CN111848477B - Preparation method of rubber vulcanization accelerator - Google Patents
Preparation method of rubber vulcanization accelerator Download PDFInfo
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- CN111848477B CN111848477B CN202010723000.XA CN202010723000A CN111848477B CN 111848477 B CN111848477 B CN 111848477B CN 202010723000 A CN202010723000 A CN 202010723000A CN 111848477 B CN111848477 B CN 111848477B
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C333/14—Dithiocarbamic acids; Derivatives thereof
- C07C333/16—Salts of dithiocarbamic acids
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
Abstract
The invention discloses a preparation method of a rubber vulcanization accelerator, which comprises the following steps: adding diethylamine into the ethanol solution, mixing, and dropwise adding a first part of sodium hydroxide solution while stirring to form a first mixed solution; dropwise adding a first part of carbon disulfide into the first mixed solution, and stirring to obtain a second mixed solution; dropwise adding the remaining second part of sodium hydroxide solution into the second mixed solution, and stirring to obtain a third mixed solution; dropwise adding the remaining second part of carbon disulfide into the third mixed solution, and stirring to obtain a fourth mixed solution; adding a catalyst 2-ethylhexanoic acid into the fourth mixed solution, then adding zinc carbonate in batches, carrying out solid-liquid separation after reaction, and carrying out aftertreatment on the solid to obtain the rubber vulcanization accelerator. The zinc diethyl dithiocarbamate prepared by the invention has higher activity, and the zinc diethyl dithiocarbamate is added into a rubber material to ensure that the activation effect of a vulcanizing agent is obvious, the vulcanizing time can be shortened, the vulcanizing temperature can be reduced, the consumption of the vulcanizing agent can be reduced, the mechanical property of rubber can be improved, and the quality of vulcanized rubber can be obviously improved.
Description
Technical Field
The invention belongs to the technical field of rubber vulcanization accelerators, relates to a preparation method of a rubber vulcanization accelerator, and particularly relates to a preparation method of zinc diethyldithiocarbamate with excellent vulcanization performance.
Background
The rubber vulcanization accelerator is a general term for a class of substances which can accelerate the vulcanization speed, reduce the vulcanization temperature, reduce the dosage of the vulcanizing agent and improve the physical and mechanical properties of rubber; which is one of the essential basic materials of the rubber industry today. The vulcanization performance of the rubber is an important index for measuring the quality of the rubber vulcanization accelerator and is also an index which is most concerned by users and is most easy to detect; the rubber vulcanization accelerator is added into the rubber material to activate the vulcanizing agent, so that the crosslinking reaction of the vulcanizing agent and rubber molecules is accelerated, the vulcanization time is shortened, the vulcanization temperature is reduced, the vulcanizing agent consumption is reduced, and the mechanical property of the rubber can be improved. When the rubber vulcanization accelerator with poor vulcanization performance is added into the rubber material, the vulcanization time can be prolonged, the vulcanization temperature can be increased, and finally the overall quality of vulcanized rubber is lowered.
The zinc diethyldithiocarbamate is a vulcanization accelerator commonly used in the rubber industry, and has a remarkable influence on the vulcanization performance of rubber, so that the preparation of the zinc diethyldithiocarbamate with excellent vulcanization performance has important significance. The zinc diethyldithiocarbamate produced in the market at present has poor vulcanization performance when being added into rubber materials, longer vulcanization time and high vulcanization temperature, so that the research of the special rubber accelerator with excellent vulcanization performance is significant.
At present, the vulcanized rubber vulcanization performance is mainly investigated from the aspects of raw rubber, a reinforcing agent, sulfur, an accelerator composition and the like in the literature, and the influence of a single accelerator and a preparation method on the vulcanized rubber vulcanization performance is not reported, which is also the key point of the invention.
Patent CN108558722A provides a preparation method of zinc diethyldithiocarbamate, which mainly comprises the following steps: 1. putting a certain amount of water into a clean reactor, turning on stirring and cooling the water, putting a certain amount of zinc oxide into the reactor, and stirring for a period of time; 2. adding organic amine into a reactor, continuing stirring for half an hour after the addition is finished, dropwise adding into the reactor, and controlling the reaction temperature to be below 40 ℃; 3. after the reaction is finished, stirring for a period of time, detecting that the pH value is neutral, and stopping stirring; 4. and (4) putting the slurry into a centrifugal machine for dehydration, drying and crushing to obtain the product. However, the zinc diethyldithiocarbamate synthesized by the process of patent CN108558722a has poor vulcanization performance when added into rubber, and the mechanical properties of the final vulcanized rubber cannot meet the requirements.
Patent CN101121683A discloses a preparation method of zinc diethyldithiocarbamate, which comprises the following steps: adding a specified amount of dibutylamine and sodium hydroxide into a reaction kettle filled with purified water at one time under a stirring state; controlling the temperature to be 10-35 ℃, beginning to dropwise add a specified amount of carbon disulfide liquid, controlling the time to be 7 hours, and stirring for a certain time after condensation is finished; controlling a proper temperature, dropwise adding a zinc chloride solution, and carrying out double decomposition reaction; after the reaction is finished, regulating the pH value of the reaction solution to be in a proper range by using sulfuric acid, namely finishing the reaction; then stirring for 1 hour for solid-liquid separation, drying the solid and crushing to obtain the product. However, the production process of patent CN101121683A has the disadvantages that the production process generates byproduct sodium chloride salt-containing wastewater, the treatment difficulty is high, the final water reuse cannot be realized, and the product contains sodium chloride, and needs to be washed with a large amount of water, and the product is also easily polluted by chlorine.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of a rubber vulcanization accelerator.
The invention discloses a preparation method of a rubber vulcanization accelerator, which comprises the following steps:
adding diethylamine into the ethanol solution, mixing, and dropwise adding a first part of sodium hydroxide solution while stirring to form a first mixed solution;
dropwise adding a first part of carbon disulfide into the first mixed solution, and stirring to obtain a second mixed solution;
dropwise adding the remaining second part of sodium hydroxide solution into the second mixed solution, and stirring to obtain a third mixed solution;
dropwise adding the remaining second part of carbon disulfide into the third mixed solution, and stirring to obtain a fourth mixed solution;
adding a catalyst 2-ethylhexanoic acid into the fourth mixed solution, then adding zinc carbonate in batches, carrying out solid-liquid separation after reaction, and carrying out aftertreatment on the solid to obtain the rubber vulcanization accelerator.
As a further improvement of the invention, the mass fraction of the ethanol solution is 30-35%.
As a further improvement of the invention, the mass fraction of the sodium hydroxide solution is 20-25%, the first part of the sodium hydroxide solution which is dripped is 55-65% of the total amount of the sodium hydroxide solution, and the second part of the sodium hydroxide solution which is dripped is 35-45% of the total amount of the sodium hydroxide solution;
the dropping temperature of the first part of the sodium hydroxide is not more than 35 ℃;
the stirring time for dripping the second part of sodium hydroxide solution is 0.5 to 1 hour.
As a further improvement of the invention, the dripped first part of carbon disulfide accounts for 35-45% of the total amount of carbon disulfide, and the dripped second part of carbon disulfide accounts for 55-65% of the total amount of carbon disulfide;
stirring the first part of carbon disulfide for 0.5 to 1 hour at the temperature of not more than 35 ℃ in the dropping process and after the dropping is finished or after the dropping is finished;
the dripping time of the second part of carbon disulfide is 0.5-1 h, the dripping temperature is not more than 40 ℃, and the heat preservation reaction is carried out for 0.5-1.5 h after the dripping is finished.
As a further improvement of the invention, the zinc carbonate is added in batches, solid-liquid separation is carried out after the reaction, and the solid is taken for post-treatment to obtain the rubber vulcanization accelerator; the method comprises the following steps:
evenly dividing 3 times, adding zinc carbonate at intervals of 0.5-1 h, wherein the adding temperature is not more than 50 ℃;
heating to 75-80 ℃, stirring and preserving heat for 2.5-3.5 h, and reacting;
after the reaction, solid-liquid separation is carried out, the liquid is discarded, and the solid is dried, crushed and sieved to obtain a white powder finished product.
As a further improvement of the invention, the mass ratio of the ethanol solution, the diethylamine, the sodium hydroxide solution, the carbon disulfide, the catalyst and the zinc carbonate is (100-110) to 36.6 (100-110) to (30-40) to (3-3.5) to 34.
Compared with the prior art, the invention has the beneficial effects that:
the zinc diethyl dithiocarbamate prepared by the invention has higher activity, and the zinc diethyl dithiocarbamate is added into a rubber material to ensure that the activation effect of a vulcanizing agent is obvious, the vulcanizing time can be shortened, the vulcanizing temperature can be reduced, the consumption of the vulcanizing agent can be reduced, the mechanical property of rubber can be improved, and the quality of vulcanized rubber can be obviously improved;
the preparation method can avoid the generation of sodium chloride wastewater, is green and environment-friendly, adopts zinc carbonate without chloride radicals, does not need distilled water to wash products, greatly reduces the generation amount of production wastewater, obviously reduces the production cost, shortens the reaction time, and obtains higher product yield.
Drawings
FIG. 1 is a flow chart of a method for preparing a rubber vulcanization accelerator according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The invention is described in further detail below with reference to the attached drawing figures:
as shown in FIG. 1, the present invention provides a method for preparing a rubber vulcanization accelerator, comprising:
s1, adding diethylamine into the ethanol solution, mixing, and dropwise adding a first part of sodium hydroxide solution while stirring to form a first mixed solution; wherein the content of the first and second substances,
the mass fraction of the ethanol solution is 30-35 percent;
the mass fraction of the sodium hydroxide solution is 20-25 percent;
the dropwise addition temperature of the first part of sodium hydroxide solution is not more than 35 ℃, and is 55-65% of the total amount of the sodium hydroxide solution;
the specific implementation method comprises the following steps:
adding a certain amount of ethanol solution into a four-neck flask, then adding weighed diethylamine, and then dropwise adding 55-65% of first part of sodium hydroxide solution, preferably 60% of first part of sodium hydroxide solution while stirring to form a first mixed solution;
s2, dropwise adding a first part of carbon disulfide into the first mixed solution, and stirring to obtain a second mixed solution; wherein the content of the first and second substances,
the first part of carbon disulfide accounts for 35 to 45 percent of the total amount of carbon disulfide, and is preferably 40 percent; stirring the first part of carbon disulfide for 0.5 to 1 hour at the temperature of not more than 35 ℃ in the dropping process and after the dropping is finished or after the dropping is finished;
s3, dropwise adding the remaining second part of sodium hydroxide solution into the second mixed solution, and stirring to obtain a third mixed solution; wherein the content of the first and second substances,
the second part of the sodium hydroxide solution accounts for 35 to 45 percent of the total amount of the sodium hydroxide solution, and is preferably 40 percent; the stirring time for dripping the second part of sodium hydroxide solution is 0.5 h-1 h, preferably 0.5 h; stirring for 0.5h to obtain a third mixed solution as a turbid solution.
S4, dropwise adding the remaining second part of carbon disulfide into the third mixed solution, and stirring to obtain a fourth mixed solution; wherein the content of the first and second substances,
the second part of carbon disulfide accounts for 55 to 65 percent of the total amount of carbon disulfide, and is preferably 60 percent; the dripping time of the second part of carbon disulfide is 0.5-1 h, the dripping temperature is not more than 40 ℃, and after the dripping is finished, the reaction is carried out for 0.5-1.5 h by heat preservation, and preferably for 0.5h by heat preservation.
S5, adding a catalyst 2-ethylhexanoic acid into the fourth mixed solution, then adding zinc carbonate in batches, carrying out solid-liquid separation after reaction, and carrying out aftertreatment on the solid to obtain a rubber vulcanization accelerator; wherein the content of the first and second substances,
the specific implementation method comprises the following steps:
equally dividing 3 times, adding zinc carbonate at intervals of 0.5-1 h, preferably at intervals of 0.5 h; the adding temperature is not more than 50 ℃; then, heating to 75-80 ℃, stirring and preserving heat for 2.5-3.5 h, and reacting; after the reaction, solid-liquid separation is carried out, the liquid is discarded, and the solid is dried, crushed and sieved to obtain a white powder finished product.
Furthermore, in the preparation method, the mass ratio of the ethanol solution, the diethylamine, the sodium hydroxide solution, the carbon disulfide, the catalyst and the zinc carbonate is (100-110) to (36.6), (100-110) to (30-40) to (3-3.5) to (34); preferably, the mass ratio of the ethanol solution, the diethylamine, the sodium hydroxide solution, the carbon disulfide, the catalyst and the zinc carbonate is (100-110): 36.6:100:40, (3-3.5): 34.
The invention has the advantages that:
the zinc diethyl dithiocarbamate prepared by the invention has higher activity, and the zinc diethyl dithiocarbamate is added into a rubber material to ensure that the activation effect of a vulcanizing agent is obvious, the vulcanizing time can be shortened, the vulcanizing temperature can be reduced, the consumption of the vulcanizing agent can be reduced, the mechanical property of rubber can be improved, and the quality of vulcanized rubber can be obviously improved; the preparation method can avoid the generation of sodium chloride wastewater, is green and environment-friendly, adopts zinc carbonate without chloride radicals, does not need distilled water to wash products, greatly reduces the generation amount of production wastewater, obviously reduces the production cost, shortens the reaction time, and obtains higher product yield.
Example 1:
the invention provides a preparation method of a rubber vulcanization accelerator, which comprises the following steps:
adding 100-110 g of ethanol solution (mass fraction is 30-35%) into a four-neck flask, adding 36.6g of diethylamine, dropwise adding about 60g of sodium hydroxide solution (mass fraction is 20-25%) while stirring, wherein the dropwise adding temperature is not more than 35 ℃, adding about 16g of carbon disulfide dropwise into the flask, stirring for 0.5-1 h at the temperature of not more than 35 ℃, adding about 40g of the remaining sodium hydroxide solution into the flask, stirring for 0.5h to obtain turbid liquid, then adding about 24g of the remaining carbon disulfide dropwise into the flask, adding for 0.5-1 h, keeping the temperature for reaction for 1h after dropwise adding is finished, adding 3-3.5 g of catalyst 2-ethylhexanoic acid, then adding 34.0g of zinc carbonate into the flask at 3-time intervals of 0.5h, heating to 75-80 ℃, keeping the temperature for reaction for 3h, solid-liquid separation is carried out, liquid is abandoned, and the white powder finished product is obtained after drying, crushing and sieving the solid, which is marked as the improvement accelerant 1.
Example 2:
the manner of adding the sodium hydroxide solution and carbon disulfide in example 1 was changed to finish the one-time dropwise addition, and the rest of the process remained the same as that in example 1, to obtain a white powder product, which is marked as improved accelerator 2.
Example 3:
the catalyst 2-ethylhexanoic acid from example 1 was removed and the remainder remained the same as in example 1 to produce a white powder product designated as modified promoter 3.
Example 4:
the zinc carbonate solids of example 1 were added to the flask in 3 average portions at 0.5h intervals instead of being added in one portion, the remainder remaining the same as in example 1, to produce a white powder finish designated as modified accelerator 4.
And (3) verification:
zinc diethyldithiocarbamate synthesized according to the methods described in patent CN108558722A and patent CN101121683a is referred to as ordinary accelerator 1 and ordinary accelerator 2, respectively; the zinc diethyldithiocarbamate (improved accelerator 1-4) modified by the method of the invention in the embodiment 1-4 is vulcanized into the common vulcanized rubber 1, the common vulcanized rubber 2, the improved vulcanized rubber 1, the improved vulcanized rubber 2, the improved vulcanized rubber 3 and the improved vulcanized rubber 4 respectively according to the same formula and conditions. The vulcanization performance was measured according to "determination of vulcanization characteristics by rotor-less vulcanizer for rubber" GB/T16584-1996. The results are shown in the following table:
from the above table it is evident that it is best to improve the cure properties of vulcanizate 1, and also that the process conditions of example 1 are optimal.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. A method for preparing a rubber vulcanization accelerator is characterized by comprising the following steps:
adding diethylamine into the ethanol solution, mixing, and dropwise adding a first part of sodium hydroxide solution while stirring to form a first mixed solution;
dropwise adding a first part of carbon disulfide into the first mixed solution, and stirring to obtain a second mixed solution;
dropwise adding the remaining second part of sodium hydroxide solution into the second mixed solution, and stirring to obtain a third mixed solution; wherein the dropwise added first part of sodium hydroxide solution accounts for 55-65% of the total amount of the sodium hydroxide solution, and the dropwise added second part of sodium hydroxide solution accounts for 35-45% of the total amount of the sodium hydroxide solution;
dropwise adding the remaining second part of carbon disulfide into the third mixed solution, and stirring to obtain a fourth mixed solution; wherein the dropwise added first part of carbon disulfide accounts for 35-45% of the total amount of carbon disulfide, and the dropwise added second part of carbon disulfide accounts for 55-65% of the total amount of carbon disulfide;
adding a catalyst 2-ethylhexanoic acid into the fourth mixed solution, then uniformly dividing for 3 times at intervals of 0.5-1 h, and adding zinc carbonate, wherein the adding temperature is not more than 50 ℃; then heating to 75-80 ℃, stirring and preserving heat for 2.5-3.5 h, and reacting; after the reaction, solid-liquid separation is carried out, the liquid is discarded, and the solid is dried, crushed and sieved to obtain a white powder finished product.
2. The method according to claim 1, wherein the ethanol solution is present in an amount of 30 to 35% by mass.
3. The preparation method according to claim 1, wherein the mass fraction of the sodium hydroxide solution is 20% to 25%;
the dropping temperature of the first part of the sodium hydroxide is not more than 35 ℃;
the stirring time for dripping the second part of sodium hydroxide solution is 0.5 to 1 hour.
4. The method according to claim 1, wherein the reaction mixture,
stirring the first part of carbon disulfide for 0.5 to 1 hour at the temperature of not more than 35 ℃ in the dropping process and after the dropping is finished or after the dropping is finished;
the dripping time of the second part of carbon disulfide is 0.5-1 h, the dripping temperature is not more than 40 ℃, and the heat preservation reaction is carried out for 0.5-1.5 h after the dripping is finished.
5. The preparation method according to any one of claims 1 to 4, wherein the mass ratio of the ethanol solution, the diethylamine, the sodium hydroxide solution, the carbon disulfide, the catalyst and the zinc carbonate is (100-110): 36.6, (100-110): 30-40): 3-3.5): 34.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101121683A (en) * | 2007-09-19 | 2008-02-13 | 濮阳蔚林化工股份有限公司 | Method for producing rubber vulcanization accelerant zinc dibutyl dithiocaarbamate |
| CN101121684A (en) * | 2007-09-19 | 2008-02-13 | 濮阳蔚林化工股份有限公司 | Method for producing rubber vulcanization accelerant zinc dibutyl dithiocarbamate |
| CN106588727B (en) * | 2016-12-12 | 2018-09-11 | 江苏连连化学股份有限公司 | The method that one-step method prepares thiofide N- ethyl, N-phenyl zinc dithiocarbamates |
| CN108558722A (en) * | 2018-04-12 | 2018-09-21 | 宜兴市鸿远精细化工有限公司 | A kind of production technology of zinc salt of dithiocarbamate class rubber accelerator |
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