CN110734547B - Method for preparing organic silicon resin through stepwise hydrolysis - Google Patents
Method for preparing organic silicon resin through stepwise hydrolysis Download PDFInfo
- Publication number
- CN110734547B CN110734547B CN201911022002.XA CN201911022002A CN110734547B CN 110734547 B CN110734547 B CN 110734547B CN 201911022002 A CN201911022002 A CN 201911022002A CN 110734547 B CN110734547 B CN 110734547B
- Authority
- CN
- China
- Prior art keywords
- hydrolysis
- organic silicon
- tower
- monomer
- silicon resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
Abstract
The invention belongs to the field of resin synthesis, and particularly relates to a method for preparing organic silicon resin by stepwise hydrolysis, which comprises the steps of adding organic silicon monomers and an organic solvent into a first hydrolysis tower in proportion, allowing the mixture to enter a second hydrolysis tower after primary hydrolysis, allowing the mixture to enter a third hydrolysis tower for full hydrolysis, performing water washing and water washing separation after hydrolysis is completed, adding a catalyst for polymerization and polycondensation, adding a regulator to reduce the degree of gelation, and regulating the mass fraction of a silicon resin solution to 50% to obtain the organic silicon resin. The method adopts a step-by-step hydrolysis method to prepare the organic silicon resin, the hydrolysis reaction is carried out step by step, the reaction does not release heat, the temperature of the hydrolysis reaction is easy to control, no external refrigerant is needed for cooling, the cost is saved, the hydrolysis reaction is relatively thorough, and the yield is improved. The hydrolyzed absorption product hydrochloric acid has wide application and creates certain economic benefit.
Description
Technical Field
The invention belongs to the field of resin synthesis, and particularly relates to a method for preparing organic silicon resin through stepwise hydrolysis.
Background
The organic silicon resin is an important member in the organic silicon material, is different from the linear structure of the organic silicon rubber and the small molecular weight of the silicon oil and the silane, is a three-dimensional net structure, and has the basic properties of the organic silicon material, such as high temperature resistance, low temperature resistance, high insulation, weather resistance, radiation resistance, chemical resistance, hydrophobicity and the like.
The prior preparation method of the organic silicon resin comprises the following processes: firstly, mixing a metered chlorosilane monomer with an aqueous solution containing an organic solvent, carrying out hydrolysis reaction, and washing and separating after the hydrolysis is finished; then, the organic silicon resin is obtained after telomerization and concentration adjustment.
In the existing process for preparing the organic silicon resin, as the organic silicon material monomer in the raw materials and the solvent are subjected to hydrolysis reaction to generate hydrogen chloride gas, the generated hydrogen chloride is dissolved in water, and the dissolution heat of the hydrogen chloride is large, a large amount of dissolution heat can be released in the process of dissolving the hydrogen chloride in the water. The hydrolysis process for preparing the organic silicon resin needs to be carried out at a lower temperature, so that a refrigerant is required to control the reaction temperature of a reaction kettle in the process of preparing the organic silicon resin, and the reaction cost is greatly increased. In addition, hydrogen chloride generated after hydrolysis is not better recovered, resources are not effectively utilized, equipment is corroded, and environmental pollution is caused.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a method for preparing organic silicon resin by stepwise hydrolysis. In the method, a hydrolysis reaction kettle is changed into three continuous hydrolysis towers in the process of preparing the organic silicon resin, and the specific technological process comprises the following steps:
adding each organic silicon monomer and an organic solvent into a first hydrolysis tower according to a certain proportion, primarily hydrolyzing, then feeding into a second hydrolysis tower, finally feeding into a third hydrolysis tower for full hydrolysis, washing with water after hydrolysis, washing with water for separation, then adding a catalyst for telomerization and polycondensation, adding a regulator to reduce the degree of gelation, and regulating the mass fraction of the silicon resin solution to 50% to obtain the organic silicon resin.
The hydrogen chloride gas generated by the first hydrolysis tower enters the hydrochloric acid absorption tower through a pipeline, the distilled water is added to recover hydrochloric acid with the mass fraction of about 20%, and the waste water generated by the hydrolysis of the second hydrolysis tower and the third hydrolysis tower and tail gas discharged by the hydrochloric acid absorption tower form dilute hydrochloric acid for the hydrolysis reaction of the first hydrolysis tower. And neutralizing and discharging the absorbed tail gas.
In the process of adding the first batch of raw materials into the first hydrolysis tower for hydrolysis reaction, 8-10% of dilute hydrochloric acid needs to be added to promote the hydrolysis reaction, and after one-time circulation, the first hydrolysis tower is hydrolyzed by adopting recovered dilute hydrochloric acid.
The raw materials for synthesizing the organic silicon resin are as follows:
basic silicone material monomer: monomethyltrichlorosilane (M1), dimethyldichlorosilane (M2), monophenyltrichlorosilane (P1), diphenyldichlorosilane (P2);
wherein, the purity of the methyl trichlorosilane is more than 99 percent; dimethyldichlorosilane with purity of more than 99.9%;
mono-phenyl trichlorosilane, purity > 99%; the purity of the diphenyl dichlorosilane is more than 99 percent;
special organosilicon monomer:
can be as follows: organosilicon monomer containing double bond group (methyl vinyl dichlorosilane), organosilicon monomer containing active hydrogen (methyl hydrogen dichlorosilane) and silane coupling agent (such as epoxy-containing triethoxysilane, ester-containing triethoxysilane, and amino-containing and acryloyl-containing triethoxysilane).
In the total organic silicon monomer, the ratio of the number of organic groups R on silicon atoms to the number of silicon atoms, R/Si is 1.0-1.6, the number of phenyl groups accounts for 20-60% of the total number of R, and the mass of the special organic silicon monomer accounts for 10-40% of the total mass of the organic silicon monomer; the mass of the organic solvent is 0.8-1.2 times of that of the monomer; the organic solvent is: ketone, ether or lipid solvents, in particular: cyclohexanone, butanone, ethyl acetate or butyl ethyl ether; the water consumption for hydrolysis is 1-2 times of the total mass of the monomers.
Wherein the added catalyst is a transition metal salt catalyst, specifically platinum chloride, cobalt naphthenate, lead acetate or zinc acetate, and the dosage of the catalyst is 1-2 per mill of the total mass of the organosilicon monomer.
The added regulator is organosilicon oligomer with hydroxyl, epoxy or ester group, and the dosage of the organosilicon oligomer is 20-30% of the total mass of the organosilicon monomer.
Has the advantages that:
(1) the method adopts a step-by-step hydrolysis method to prepare the organic silicon resin, the hydrolysis reaction is carried out step by step, the reaction does not release heat, the temperature of the hydrolysis reaction is easy to control, no external refrigerant is needed for cooling, the cost is saved, the hydrolysis reaction is relatively thorough, the yield is improved, and the performance of the prepared organic silicon resin is not influenced.
(2) The hydrolyzed absorption product hydrochloric acid has wide application and creates certain economic benefit.
Drawings
FIG. 1 is a flow chart of the hydrolysis internal circulation process of the present invention.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
The raw materials for synthesizing the organic silicon resin comprise the following components in percentage by mass:
120 parts of methyltrichlorosilane (M1);
80 parts of dimethyldichlorosilane (M2);
80 parts of phenyltrichlorosilane (P1);
120 parts of diphenyldichlorosilane (P2);
120 parts of ester-containing organosilicon coupling agent.
The preparation method comprises the steps of fully mixing the organic silicon monomers according to a certain proportion, adding the mixture into 600 parts of benzene, adding 1200 parts of butanone and 600 parts of water (dilute hydrochloric acid with the mass concentration of 8%), adding the mixture into a first hydrolysis tower, performing primary hydrolysis, then entering a second hydrolysis tower, finally entering a third hydrolysis tower for full hydrolysis, completing hydrolysis after 5 hours, performing water washing and water washing separation after the hydrolysis is completed, then adding 1 part of lead naphthenate catalyst, adding 140 parts of epoxy group organic silicon low molecules serving as a regulator, reducing the gel degree, then adding toluene, and adjusting the solid content to be 50% solution to obtain the organic silicon resin.
The silicone resin yield was 63%.
Example 2
The raw materials for synthesizing the organic silicon resin comprise the following components in percentage by mass:
110 parts of methyltrichlorosilane (M1);
60 parts of dimethyldichlorosilane (M2);
60 parts of phenyltrichlorosilane (P1);
110 parts of diphenyldichlorosilane (P2);
220 parts of methylvinyldichlorosilane.
Fully mixing the organic silicon monomers according to a certain proportion, adding the mixture into 800 parts of benzene, adding 1800 parts of butyl ether and 600 parts of water (dilute hydrochloric acid with the mass concentration of 9%), adding the mixture into a first hydrolysis tower, initially hydrolyzing, then entering a second hydrolysis tower, finally entering a third hydrolysis tower for full hydrolysis, completing hydrolysis after 4 hours, washing with water after the hydrolysis is completed, separating by washing with water, then adding 0.8 part of platinum chloride catalyst, adding 180 parts of regulator hydroxyl organic silicon low molecules, reducing the gel degree, then adding toluene, and regulating the solid content to be 50% solution, thus obtaining the organic silicon resin.
The silicone resin yield was 61%.
Example 3
The raw materials for synthesizing the organic silicon resin comprise the following components in percentage by mass:
120 parts of methyltrichlorosilane (M1);
60 parts of dimethyldichlorosilane (M2);
60 parts of phenyltrichlorosilane (P1);
110 parts of diphenyldichlorosilane (P2);
140 parts of epoxy-containing organosilicon coupling agent.
Fully mixing the organic silicon monomers according to a certain proportion, adding the mixture into 500 parts of benzene, adding 1800 parts of butanone and 600 parts of water (dilute hydrochloric acid with the mass concentration of 10%), adding the mixture into a first hydrolysis tower, performing primary hydrolysis, then entering a second hydrolysis tower, finally entering a third hydrolysis tower for full hydrolysis, completing hydrolysis after 4 hours, performing water washing and water washing separation after the hydrolysis is completed, then adding 1 part of zinc acetate catalyst, adding 140 parts of regulator hydroxyl organic silicon low molecules, reducing the gel degree, then adding toluene, and regulating the solid content to be 50% solution, thus obtaining the organic silicon resin.
The silicone resin yield was 62%.
Comparative example 1
The raw materials for synthesizing the organic silicon resin comprise the following components in percentage by mass:
120 parts of methyltrichlorosilane (M1);
80 parts of dimethyldichlorosilane (M2);
80 parts of phenyltrichlorosilane (P1);
120 parts of diphenyldichlorosilane (P2);
120 parts of ester-containing organosilicon coupling agent.
Fully mixing the organic silicon monomers according to a certain proportion, adding the mixture into 600 parts of benzene, adding 1200 parts of butanone and 600 parts of water into a reaction kettle, controlling the hydrolysis temperature at 5 ℃, completing hydrolysis within 5 hours, performing water washing and water washing separation after the hydrolysis is completed, then adding 1 part of lead naphthenate catalyst, adding 140 parts of epoxy group organic silicon low molecule serving as an adjusting agent, reducing the degree of gelation, then adding toluene, and adjusting the solid content to be 50% solution to obtain the organic silicon resin.
The silicone resin yield was 59%.
The properties of the silicone resins prepared in the examples of the invention and comparative examples are shown in table 1:
TABLE 1
Claims (3)
1. A method for preparing organic silicon resin by stepwise hydrolysis is characterized in that the method comprises the following steps: adding each organic silicon monomer and an organic solvent into a first hydrolysis tower according to a certain proportion, entering a second hydrolysis tower after primary hydrolysis, finally entering a third hydrolysis tower for full hydrolysis, washing with water after the hydrolysis is finished, separating by washing with water, then adding a catalyst for telomerization and polycondensation, adding a regulator to reduce the degree of gelation, and regulating the mass fraction of a silicon resin solution to 50% to obtain the organic silicon resin;
hydrogen chloride gas generated by the first hydrolysis tower enters a hydrochloric acid absorption tower through a pipeline, distilled water is added to recover hydrochloric acid with the mass fraction of 20%, waste water generated by hydrolysis of the second hydrolysis tower and the third hydrolysis tower and tail gas discharged by the hydrochloric acid absorption tower form dilute hydrochloric acid for hydrolysis reaction of the first hydrolysis tower, and the absorbed tail gas is neutralized and discharged;
in the process of adding a first batch of raw materials into a first hydrolysis tower for hydrolysis reaction, 8-10% of dilute hydrochloric acid needs to be added to promote the hydrolysis reaction, and the first hydrolysis tower is hydrolyzed by adopting recovered dilute hydrochloric acid after one-time circulation;
the organosilicon monomer comprises a basic organosilicon monomer and a special organosilicon monomer; wherein the basic silicone monomers are: methyl trichlorosilane, dimethyl dichlorosilane, phenyl trichlorosilane, diphenyl dichlorosilane; the special organic silicon monomer is as follows: epoxy-containing triethoxysilane or ester-containing triethoxysilane;
in the total organic silicon monomer, the ratio of the number of organic groups R on silicon atoms to the number of silicon atoms, R/Si is 1.0-1.6, the number of phenyl groups accounts for 15-60% of the total number of R, and the mass of the special organic silicon monomer accounts for 10-40% of the total mass of the organic silicon monomer; the mass of the organic solvent is 0.8-1.2 times of that of the monomer; the water consumption for hydrolysis is 1-2 times of the total mass of the monomers.
2. The method for preparing silicone resin by stepwise hydrolysis according to claim 1, wherein the catalyst is platinum chloride, cobalt naphthenate, lead acetate or zinc acetate in an amount of 1 to 2% by weight based on the total weight of the silicone monomer.
3. The method for preparing silicone resin by stepwise hydrolysis according to claim 1, wherein the modifier is silicone oligomer having hydroxyl, epoxy or ester groups and is used in an amount of 20% to 30% by weight based on the total weight of the silicone monomer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911022002.XA CN110734547B (en) | 2019-10-25 | 2019-10-25 | Method for preparing organic silicon resin through stepwise hydrolysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911022002.XA CN110734547B (en) | 2019-10-25 | 2019-10-25 | Method for preparing organic silicon resin through stepwise hydrolysis |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110734547A CN110734547A (en) | 2020-01-31 |
| CN110734547B true CN110734547B (en) | 2022-04-08 |
Family
ID=69271408
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911022002.XA Active CN110734547B (en) | 2019-10-25 | 2019-10-25 | Method for preparing organic silicon resin through stepwise hydrolysis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110734547B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112979952B (en) * | 2021-03-11 | 2023-03-14 | 江西蓝星星火有机硅有限公司 | High-hydrogen-content silicone oil production system with low waste acid discharge and preparation method |
| CN113683941A (en) * | 2021-09-18 | 2021-11-23 | 航佳彩新材料(广东)有限公司 | Open fire-resistant high-temperature powder coating special for fireplace and preparation method thereof |
| CN114133566B (en) * | 2021-12-09 | 2023-02-03 | 常州市嘉诺有机硅有限公司 | Method for preparing organic silicon resin by adopting ethoxy silane |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5169970A (en) * | 1988-06-27 | 1992-12-08 | Toshiba Silicone Co., Ltd. | Method for hydrolyzing organochlorosilanes |
| CN101165130A (en) * | 2007-09-20 | 2008-04-23 | 胡孟进 | Preparation technique of organic silicon resin for high temperature resisting powder paint |
| CN101875726A (en) * | 2009-04-30 | 2010-11-03 | 中国石油天然气股份有限公司 | Method for preparing polysiloxane by hydrolyzing dimethyl dichlorosilane |
| CN103881031A (en) * | 2014-02-20 | 2014-06-25 | 常州市嘉诺有机硅有限公司 | Special organic silicon resin for photocureable coating and preparation process of organic silicon resin |
| CN105732986A (en) * | 2016-01-27 | 2016-07-06 | 江西品汉新材料有限公司 | Technology for preparing methyl hydrogen silicone oil |
-
2019
- 2019-10-25 CN CN201911022002.XA patent/CN110734547B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5169970A (en) * | 1988-06-27 | 1992-12-08 | Toshiba Silicone Co., Ltd. | Method for hydrolyzing organochlorosilanes |
| CN101165130A (en) * | 2007-09-20 | 2008-04-23 | 胡孟进 | Preparation technique of organic silicon resin for high temperature resisting powder paint |
| CN101875726A (en) * | 2009-04-30 | 2010-11-03 | 中国石油天然气股份有限公司 | Method for preparing polysiloxane by hydrolyzing dimethyl dichlorosilane |
| CN103881031A (en) * | 2014-02-20 | 2014-06-25 | 常州市嘉诺有机硅有限公司 | Special organic silicon resin for photocureable coating and preparation process of organic silicon resin |
| CN105732986A (en) * | 2016-01-27 | 2016-07-06 | 江西品汉新材料有限公司 | Technology for preparing methyl hydrogen silicone oil |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110734547A (en) | 2020-01-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110734547B (en) | Method for preparing organic silicon resin through stepwise hydrolysis | |
| CN105254661A (en) | Cage-shaped oligomerization polyhedral silsesquioxane with eight phenolic hydroxyl groups and preparation method thereof | |
| CN102061142B (en) | Process for preparing organic silicon pressure-sensitive adhesive | |
| CN101985513A (en) | POSS/epoxy nanometer hybrid material and preparation method and application thereof | |
| CN105254828B (en) | The preparation method of eight phenolic hydroxyl group polyhedral oligomeric silsesquioxane hybrid phenol-formaldehyde resins | |
| CN102643304A (en) | Preparation method of cage poly (phenylsilsequioxane) | |
| CN103450797A (en) | Room-temperature cured epoxy polysiloxane resin | |
| CN1865313A (en) | Preparation method of amino silane modified urethane acrylate resin | |
| CN102167831A (en) | Functional trapezoid polysilsequioxane and preparation method thereof | |
| CN106543391A (en) | A kind of preparation method of double modified borosilicate phenolic resin | |
| CN101857789A (en) | Epoxy silsesquioxane/epoxy resin hybridized glue for packaging photoelectric devices and preparation method thereof | |
| KR20140024244A (en) | Hydrosilicone resin and preparation process thereof | |
| CN111205462B (en) | Preparation method of silicone resin containing perfluor cyclobutyl aryl ether structure | |
| CN108659226B (en) | Preparation method and application of n-butyl terminated poly-bis-phenyl methyl silazane | |
| CN104927058B (en) | A kind of hydroxyl polysiloxane blocking modification method | |
| CN106433146A (en) | Room-temperature vulcanization heat-resistant silicon rubber with active hydrogen based cage structure and preparation method thereof | |
| CN114456128A (en) | Application of novel isovanillin epoxy resin monomer in preparation of silicon-containing polymer | |
| CN104086587A (en) | Preparation method for cage-type dec(glycidyl silsesquioxane) | |
| CN112876685B (en) | Tetraepoxy group liquid cage type silsesquioxane as well as preparation method and application thereof | |
| CN103881100B (en) | Toughness reinforcing organic silicon high-temperature adhering resin and preparation technology thereof | |
| CN110804184A (en) | Method for preparing organic silicon resin by adopting hydrolysis internal circulation process | |
| CN104962230A (en) | Modified vinyl polysiloxane adhesive and preparation method thereof | |
| CN103804691B (en) | The preparation method of toughness reinforcing high-temperature-resistant silicon resin | |
| CN110818905B (en) | Decolorizing and deionizing method of organic silicon resin | |
| CN110760068A (en) | Modified MQ resin, synthesis method and application in pressure-sensitive adhesive |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |