained mixture A in dimethylformamide, adding fatty acid ester, reacting at the temperature of 60-80 ℃ for 4-5 hours, and after the reaction is finished, purifying reactants to obtain a modified plasticizer;
the bactericide microsphere is prepared by the following method: adding bactericide into the solution containing 2-3% of chitosan to prepare microspheres, and freeze-drying to obtain the bactericide microspheres.
2. Biodegradable composite material having antibacterial properties, according to claim 1, characterized in that said fatty acid ester is a fatty acid methyl ester; the mass-volume ratio of the mixture A to the fatty acid ester is 1:1-5 mg/ml.
3. The biodegradable composite material having antibacterial properties according to claim 2, characterized in that the fatty acid methyl ester is a mixture of methyl stearate, methyl oleate and methyl laurate in a volume ratio of 2-3:0.5-1: 1-2.
4. Biodegradable composite material having antibacterial properties, according to claim 1, characterized in that said irradiation treatment is with Co60Is used as irradiation light source, and the irradiation dose rate is 3-4 kGy. H-1The irradiation time is 2-3 h.
5. The biodegradable composite material with antibacterial properties as claimed in claim 1, wherein the output power of the ultrasonic treatment is 200-300W.
6. The biodegradable composite material having antibacterial properties according to claim 1, characterized in that the mass-to-volume ratio of said composite fiber to said epichlorohydrin is 1:10-15 mg/ml.
7. The biodegradable composite material having antibacterial properties according to claim 1, characterized in that said bactericide microspheres are prepared by the following method: adding polyhexamethylene guanidine bactericide into a solution containing 2-3% of chitosan, carrying out ultrasonic treatment for 20-30min under the condition of 25KW power, and after the ultrasonic treatment is finished, carrying out freeze drying on the mixed solution to obtain bactericide microspheres.
8. The biodegradable composite material having antibacterial properties as claimed in claim 7, characterized in that the volume ratio of said chitosan solution to said polyhexamethylene guanidine bactericide is 100: 1-2.
9. Method for the preparation of a biodegradable composite material having antibacterial properties according to any one of claims 1-8, characterized in that it comprises the following steps:
(1) preparing modified composite fiber: mixing bamboo fiber, flax fiber, hemp fiber and cotton fiber according to the mass ratio of 2-3:1:0.3-1:0.5-1, adding 5-10% of sodium hydroxide aqueous solution to soak for 2-3h at the temperature of 90-95 ℃, then carrying out ultrasonic treatment on the solution for 20-30min, washing and drying the composite fiber after ultrasonic treatment, dispersing the dried composite fiber in dimethylformamide, adding epoxy chloropropane, carrying out esterification at the temperature of 110-120 ℃, wherein the reaction time is 6-8h, after the reaction is finished, purifying reactants to obtain modified composite fiber, and carrying out Co-based modification on the obtained reactants in an air atmosphere60Is used as irradiation light source, and the irradiation dose rate is 3-4 kGy. H-1Irradiating for 2-3h to obtain modified composite fiber;
(2) preparation of modified plasticizer: mixing starch, chitosan, carboxymethyl cellulose, hemicellulose and hyaluronic acid according to the mass ratio of 2-5:1-2:0.5-1:0.2-0.5:1-2 to obtain a mixture A, dispersing the obtained mixture A in dimethylformamide, adding fatty acid ester, reacting at the temperature of 60-80 ℃ for 4-5 hours, and after the reaction is finished, purifying reactants to obtain a modified plasticizer;
(3) preparation of the bactericide microspheres: adding polyhexamethylene guanidine bactericide into a solution containing 2-3% of chitosan, carrying out ultrasonic treatment for 20-30min under the condition of 25KW power, and after the ultrasonic treatment is finished, carrying out freeze drying on the obtained mixed solution to obtain bactericide microspheres;
(4) according to parts by weight, melting 40-50 parts of polylactic acid, 10-20 parts of polyamide, 15-20 parts of modified composite fiber obtained in the step (1), 10-15 parts of modified plasticizer obtained in the step (2), 3-5 parts of poly epsilon-caprolactone, 2-6 parts of silane coupling agent, 3-5 parts of bactericide microspheres, 3-5 parts of polyethylene wax and 10-20 parts of white carbon black at the temperature of 180-200 ℃, then adding 10-20 parts of polyamide into an internal mixer, melting at the temperature of 260-280 ℃, and mixing for 20-30min to obtain the biodegradable composite material with antibacterial property.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811140276.4A CN110964300A (en) | 2018-09-28 | 2018-09-28 | Biodegradable composite material with antibacterial property and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811140276.4A CN110964300A (en) | 2018-09-28 | 2018-09-28 | Biodegradable composite material with antibacterial property and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110964300A true CN110964300A (en) | 2020-04-07 |
Family
ID=70027818
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811140276.4A Withdrawn CN110964300A (en) | 2018-09-28 | 2018-09-28 | Biodegradable composite material with antibacterial property and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110964300A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100216909A1 (en) * | 2007-10-03 | 2010-08-26 | Universidad De Concepcion | Biodegradable composition, preparation method and their application in the manufacture of functional containers for agricultural and/or forestry use |
| CN105778450A (en) * | 2016-05-06 | 2016-07-20 | 王泽陆 | Fiber-reinforced polylactic-acid composite material and preparation method thereof |
| CN105968743A (en) * | 2016-03-01 | 2016-09-28 | 安徽猛牛彩印包装有限公司 | Antibacterial polylactic acid and starch compound fully-degradable plastic film and manufacturing method thereof |
| CN106009565A (en) * | 2016-06-22 | 2016-10-12 | 沈阳浩博实业有限公司 | Nylon-reinforced polylactic acid composite material and preparation method thereof |
-
2018
- 2018-09-28 CN CN201811140276.4A patent/CN110964300A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100216909A1 (en) * | 2007-10-03 | 2010-08-26 | Universidad De Concepcion | Biodegradable composition, preparation method and their application in the manufacture of functional containers for agricultural and/or forestry use |
| CN105968743A (en) * | 2016-03-01 | 2016-09-28 | 安徽猛牛彩印包装有限公司 | Antibacterial polylactic acid and starch compound fully-degradable plastic film and manufacturing method thereof |
| CN105778450A (en) * | 2016-05-06 | 2016-07-20 | 王泽陆 | Fiber-reinforced polylactic-acid composite material and preparation method thereof |
| CN106009565A (en) * | 2016-06-22 | 2016-10-12 | 沈阳浩博实业有限公司 | Nylon-reinforced polylactic acid composite material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112521730B (en) | Biodegradable composite material and preparation method thereof | |
| CN105440606A (en) | Preparation method of fully biodegradable starch/polylactic acid base resin | |
| CN113717505B (en) | Degradable plastic and preparation method thereof | |
| CN109251494B (en) | Natural gutta-percha/cellulose modified polylactic acid composite material and preparation method thereof | |
| CN114316542B (en) | High-strength biodegradable plastic and preparation method thereof | |
| CN111393717B (en) | Degradable plastic and preparation method thereof | |
| Won et al. | Mechanical properties and biodegradability of the kenaf/soy protein isolate-PVA biocomposites | |
| CN111471285A (en) | Epoxidized lignin modified biodegradable film and preparation method thereof | |
| Gulati et al. | Synthesis and characterization of PVA/Starch/CMC composite films reinforced with walnut (Juglans regia L.) shell flour | |
| Husseinsyah et al. | Kapok husk-reinforced soy protein isolate biofilms: tensile properties and enzymatic hydrolysis | |
| JP2007222704A (en) | Manufacturing method for starch based water absorbent material | |
| CN111574755B (en) | Biodegradable plastic and preparation method thereof | |
| CN112250911A (en) | Method for preparing degradable plastic straw by using rice flour-amylose-wheat gluten | |
| CN110964300A (en) | Biodegradable composite material with antibacterial property and preparation method thereof | |
| CN111704790A (en) | Preparation method of polylactic acid-based composite wire for 3D printing | |
| CN102030830A (en) | Bamboo fiber nano crystal and reinforced biological nano composite material and preparation method thereof | |
| CN110964299A (en) | Preparation method and application of biodegradable composite material | |
| Elsayed et al. | Characterization of plastic composite based on HIPS loaded with bagasse | |
| CN114395234A (en) | Antibacterial environment-friendly tableware and preparation method thereof | |
| CN113563702A (en) | Degradable plastic bag and preparation method thereof | |
| WO2023277145A1 (en) | Polysaccharide nanofiber-blended polysaccharide composition production method | |
| Ghozali et al. | Effect of lignin on bio-based/oil-based polymer blends | |
| CN114149669B (en) | Degradable tableware and preparation method thereof | |
| CN111484590B (en) | Preparation method and application of feather keratin modified urea-formaldehyde resin | |
| CN115627080A (en) | Plant fiber degradable master batch 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 | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20200407 |
|
| WW01 | Invention patent application withdrawn after publication |