CN116023112A - Gypsum material for jewelry mold and preparation method thereof - Google Patents
Gypsum material for jewelry mold and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of gypsum material preparation methods, and provides a gypsum material for jewelry molds and a preparation method thereof, wherein a polycarboxylic acid macromolecule modified component generated by taking methyl alkenyl polyoxyethylene polyoxypropylene block ether, sodium methacrylate, acrylic acid and methyl acrylate as monomers for polymerization is added into the gypsum material, so that the flexural strength of the gypsum material can be improved to a certain extent; secondly, modified polypropylene alcohol fibers, modified basalt fibers and modified lignocellulose are added into the gypsum material according to different mixing amounts after being modified, so that the compressive strength and the water resistance of the gypsum material can be improved; and the first component and the second component are added, so that the gypsum material has more stable antibacterial performance, the flame retardant and fireproof performance of the gypsum material can be improved, the probability of smoldering and mildew of the gypsum material due to the addition of fibers and organic components is reduced, and the market application value of the gypsum material is improved.
Description
Technical Field
The invention relates to the technical field of gypsum material preparation methods, in particular to a gypsum material for jewelry molds and a preparation method thereof.
Background
Gypsum is monoclinic mineral, is a hydrate with calcium sulfate as main chemical component, is an industrial material and building material with wide application, and can be used for cement retarder, gypsum building products, model making, medical food additives, sulfuric acid production, paper filler, paint filler and the like. Compared with cement products, gypsum products have obvious advantages, and gypsum has better heat insulation effect, and the production cost is far lower than that of cement products, and particularly, in recent years, great economic and social benefits are obtained for recycling industrial byproduct gypsum. However, the water resistance and mechanical properties of gypsum generally limit the development of gypsum materials, and a lot of products for improving the mechanical properties of gypsum materials through modification are presented on the market at present, but most of products do not achieve ideal and optimal effects, so how to further improve the preparation method of gypsum materials, so that the performance of gypsum materials is more excellent, and the technical problem to be solved by those skilled in the art is urgent.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects existing in the prior art, the invention provides a gypsum material for jewelry molds and a preparation method thereof, which aim to ensure that the gypsum material prepared by the invention has better water resistance and mechanical property and improve the market popularization value.
Technical proposal
In order to achieve the above purpose, the invention is realized by the following technical scheme:
the gypsum material for the jewelry mold comprises the following raw materials in parts by weight: 1000 parts of desulfurized gypsum, 300 parts of polycarboxylic acid macromolecule modified components, 15-16 parts of modified polypropylene alcohol fibers, 18-20 parts of modified basalt fibers, 10-15 parts of modified lignocellulose, 20-22 parts of antibacterial components, 15-18 parts of flame retardant components, 30-35 parts of nano titanium dioxide particles, 0.5-0.8 part of citric acid retarder, a proper amount of ethanol solution and pure water.
Further, the preparation method of the polycarboxylic acid macromolecule modified component comprises the following steps:
step one, according to 8:5:12: weighing calculated amount of methyl alkenyl polyoxyethylene polyoxypropylene block ether, sodium methacrylate sulfonate, acrylic acid and methyl acrylate for standby, pouring the methyl alkenyl polyoxyethylene polyoxypropylene block ether and the sodium methacrylate sulfonate into a three-neck flask, adding pure water with the volume of 5-8 times of the methyl alkenyl polyoxyethylene polyoxypropylene block ether and the sodium methacrylate sulfonate, mixing and stirring until the pure water is dissolved, and dissolving ammonium persulfate in the pure water with the volume of 10 times for standby, wherein the dosage of the ammonium persulfate is 0.6% of the total system;
step two, heating the three-neck flask in the step one to 80 ℃ in a water bath, and dropwise adding the calculated amount of acrylic acid and methyl acrylate into the three-neck flask through a titration funnel, wherein pure water dissolved with ammonium persulfate in the step one is also dropwise added into the three-neck flask by using the titration funnel while dropwise adding;
and thirdly, after the dripping is finished, reacting for 8-10 hours at the temperature of 80 ℃ and the stirring speed of 200-300r/min, and adjusting the pH value to 7 after the reaction is finished, thus obtaining the polycarboxylic acid macromolecule modified component.
Further, the preparation method of the modified polypropylene alcohol fiber comprises the following steps:
step1, weighing 3-4 parts by weight of concentrated nitric acid and 40-45 parts by weight of pure water, pouring the concentrated nitric acid and the pure water into a beaker, mixing, adding 1 part by weight of ceric ammonium nitrate, mixing, and recording the obtained mixture as a titration component;
and 2, pouring 300 parts by weight of pure water, 10 parts by weight of polyvinyl alcohol fibers and 20 parts by weight of glycidyl methacrylate into a three-neck flask for mixing, dropwise adding a titration component into the flask under the condition of stirring, reacting for 5 hours under the water bath condition of 40 ℃, filtering, washing with water, filtering with acetone, and drying in a drying oven of 28 ℃ until the weight is constant, thus obtaining the modified polypropylene alcohol fibers.
Further, the preparation method of the modified basalt fiber comprises the following steps: soaking basalt fiber in acetone solution for 24 hours, washing for 3 times by pure water, then placing in a drying oven at 65 ℃ for drying for standby, then mixing 5-8 parts by weight of silane coupling agent with 70-80 parts by weight of ethanol solution with the concentration of 80% to prepare modified liquid, adding 10-12 parts by weight of basalt fiber subjected to the treatment and drying into the modified liquid, standing for 5-6 hours after uniformly mixing, filtering the obtained product, washing by absolute ethyl alcohol, and drying to obtain the modified basalt fiber.
Further, the preparation method of the modified lignocellulose comprises the following steps:
s1, weighing 10-12 parts by weight of a silane coupling agent and 6-8 parts by weight of pure water, mixing, stirring for 12 hours to obtain a hydrolysate, weighing 16-18 parts by weight of nano silicon dioxide, adding the nano silicon dioxide into 200 parts by weight of toluene, stirring for 2 hours, and performing ultrasonic dispersion for 20 minutes after stirring to obtain a dispersion;
s2, pouring the hydrolysate into the dispersion liquid, stirring uniformly, carrying out reflux reaction at 50 ℃, adding 1-2 parts by weight of triethylene diamine for mixing and stirring after reacting for 6 hours, then adding 15-16 parts by weight of lignocellulose, stirring for 2 hours at 110 ℃, and obtaining the modified lignocellulose after filtering and drying treatment.
Further, the stirring speed in the step S1 is 800-1000r/min, and the ultrasonic dispersion frequency is 26-28kHz.
Further, the antibacterial component is prepared by mixing tetradecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, tetradecyltrimethylammonium bromide, dodecyl dimethyl benzyl ammonium chloride, octadecyl dimethyl benzyl ammonium bromide and dodecyl dimethyl benzyl ammonium bromide according to the equal weight ratio.
Still further, the flame retardant components are triphenyl phosphate, ammonium polyphosphate, dimethyl methylphosphonate, magnesium hydroxide and aluminum hydroxide according to 3:2:5:2:1 weight ratio.
Further, the mass concentration of the ethanol solution is 80%.
A method of preparing a gypsum material for jewelry molds, the method comprising the steps of:
step1, mixing the modified polypropylene alcohol fiber, the modified basalt fiber, the modified lignocellulose and the antibacterial component in parts by weight to prepare a first mixture, adding an ethanol solution with the dosage of 8-10 times of that of the first mixture and an emulsifier T-80 with the dosage of 4-5% of the total system, uniformly stirring, performing ultrasonic dispersion for 30min under the condition of the frequency of 26-28kHz, and finally drying in an oven at the temperature of 40-45 ℃ and grinding to prepare the first component;
step2, pouring the flame retardant component and the nano titanium dioxide particles in parts by weight into a ball mill for grinding and mixing to obtain a second mixture, then adding an ethanol solution with the dosage of 5-6 times of that of the second mixture and an emulsifier T-80 with the dosage of 3-5% of the total system, uniformly stirring, performing ultrasonic dispersion for 30min under the condition of 26-28kHz, and finally drying in an oven at 55-60 ℃ for grinding to obtain a second component;
step3, adding the first component in Step1 and the second component in Step2 into the polycarboxylic acid macromolecule modified component in parts by weight, stirring for 10-15min at a stirring speed of 500-600r/min, then mixing and stirring the mixture with the desulfurized gypsum in parts by weight, adding pure water with 3-5 times of the total amount of the desulfurized gypsum dispersed with the citric acid retarder in parts by weight, stirring for 20-30min at a stirring speed of 300-400r/min, and finally drying for 24h at 45-50 ℃ to obtain the gypsum material for jewelry molds.
Advantageous effects
The invention provides a gypsum material for jewelry molds and a preparation method thereof, and compared with the prior art, the gypsum material has the following beneficial effects:
1. according to the invention, the silane coupling agent and the nano silicon dioxide are used for modifying the lignocellulose, so that the silane coupling agent and the nano silicon dioxide can be grafted, the silane coupling agent can be used as an intermediate for connecting the nano silicon dioxide and the lignocellulose, and the nano silicon dioxide is firmly carried on the surface of the lignocellulose, so that the modified lignocellulose has better adhesive force; secondly, in the process of preparing the first component, due to the porous structure of the surface of the nano silicon dioxide, antibacterial molecules in the antibacterial component can be dispersed and adsorbed in the porous structure of the nano silicon dioxide, so that the antibacterial component can be more uniformly dispersed between the modified polypropylene alcohol fiber and the modified basalt fiber, and the first component has stable antibacterial performance.
2. In the process of preparing the second component, the flame-retardant component and the nano titanium dioxide particles are mixed in a grinding and mixing mode, so that the molecular structure in the flame-retardant component is adsorbed in the porous structure on the surface of the nano titanium dioxide particles, and the solid component in the flame-retardant component is more uniformly mixed with the nano titanium dioxide particles, so that the second component has stable flame retardant property.
3. According to the invention, the polycarboxylic acid macromolecule modified component polymerized by taking the methyl alkenyl polyoxyethylene polyoxypropylene block ether, the sodium methacrylate, the acrylic acid and the methyl acrylate as monomers is added into the gypsum material, so that the flexural strength of the gypsum material can be improved to a certain extent; secondly, modified polypropylene alcohol fibers, modified basalt fibers and modified lignocellulose are added into the gypsum material according to different mixing amounts after being modified, so that the compressive strength and the water resistance of the gypsum material can be improved; and the first component and the second component are added, so that the gypsum material has more stable antibacterial performance, the flame retardant and fireproof performance of the gypsum material can be improved, the probability of smoldering and mildew of the gypsum material due to the addition of fibers and organic components is reduced, and the market application value of the gypsum material is improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention is further described below with reference to examples.
Example 1
The gypsum material for jewelry molds of the embodiment comprises the following raw materials in parts by weight: 1000 parts of desulfurized gypsum, 300 parts of polycarboxylic acid macromolecule modified components, 15 parts of modified polypropylene alcohol fibers, 18 parts of modified basalt fibers, 10 parts of modified lignocellulose, 20 parts of antibacterial components, 15 parts of flame retardant components, 30 parts of nano titanium dioxide particles, 0.5 part of citric acid retarder, a proper amount of ethanol solution and pure water.
The preparation method of the polycarboxylic acid macromolecule modified component comprises the following steps:
step one, according to 8:5:12:10, weighing calculated amount of methyl alkenyl polyoxyethylene polyoxypropylene block ether, sodium methacrylate sulfonate, acrylic acid and methyl acrylate for standby, then pouring the methyl alkenyl polyoxyethylene polyoxypropylene block ether and the sodium methacrylate sulfonate into a three-neck flask, adding pure water with the volume being 5 times of that of the methyl alkenyl polyoxyethylene polyoxypropylene block ether and the sodium methacrylate sulfonate, mixing and stirring until the mixture is dissolved, and then dissolving ammonium persulfate in the pure water with the volume being 10 times of that of the mixture for standby, wherein the dosage of the ammonium persulfate is 0.6% of that of the total system;
step two, heating the three-neck flask in the step one to 80 ℃ in a water bath, and dropwise adding the calculated amount of acrylic acid and methyl acrylate into the three-neck flask through a titration funnel, wherein the titration funnel is used for dropwise adding pure water dissolved with ammonium persulfate in the step one into the three-neck flask at the same time;
and thirdly, after the dripping is finished, reacting for 8 hours at the temperature of 80 ℃ and the stirring speed of 200r/min, and adjusting the pH value to 7 after the reaction is finished, thus obtaining the polycarboxylic acid macromolecule modified component.
The preparation method of the modified polypropylene alcohol fiber comprises the following steps:
step1, weighing 3 parts by weight of concentrated nitric acid and 40 parts by weight of pure water, pouring the concentrated nitric acid and the pure water into a beaker, mixing, and then adding 1 part by weight of ammonium cerium nitrate for mixing, wherein the obtained mixture is recorded as a titration component;
and 2, pouring 300 parts by weight of pure water, 10 parts by weight of polyvinyl alcohol fibers and 20 parts by weight of glycidyl methacrylate into a three-neck flask for mixing, dropwise adding a titration component into the flask under the condition of stirring, reacting for 5 hours under the water bath condition of 40 ℃, filtering, washing with water, filtering with acetone, and drying in a drying oven of 28 ℃ until the weight is constant, thus obtaining the modified polypropylene alcohol fibers.
The preparation method of the modified basalt fiber comprises the following steps: soaking basalt fiber in acetone solution for 24 hours, washing for 3 times by pure water, then placing in a drying oven at 65 ℃ for drying for standby, then mixing 5 parts by weight of silane coupling agent with 70 parts by weight of ethanol solution with the concentration of 80% to prepare modified liquid, adding 10 parts by weight of basalt fiber subjected to the treatment and drying into the modified liquid, standing for 5 hours after uniformly mixing, filtering the obtained product, washing by absolute ethyl alcohol, and drying to obtain the modified basalt fiber.
The preparation method of the modified lignocellulose comprises the following steps:
s1, weighing 10 parts by weight of silane coupling agent and 6 parts by weight of pure water, mixing, stirring for 12 hours to obtain hydrolysate, weighing 16 parts by weight of nano silicon dioxide, adding the hydrolysate into 200 parts by weight of toluene, stirring for 2 hours, and performing ultrasonic dispersion for 20 minutes after stirring to obtain dispersion;
s2, pouring the hydrolysate into the dispersion liquid, uniformly stirring, carrying out reflux reaction at 50 ℃, adding 1 part by weight of triethylene diamine for mixing and stirring after reacting for 6 hours, then adding 15 parts by weight of lignocellulose, stirring for 2 hours at 110 ℃, and obtaining the modified lignocellulose after filtering and drying treatment.
The stirring speed in S1 is 800r/min, and the ultrasonic dispersion frequency is 26kHz.
The antibacterial component is prepared by mixing tetradecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium bromide, dodecyl dimethyl benzyl ammonium chloride, octadecyl dimethyl benzyl ammonium bromide and dodecyl dimethyl benzyl ammonium bromide according to the equal weight ratio.
The flame retardant components are triphenyl phosphate, ammonium polyphosphate, dimethyl methylphosphonate, magnesium hydroxide and aluminum hydroxide according to the following weight ratio of 3:2:5:2:1 weight ratio.
The mass concentration of the ethanol solution is 80%.
The preparation method of the gypsum material for the jewelry mold comprises the following steps:
step1, mixing the modified polypropylene alcohol fiber, the modified basalt fiber, the modified lignocellulose and the antibacterial component in parts by weight to prepare a first mixture, adding an ethanol solution with the dosage of 8 times of that of the first mixture and an emulsifier T-80 with the dosage of 4% of the total system, uniformly stirring, performing ultrasonic dispersion for 30min under the condition of 26kHz, and finally drying in a baking oven at 40 ℃ to prepare the first component by grinding;
step2, pouring the flame retardant component and the nano titanium dioxide particles in parts by weight into a ball mill, grinding and mixing to obtain a second mixture, adding an ethanol solution with the dosage being 5 times that of the second mixture and an emulsifier T-80 with the dosage being 3% of the total system, uniformly stirring, performing ultrasonic dispersion for 30min under the condition of 26kHz, drying in a drying oven at 55 ℃, and grinding to obtain a second component;
step3, adding the first component in Step1 and the second component in Step2 into the polycarboxylic acid macromolecule modified component in parts by weight, stirring for 10min at a stirring speed of 500r/min, then mixing and stirring the mixture with the desulfurized gypsum in parts by weight, adding pure water with the total amount of 3 times of the desulfurized gypsum and the citric acid retarder dispersed in parts by weight, stirring for 20min at a stirring speed of 300r/min, and finally drying at 45 ℃ for 24h to obtain the gypsum material for jewelry molds.
Example 2
The gypsum material for jewelry molds of the embodiment comprises the following raw materials in parts by weight: 1000 parts of desulfurized gypsum, 300 parts of polycarboxylic acid macromolecule modified components, 16 parts of modified polypropylene alcohol fibers, 20 parts of modified basalt fibers, 15 parts of modified lignocellulose, 22 parts of antibacterial components, 18 parts of flame retardant components, 35 parts of nano titanium dioxide particles, 0.8 part of citric acid retarder, a proper amount of ethanol solution and pure water.
The preparation method of the polycarboxylic acid macromolecule modified component comprises the following steps:
step one, according to 8:5:12:10, weighing calculated amount of methyl alkenyl polyoxyethylene polyoxypropylene block ether, sodium methacrylate sulfonate, acrylic acid and methyl acrylate for standby, then pouring the methyl alkenyl polyoxyethylene polyoxypropylene block ether and the sodium methacrylate sulfonate into a three-neck flask, adding pure water with the volume being 8 times of that of the methyl alkenyl polyoxyethylene polyoxypropylene block ether and the sodium methacrylate sulfonate, mixing and stirring until the pure water is dissolved, and then dissolving ammonium persulfate in the pure water with the volume being 10 times of that of the pure water for standby, wherein the dosage of the ammonium persulfate is 0.6% of that of the total system;
step two, heating the three-neck flask in the step one to 80 ℃ in a water bath, and dropwise adding the calculated amount of acrylic acid and methyl acrylate into the three-neck flask through a titration funnel, wherein the titration funnel is used for dropwise adding pure water dissolved with ammonium persulfate in the step one into the three-neck flask at the same time;
and thirdly, reacting for 10 hours at the temperature of 80 ℃ and the stirring speed of 300r/min after the dripping is finished, and regulating the pH value to 7 after the reaction is finished to obtain the polycarboxylic acid macromolecule modified component.
The preparation method of the modified polypropylene alcohol fiber comprises the following steps:
step1, weighing 4 parts by weight of concentrated nitric acid and 45 parts by weight of pure water, pouring the concentrated nitric acid and the pure water into a beaker, mixing, then adding 1 part by weight of ammonium cerium nitrate, mixing, and recording the obtained mixture as a titration component;
and 2, pouring 300 parts by weight of pure water, 10 parts by weight of polyvinyl alcohol fibers and 20 parts by weight of glycidyl methacrylate into a three-neck flask for mixing, dropwise adding a titration component into the flask under the condition of stirring, reacting for 5 hours under the water bath condition of 40 ℃, filtering, washing with water, filtering with acetone, and drying in a drying oven of 28 ℃ until the weight is constant, thus obtaining the modified polypropylene alcohol fibers.
The preparation method of the modified basalt fiber comprises the following steps: soaking basalt fiber in acetone solution for 24 hours, washing for 3 times by pure water, then placing in a drying oven at 65 ℃ for drying for standby, then mixing 8 parts by weight of silane coupling agent with 80 parts by weight of ethanol solution with the concentration of 80% to prepare modified liquid, adding 12 parts by weight of basalt fiber subjected to the treatment and drying into the modified liquid, standing for 6 hours after uniformly mixing, filtering the obtained product, washing by absolute ethyl alcohol, and drying to obtain the modified basalt fiber.
The preparation method of the modified lignocellulose comprises the following steps:
s1, weighing 12 parts by weight of silane coupling agent and 8 parts by weight of pure water, mixing, stirring for 12 hours to obtain hydrolysate, weighing 18 parts by weight of nano silicon dioxide, adding into 200 parts by weight of toluene, stirring for 2 hours, and performing ultrasonic dispersion for 20 minutes after stirring to obtain dispersion;
s2, pouring the hydrolysate into the dispersion liquid, uniformly stirring, carrying out reflux reaction at 50 ℃, adding 2 parts by weight of triethylene diamine for mixing and stirring after reacting for 6 hours, then adding 16 parts by weight of lignocellulose, stirring for 2 hours at 110 ℃, and obtaining the modified lignocellulose after filtering and drying treatment.
The stirring speed in S1 is 1000r/min, and the ultrasonic dispersion frequency is 28kHz.
The antibacterial component is prepared by mixing tetradecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium bromide, dodecyl dimethyl benzyl ammonium chloride, octadecyl dimethyl benzyl ammonium bromide and dodecyl dimethyl benzyl ammonium bromide according to the equal weight ratio.
The flame retardant components are triphenyl phosphate, ammonium polyphosphate, dimethyl methylphosphonate, magnesium hydroxide and aluminum hydroxide according to the following weight ratio of 3:2:5:2:1 weight ratio.
The mass concentration of the ethanol solution is 80%.
The preparation method of the gypsum material for the jewelry mold comprises the following steps:
step1, mixing the modified polypropylene alcohol fiber, the modified basalt fiber, the modified lignocellulose and the antibacterial component in parts by weight to prepare a first mixture, adding an ethanol solution with the dosage being 10 times that of the first mixture and an emulsifier T-80 with the dosage being 5% of the total system, uniformly stirring, performing ultrasonic dispersion for 30min under the condition of 28kHz, and finally drying in a baking oven at 45 ℃ to prepare the first component by grinding;
step2, pouring the flame retardant component and the nano titanium dioxide particles in parts by weight into a ball mill, grinding and mixing to obtain a second mixture, adding an ethanol solution with the dosage of 6 times of that of the second mixture and an emulsifier T-80 with the dosage of 5% of the total system, uniformly stirring, performing ultrasonic dispersion for 30min under the condition of 28kHz, drying in a baking oven at 60 ℃, and grinding to obtain a second component;
step3, adding the first component in Step1 and the second component in Step2 into the polycarboxylic acid macromolecule modified component in parts by weight, stirring for 15min at a stirring speed of 600r/min, then mixing and stirring the mixture with the desulfurized gypsum in parts by weight, adding pure water with the total amount of 5 times of the desulfurized gypsum dispersed with the citric acid retarder in parts by weight, stirring for 30min at a stirring speed of 400r/min, and finally drying for 24h at 50 ℃ to obtain the gypsum material for jewelry molds.
Example 3
The gypsum material for jewelry molds of the embodiment comprises the following raw materials in parts by weight: 1000 parts of desulfurized gypsum, 300 parts of polycarboxylic acid macromolecule modified components, 16 parts of modified polypropylene alcohol fibers, 19 parts of modified basalt fibers, 13 parts of modified lignocellulose, 21 parts of antibacterial components, 16 parts of flame retardant components, 33 parts of nano titanium dioxide particles, 0.7 part of citric acid retarder, a proper amount of ethanol solution and pure water.
The preparation method of the polycarboxylic acid macromolecule modified component comprises the following steps:
step one, according to 8:5:12:10, weighing calculated amount of methyl alkenyl polyoxyethylene polyoxypropylene block ether, sodium methacrylate sulfonate, acrylic acid and methyl acrylate for standby, then pouring the methyl alkenyl polyoxyethylene polyoxypropylene block ether and the sodium methacrylate sulfonate into a three-neck flask, adding pure water with the volume being 7 times of that of the methyl alkenyl polyoxyethylene polyoxypropylene block ether and the sodium methacrylate sulfonate, mixing and stirring until the pure water is dissolved, and then dissolving ammonium persulfate in the pure water with the volume being 10 times of that of the pure water for standby, wherein the dosage of the ammonium persulfate is 0.6% of that of the total system;
step two, heating the three-neck flask in the step one to 80 ℃ in a water bath, and dropwise adding the calculated amount of acrylic acid and methyl acrylate into the three-neck flask through a titration funnel, wherein the titration funnel is used for dropwise adding pure water dissolved with ammonium persulfate in the step one into the three-neck flask at the same time;
and thirdly, reacting for 9 hours at the temperature of 80 ℃ and the stirring speed of 300r/min after the dripping is finished, and regulating the pH value to 7 after the reaction is finished, thus obtaining the polycarboxylic acid macromolecule modified component.
The preparation method of the modified polypropylene alcohol fiber comprises the following steps:
step1, weighing 4 parts by weight of concentrated nitric acid and 43 parts by weight of pure water, pouring the concentrated nitric acid and the 43 parts by weight of pure water into a beaker, mixing, and then adding 1 part by weight of ammonium cerium nitrate for mixing, wherein the obtained mixture is recorded as a titration component;
and 2, pouring 300 parts by weight of pure water, 10 parts by weight of polyvinyl alcohol fibers and 20 parts by weight of glycidyl methacrylate into a three-neck flask for mixing, dropwise adding a titration component into the flask under the condition of stirring, reacting for 5 hours under the water bath condition of 40 ℃, filtering, washing with water, filtering with acetone, and drying in a drying oven of 28 ℃ until the weight is constant, thus obtaining the modified polypropylene alcohol fibers.
The preparation method of the modified basalt fiber comprises the following steps: soaking basalt fiber in acetone solution for 24 hours, washing for 3 times by pure water, then placing in a drying oven at 65 ℃ for drying for standby, then mixing 7 parts by weight of silane coupling agent and 75 parts by weight of ethanol solution with the concentration of 80% to prepare modified liquid, adding 11 parts by weight of basalt fiber subjected to the treatment and drying into the modified liquid, standing for 6 hours after uniformly mixing, filtering the obtained product, washing by absolute ethyl alcohol, and drying to obtain the modified basalt fiber.
The preparation method of the modified lignocellulose comprises the following steps:
s1, weighing 11 parts by weight of silane coupling agent and 7 parts by weight of pure water, mixing, stirring for 12 hours to obtain hydrolysate, weighing 17 parts by weight of nano silicon dioxide, adding into 200 parts by weight of toluene, stirring for 2 hours, and performing ultrasonic dispersion for 20 minutes after stirring to obtain dispersion;
s2, pouring the hydrolysate into the dispersion liquid, uniformly stirring, carrying out reflux reaction at 50 ℃, adding 2 parts by weight of triethylene diamine for mixing and stirring after reacting for 6 hours, then adding 15 parts by weight of lignocellulose, stirring for 2 hours at 110 ℃, and obtaining the modified lignocellulose after filtering and drying treatment.
The stirring speed in S1 is 900r/min, and the ultrasonic dispersion frequency is 27kHz.
The antibacterial component is prepared by mixing tetradecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium bromide, dodecyl dimethyl benzyl ammonium chloride, octadecyl dimethyl benzyl ammonium bromide and dodecyl dimethyl benzyl ammonium bromide according to the equal weight ratio.
The flame retardant components are triphenyl phosphate, ammonium polyphosphate, dimethyl methylphosphonate, magnesium hydroxide and aluminum hydroxide according to the following weight ratio of 3:2:5:2:1 weight ratio.
The mass concentration of the ethanol solution is 80%.
The preparation method of the gypsum material for the jewelry mold comprises the following steps:
step1, mixing the modified polypropylene alcohol fiber, the modified basalt fiber, the modified lignocellulose and the antibacterial component in parts by weight to prepare a first mixture, adding an ethanol solution with the dosage being 9 times that of the first mixture and an emulsifier T-80 with the dosage being 4% of the total system, uniformly stirring, performing ultrasonic dispersion for 30min under the condition of the frequency being 27kHz, and finally drying in a baking oven at 43 ℃ to prepare the first component by grinding;
step2, pouring the flame retardant component and the nano titanium dioxide particles in parts by weight into a ball mill, grinding and mixing to obtain a second mixture, adding an ethanol solution with the dosage being 5 times that of the second mixture and an emulsifier T-80 with the dosage being 4% of the total system, uniformly stirring, performing ultrasonic dispersion for 30min under the condition of the frequency of 27kHz, and finally drying in a baking oven at 57 ℃ to obtain the second component through grinding;
step3, adding the first component in Step1 and the second component in Step2 into the polycarboxylic acid macromolecule modified component in parts by weight, stirring for 13min at a stirring speed of 500r/min, then mixing and stirring the mixture with the desulfurized gypsum in parts by weight, adding pure water with the total amount of 4 times of the desulfurized gypsum and the citric acid retarder dispersed in parts by weight, stirring for 25min at a stirring speed of 400r/min, and finally drying for 24h at 47 ℃ to obtain the gypsum material for jewelry molds.
Comparative example 1: the gypsum material for jewelry mold and the preparation method thereof provided in this embodiment are substantially the same as those in embodiment 1, and the main differences are that: the polycarboxylic acid macromolecular modifying component of example 1 was not added to comparative example 1.
Comparative example 2: the gypsum material for jewelry mold and the preparation method thereof provided in this embodiment are substantially the same as those in embodiment 2, and the main differences are that: the modified lignocellulose in example 2 was not added to comparative example 2.
Comparative example 3: the gypsum material for jewelry mold and the preparation method thereof provided in this embodiment are substantially the same as those in embodiment 3, and the main differences are that: the flame retardant component and the nano titania particles in example 3 were not added to comparative example 3.
Performance testing
The gypsum materials prepared in examples 1 to 3 were labeled as example 1, example 2, example 3, respectively, the gypsum materials prepared in comparative examples 1 to 3 were labeled as comparative example 1, comparative example 2, comparative example 3, respectively, and then the properties of examples 1 to 3 and comparative example were examined in the following manner:
1. the compressive and flexural strength of the gypsum materials of examples 1-3 and comparative examples 1-3 were tested in accordance with the standard and manner of QB T1640-1992.
2. The detection method of the comprehensive antibacterial rate comprises the following steps:
(1) Culturing staphylococcus aureus and escherichia coli according to the standard and mode of GB/T20944.2-2007, culturing to obtain detection bacterial liquid with bacterial liquid concentration of 1X 105 CFU/mL-3X 105CFU/mL, cutting gypsum materials in examples 1-3 and comparative examples 1-3 into detection sample blocks with the same volume, and preparing blank sample blocks with the same volume by taking any gypsum material in examples 1-3 and comparative examples 1-3 as a raw material, wherein the length, width and height of each detection sample block and each blank sample block are 5cm, 5cm and 1cm respectively;
(2) Respectively placing the detection sample block and the blank control sample block into beakers with proper sizes after sterilization treatment, then using a pipettor to absorb 0.2mL of detection bacterial liquid to respectively smear and inoculate on the surfaces of the detection sample block and the blank control sample block, covering the surfaces of the detection sample block and the blank control sample block by using a sterile cover body after inoculation, placing the beakers with the detection sample block at the temperature of 35-39 ℃ for culturing for 18-24 hours, respectively pouring SCDLP culture mediums into the beakers with the detection sample block after the culturing is finished, immediately pouring the beakers with the blank control sample block into the SCDLP culture mediums after smearing and inoculation, wherein the volume of the poured SCDLP culture mediums in each beakers is the same;
(3) Pouring SCDLP culture medium to soak test sample blocks and blank control sample blocks for 1min, washing bacteria on the surfaces of the test sample blocks and the blank control sample blocks, respectively sucking 1mL of the washed SCDLP culture medium into a culture dish, filling the culture dish with the same volume of culture medium prepared according to the GB/T20944.2-2007 standard, culturing for 24-48h at the temperature of 35-39 ℃, collecting colonies on the culture dish after culturing, drying and weighing the colonies, and respectively marking the dry weights of the test sample blocks and the blank control sample blocks as example 1 dry weight, example 2 dry weight, example 3 dry weight, comparative example 1 dry weight, comparative example 2 dry weight, comparative example 3 dry weight and blank test sample block dry weight;
(4) The comprehensive antibacterial rates of the test specimens of examples 1 to 3 and comparative examples 1 to 3 were calculated by taking example 1 as an example: the comprehensive antibacterial ratio of example 1= (dry weight of blank test sample block-dry weight of example 1)/dry weight of blank test sample block, and so on, the comprehensive antibacterial ratios of examples 2 to 3 and comparative examples 1 to 3 were calculated.
3. The smoldering time detection mode is as follows: the gypsum materials in examples 1-3 and comparative examples 1-3 were cut into test pieces of the same size in terms of length, width and height, each of which was 1cm, 1cm and 10cm, and the test pieces in examples 2-3 and comparative examples 1-3 were burned using an open fire source, the open fire source was removed after the burning, and the smoldering time of the test pieces after the removal of the open fire source was recorded.
The test results are recorded in table 1:
as is apparent from the above table data, the gypsum material prepared in example 1 has better compressive strength and flexural strength than those of the comparative example, thereby demonstrating that the addition of the macromolecular components to the gypsum material can improve the mechanical properties thereof; secondly, compared with comparative example 2, the gypsum material prepared in this example 2 has better antibacterial effect, so that nano silica particles are introduced into the modified lignocellulose, and the particles can better adsorb antibacterial molecules in antibacterial components, so that the gypsum material has more stable antibacterial performance; finally, compared with comparative example 3, the gypsum material prepared in this example 3 has better flame retardant property, and because the gypsum material is added with fiber, organic matter and other inflammable components, there is a risk of smoldering under open fire, and better flame retardant effect can be achieved by adding the flame retardant components and nano titanium dioxide particles. Therefore, the gypsum material for jewelry molds prepared by the invention has better performance and better market application prospect.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (7)
1. The gypsum material for the jewelry mold is characterized by comprising the following raw materials in parts by weight: 1000 parts of desulfurized gypsum, 300 parts of polycarboxylic acid macromolecule modified components, 15-16 parts of modified polypropylene alcohol fibers, 18-20 parts of modified basalt fibers, 10-15 parts of modified lignocellulose, 20-22 parts of antibacterial components, 15-18 parts of flame retardant components, 30-35 parts of nano titanium dioxide particles, 0.5-0.8 part of citric acid retarder, a proper amount of ethanol solution and pure water;
the preparation method of the modified lignocellulose comprises the following steps:
s1, weighing 10-12 parts by weight of a silane coupling agent and 6-8 parts by weight of pure water, mixing, stirring for 12 hours to obtain a hydrolysate, weighing 16-18 parts by weight of nano silicon dioxide, adding the nano silicon dioxide into 200 parts by weight of toluene, stirring for 2 hours, and performing ultrasonic dispersion for 20 minutes after stirring to obtain a dispersion;
s2, pouring the hydrolysate into the dispersion liquid, uniformly stirring, carrying out reflux reaction at 50 ℃, adding 1-2 parts by weight of triethylene diamine for mixing and stirring after reacting for 6 hours, then adding 15-16 parts by weight of lignocellulose, stirring for 2 hours at 110 ℃, and obtaining the modified lignocellulose after filtering and drying treatment;
the stirring speed in the step S1 is 800-1000r/min, and the ultrasonic dispersion frequency is 26-28kHz;
the preparation method of the polycarboxylic acid macromolecule modified component comprises the following steps:
step one, according to 8:5:12: weighing calculated amount of methyl alkenyl polyoxyethylene polyoxypropylene block ether, sodium methacrylate sulfonate, acrylic acid and methyl acrylate for standby, pouring the methyl alkenyl polyoxyethylene polyoxypropylene block ether and the sodium methacrylate sulfonate into a three-neck flask, adding pure water with the volume of 5-8 times of the methyl alkenyl polyoxyethylene polyoxypropylene block ether and the sodium methacrylate sulfonate, mixing and stirring until the pure water is dissolved, and dissolving ammonium persulfate in the pure water with the volume of 10 times for standby, wherein the dosage of the ammonium persulfate is 0.6% of the total system;
step two, heating the three-neck flask in the step one to 80 ℃ in a water bath, and dropwise adding the calculated amount of acrylic acid and methyl acrylate into the three-neck flask through a titration funnel, wherein pure water dissolved with ammonium persulfate in the step one is also dropwise added into the three-neck flask by using the titration funnel while dropwise adding;
and thirdly, after the dripping is finished, reacting for 8-10 hours at the temperature of 80 ℃ and the stirring speed of 200-300r/min, and adjusting the pH value to 7 after the reaction is finished, thus obtaining the polycarboxylic acid macromolecule modified component.
2. The gypsum material for jewelry mold according to claim 1, wherein the preparation method of the modified polypropylene alcohol fiber comprises the steps of:
step1, weighing 3-4 parts by weight of concentrated nitric acid and 40-45 parts by weight of pure water, pouring the concentrated nitric acid and the pure water into a beaker, mixing, adding 1 part by weight of ceric ammonium nitrate, mixing, and recording the obtained mixture as a titration component;
and 2, pouring 300 parts by weight of pure water, 10 parts by weight of polyvinyl alcohol fibers and 20 parts by weight of glycidyl methacrylate into a three-neck flask for mixing, dropwise adding a titration component into the flask under the condition of stirring, reacting for 5 hours under the water bath condition of 40 ℃, filtering, washing with water, filtering with acetone, and drying in a drying oven of 28 ℃ until the weight is constant, thus obtaining the modified polypropylene alcohol fibers.
3. The gypsum material for jewelry mold according to claim, wherein the preparation method of the modified basalt fiber comprises the following steps: soaking basalt fiber in acetone solution for 24 hours, washing for 3 times by pure water, then placing in a drying oven at 65 ℃ for drying for standby, then mixing 5-8 parts by weight of silane coupling agent with 70-80 parts by weight of ethanol solution with the concentration of 80% to prepare modified liquid, adding 10-12 parts by weight of basalt fiber subjected to the treatment and drying into the modified liquid, standing for 5-6 hours after uniformly mixing, filtering the obtained product, washing by absolute ethyl alcohol, and drying to obtain the modified basalt fiber.
4. The gypsum material for jewelry mold according to claim 1, wherein the antibacterial component is made by mixing tetradecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, tetradecyltrimethylammonium bromide, dodecyl dimethyl benzyl ammonium chloride, octadecyl dimethyl benzyl ammonium bromide and dodecyl dimethyl benzyl ammonium bromide in equal weight ratio.
5. A gypsum material for jewelry molds according to claim 1, wherein said flame retardant component is triphenyl phosphate, ammonium polyphosphate, dimethyl methylphosphonate, magnesium hydroxide and aluminum hydroxide according to 3:2:5:2:1 weight ratio.
6. A gypsum material for jewelry molds as claimed in claim 1, wherein said ethanol solution has a mass concentration of 80%.
7. A method of preparing a gypsum material for jewelry molds as claimed in claim 1, wherein said method of preparing comprises the steps of:
step1, mixing the modified polypropylene alcohol fiber, the modified basalt fiber, the modified lignocellulose and the antibacterial component in parts by weight to prepare a first mixture, adding an ethanol solution with the dosage of 8-10 times of that of the first mixture and an emulsifier T-80 with the dosage of 4-5% of the total system, uniformly stirring, performing ultrasonic dispersion for 30min under the condition of the frequency of 26-28kHz, and finally drying in an oven at the temperature of 40-45 ℃ and grinding to prepare the first component;
step2, pouring the flame retardant component and the nano titanium dioxide particles in parts by weight into a ball mill for grinding and mixing to obtain a second mixture, then adding an ethanol solution with the dosage of 5-6 times of that of the second mixture and an emulsifier T-80 with the dosage of 3-5% of the total system, uniformly stirring, performing ultrasonic dispersion for 30min under the condition of 26-28kHz, and finally drying in an oven at 55-60 ℃ for grinding to obtain a second component;
step3, adding the first component in Step1 and the second component in Step2 into the polycarboxylic acid macromolecule modified component in parts by weight, stirring for 10-15min at a stirring speed of 500-600r/min, then mixing and stirring the mixture with the desulfurized gypsum in parts by weight, adding pure water with 3-5 times of the total amount of the desulfurized gypsum dispersed with the citric acid retarder in parts by weight, stirring for 20-30min at a stirring speed of 300-400r/min, and finally drying for 24h at 45-50 ℃ to obtain the gypsum material for jewelry molds.
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