CN112795053A - Method for recycling melamine formaldehyde resin foam waste and flame retardant prepared by method - Google Patents
Method for recycling melamine formaldehyde resin foam waste and flame retardant prepared by method Download PDFInfo
- Publication number
- CN112795053A CN112795053A CN202110134095.6A CN202110134095A CN112795053A CN 112795053 A CN112795053 A CN 112795053A CN 202110134095 A CN202110134095 A CN 202110134095A CN 112795053 A CN112795053 A CN 112795053A
- Authority
- CN
- China
- Prior art keywords
- formaldehyde resin
- melamine formaldehyde
- resin foam
- foam waste
- flame retardant
- 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.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08J2361/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08J2361/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2231—Oxides; Hydroxides of metals of tin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention belongs to the field of resource regeneration, and discloses a method for recycling melamine formaldehyde resin foam waste and a flame retardant prepared by the method. S1, adjusting the pH value of the stannous ion wastewater solution to 7-8 by using alkali; s2, putting the melamine formaldehyde resin foam waste into the solution obtained in the S1, and keeping the solution for 5-200 min; s3, taking out the melamine formaldehyde resin foam waste in the S2, and keeping the temperature of 280-320 ℃ for 30-180 min; s4, grinding the product of the S3 into particles, and using the particles as a flame retardant for standby. The method uses the melamine formaldehyde resin foam waste for treating the tin-containing wastewater, the removal rate is more than 99.99 percent, and the concentration content of tin in the final wastewater is less than the discharge requirement in GB30770-2014 discharge Standard of tin, antimony and mercury industrial pollutants; meanwhile, the foam after tin adsorption has good flame retardant performance after simple heat treatment and grinding, and is a novel composite flame retardant.
Description
Technical Field
The invention belongs to the field of resource regeneration, and particularly relates to a method for recycling melamine formaldehyde resin foam waste and a flame retardant prepared by the method.
Background
The melamine formaldehyde resin foam has good flame retardant, sound absorption and heat insulation properties, so that the melamine formaldehyde resin foam is widely applied to production and life of people. However, melamine formaldehyde resin foam is a thermosetting polymer, and like other thermosetting polymer materials, it is difficult to dissolve, melt, and decompose after forming a foam material, and therefore, it is difficult to recycle waste melamine formaldehyde resin foam. The common incineration and landfill method inevitably causes pollution to the environment. Therefore, the method has important significance on recycling the melamine formaldehyde resin foam.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a method for recycling melamine formaldehyde resin foam waste and a flame retardant prepared by the method.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for recycling melamine formaldehyde resin foam waste comprises the following steps:
s1, adjusting the pH value of the stannous ion wastewater solution to 7-8 by using alkali;
s2, putting the melamine formaldehyde resin foam waste into the solution obtained in the S1, and keeping the solution for 5-200 min;
s3, taking out the melamine formaldehyde resin foam waste in the S2, and keeping the temperature of 280-320 ℃ for 30-180 min;
s4, grinding the product of the S3 into particles, and using the particles as a flame retardant for standby.
Preferably, the concentration of the divalent tin ion wastewater solution is 2000-3000 mg/L.
Preferably, the alkali is one or a combination of more than two of sodium carbonate, sodium acetate, ammonia water, sodium hydroxide and potassium hydroxide.
Preferably, in S2, the amount of the stannous ion wastewater solution is such that the melamine formaldehyde resin foam waste can be completely immersed, and preferably the amount of the melamine formaldehyde resin foam waste and the stannous ion wastewater solution is = (0.2-1) g: (100-500) mL.
The flame retardant is prepared by the method for recycling the melamine formaldehyde resin foam waste.
Furthermore, the flame retardant is a composite material of melamine formaldehyde resin and tin dioxide, the melamine formaldehyde resin is dendritic, and tin dioxide particles are distributed on the surface of the dendritic melamine formaldehyde resin.
Has the advantages that: the method uses the melamine formaldehyde resin foam waste for treating the tin-containing wastewater, the removal rate is more than 99.99 percent, and the concentration content of tin in the final wastewater is less than the discharge requirement in GB30770-2014 discharge Standard of tin, antimony and mercury industrial pollutants; meanwhile, the foam after tin adsorption has good flame retardant performance after simple heat treatment and grinding, and is a novel composite flame retardant; in addition, the recycling method provided by the invention has the characteristics of simple steps, cheap and easily-obtained raw materials, mild reaction conditions and the like, is high in yield and low in production cost, and is suitable for large-scale industrial production.
Drawings
FIG. 1: scanning electron micrographs (200 x) of the product obtained in example 1;
FIG. 2: scanning electron micrographs (20000 times) of the product obtained in example 1;
FIG. 3: x-ray powder diffractogram of the product obtained in example 1;
FIG. 4: the product obtained in example 1 and the Limiting Oxygen Index (LOI) and UL94 vertical burning rating chart;
FIG. 5: the heat release rate profile obtained from cone calorimetry tests of the product obtained in example 1 and a comparative sample;
FIG. 6: total heat released curve obtained from cone calorimetry test of the product obtained in example 1 and a comparative sample;
FIG. 7: example 1 total smoke yield profile obtained from cone calorimetry testing of the product and comparative samples.
Detailed Description
The technical solutions of the present invention will be further described in detail and clearly in the following with reference to specific examples, but the scope of the present invention is not limited thereto.
Example 1
A method for recycling melamine formaldehyde resin foam waste comprises the following steps:
s1, measuring a waste water solution of stannous ions with the concentration of 2706 mg/L, and adjusting the pH value of the solution to 7 by using ammonia water;
s2, putting 0.5 g of melamine formaldehyde resin foam waste into 200 mL of the solution obtained in the S1, and keeping the solution at room temperature for 30 min;
s3, taking out the melamine formaldehyde resin foam waste in the S2, and keeping the temperature at 320 ℃ for 60 min;
s4, grinding the product of S3 into micron-sized particles as a product, marked as MF-SnO2。
Product morphology and Structure characterization
FIGS. 1 and 2 are scanning electron micrographs (different magnifications) of the product obtained in example 1. As can be seen from fig. 1 (multiple 200): after grinding, the three-dimensional network structure of the melamine formaldehyde resin foam is destroyed to form a dendritic structure, and the particle size is about 50 microns. As can be seen from fig. 2 (multiples of 20000): the dendritic surface has many small particles.
FIG. 3 is an x-ray powder diffraction pattern of the product obtained in example 1, as can be seen from FIG. 3: diffraction peaks and SnO of the product2The peaks of (JCPDF 29-1484) correspond one-to-one, indicating that the adsorbed tin becomes tin dioxide after heat treatment. Thus, in fig. 2, the small particles on the dendritic surface are tin dioxide.
Adsorption Property
The divalent tin ion wastewater solution was subjected to concentration tests before and after the recycling method of example 1, and the results of conversion of the tin ion removal rate are shown in table 1. As can be seen from Table 1: the removal rate of tin ions is more than 99.99 percent, and the concentration content of tin in the final wastewater is less than the discharge requirement in GB30770-2014 discharge Standard of tin, antimony and mercury industrial pollutants.
Flame retardant properties
According to the formula shown in the table 2, polyvinyl chloride (PVC), a processing aid and a flame retardant are put into an open mill and mixed for 10min at the temperature of 110 ℃; then transferring the mixture to a flat vulcanizing machine, and hot-pressing and forming the mixture under the conditions of 170 ℃ and 20 MPa to respectively prepare samples of PVC, PVC/MF-2.5 and PVC/SnO2-2.5、PVC/MF-SnO2-2.5. In table 2, PVC represents a sample with only processing aid added, no flame retardant added; PVC/MF-2.5 shows that in addition to the processing aid, 2.5wt% of melamine formaldehyde resin foam powder (obtained by calcining melamine formaldehyde resin foam waste at 320 ℃ for 60 min and then grinding, and labeled as MF) is added to PVC; PVC/SnO2-2.5 shows that in addition to the processing aid, 2.5wt% of tin dioxide micropowder is added to the PVC (the tin dioxide micropowder is obtained by adding alkali to a stannous ion wastewater solution which is not adsorbed by melamine formaldehyde resin foam to obtain a precipitate, then calcining the precipitate at 320 ℃ for 60 min, and grinding the precipitate, wherein the mark is SnO2）；PVC/MF-SnO2-2.5 indicates that 2.5% by weight of the product of example 1 is added to the PVC in addition to the processing aid.
(1) Limiting oxygen index LOI test: the resulting prototype (self-supporting material, type IV, sample size 100 mm. times.6.5 mm. times.3 mm) was used to test the limiting oxygen index LOI, see GB/T2406-1993, data in Table 3 and FIG. 4;
(2) and (3) testing the vertical burning grade: referring to GB/T2408-;
(3) cone calorimetry test: the cone calorimetry was measured according to ISO 5660 standard with sample dimensions of 125 mm by 13mm by 3mm and with a heat radiation of 35kW/m2The data are shown in Table 3. Fig. 5, 6 and 7 are graphs of heat release rate, total heat released and total smoke yield, respectively, for cone calorimetry test samples.
As can be seen from the data in table 3: the product obtained in example 1 is comparable to the control (pure PVC, PVC/MF-2.5 and PVC/SnO)22.5) with the highest oxygen index LOI, the UL94 achieving a V0 rating, and the lowest values of the peak heat release rate (pHRR), Total Heat Release (THR), Total Smoke Release (TSR), indicate that the product obtained in example 1 exhibits the best flame and smoke suppression performance relative to the control.
Example 2
A method for recycling melamine formaldehyde resin foam waste comprises the following steps:
s1, weighing a divalent tin ion aqueous solution with the concentration of 2000 mg/L, and adjusting the pH value of the solution to 8 by using sodium hydroxide;
s2, putting 0.2 g of melamine formaldehyde resin foam waste into 100 mL of the solution obtained in the S1, and keeping the solution at room temperature for 200 min;
s3, taking out the melamine formaldehyde resin foam waste in the S2, and keeping the temperature at 300 ℃ for 30 min;
s4, grinding the product of the S3 into micron-sized particles, and using the micron-sized particles as a flame retardant.
Example 3
A method for recycling melamine formaldehyde resin foam waste comprises the following steps:
s1, weighing a stannous ion aqueous solution with the concentration of 3000 mg/L, and adjusting the pH value of the solution to 7.5 by using potassium hydroxide;
s2, 1 g of melamine formaldehyde resin foam waste is put into 500 mL of the solution obtained in the S1, and the solution is kept for 5 min at room temperature;
s3, taking out the melamine formaldehyde resin foam waste in the S2, and keeping the temperature at 280 ℃ for 180 min;
s4, grinding the product of the S3 into micron-sized particles, and using the micron-sized particles as a flame retardant.
Example 4
A method for recycling melamine formaldehyde resin foam waste comprises the following steps:
s1, weighing a stannous ion aqueous solution with the concentration of 2500 mg/L, and adjusting the pH value of the solution to 7 by using ammonia water;
s2, putting 0.6 g of melamine formaldehyde resin foam waste into 400 mL of solution obtained in S1, and keeping the solution at room temperature for 60 min;
s3, taking out the melamine formaldehyde resin foam waste in the S2, and keeping the temperature at 310 ℃ for 80 min;
s4, grinding the product of the S3 into micron-sized particles, and using the micron-sized particles as a flame retardant.
Claims (7)
1. A method for recycling melamine formaldehyde resin foam waste is characterized by comprising the following steps:
s1, adjusting the pH value of the stannous ion wastewater solution to 7-8 by using alkali;
s2, putting the melamine formaldehyde resin foam waste into the solution obtained in the S1, and keeping the solution for 5-200 min;
s3, taking out the melamine formaldehyde resin foam waste in the S2, and keeping the temperature of 280-320 ℃ for 30-180 min;
s4, grinding the product of the S3 into particles, and using the particles as a flame retardant for standby.
2. The method of claim 1, wherein the melamine formaldehyde resin foam waste is recycled by: the concentration of the divalent tin ion wastewater solution is 2000-3000 mg/L.
3. The method of claim 1, wherein the melamine formaldehyde resin foam waste is recycled by: the alkali is one or the combination of more than two of sodium carbonate, sodium acetate, ammonia water, sodium hydroxide and potassium hydroxide.
4. The method of claim 1, wherein the melamine formaldehyde resin foam waste is recycled by: in S2, the divalent tin ion wastewater solution is used in an amount that can completely immerse the melamine formaldehyde resin foam waste.
5. The method of claim 4, wherein the method comprises the steps of: in S2, the melamine formaldehyde resin foam waste and the stannous ion wastewater solution are in a ratio of (0.2-1) g to (100-500) mL.
6. A flame retardant prepared by the method of recycling the melamine formaldehyde resin foam waste as claimed in any one of claims 1 to 5.
7. The flame retardant of claim 6, wherein: the flame retardant is a composite material of melamine formaldehyde resin and tin dioxide, the melamine formaldehyde resin is dendritic, and tin dioxide particles are distributed on the surface of the dendritic melamine formaldehyde resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110134095.6A CN112795053B (en) | 2021-02-01 | 2021-02-01 | Method for recycling melamine formaldehyde resin foam waste and flame retardant prepared by method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110134095.6A CN112795053B (en) | 2021-02-01 | 2021-02-01 | Method for recycling melamine formaldehyde resin foam waste and flame retardant prepared by method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112795053A true CN112795053A (en) | 2021-05-14 |
| CN112795053B CN112795053B (en) | 2022-03-18 |
Family
ID=75813278
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110134095.6A Active CN112795053B (en) | 2021-02-01 | 2021-02-01 | Method for recycling melamine formaldehyde resin foam waste and flame retardant prepared by method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112795053B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022263228A1 (en) | 2021-06-17 | 2022-12-22 | Basf Se | Method for preparing melamine resin foams using grinded melamine foam particles |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5721281A (en) * | 1996-07-01 | 1998-02-24 | Blount; David H. | Flame retardant porous plastics |
| CN1318464A (en) * | 2000-04-15 | 2001-10-24 | 巴斯福股份公司 | Melamine resin foams |
| CN103408789A (en) * | 2013-05-13 | 2013-11-27 | 四川大学 | High-efficiency flame-retardant modified melamino-formaldehyde foams and preparation method thereof |
-
2021
- 2021-02-01 CN CN202110134095.6A patent/CN112795053B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5721281A (en) * | 1996-07-01 | 1998-02-24 | Blount; David H. | Flame retardant porous plastics |
| CN1318464A (en) * | 2000-04-15 | 2001-10-24 | 巴斯福股份公司 | Melamine resin foams |
| CN103408789A (en) * | 2013-05-13 | 2013-11-27 | 四川大学 | High-efficiency flame-retardant modified melamino-formaldehyde foams and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 贺少蕊: ""活性炭球负载SnO2基杂化阻燃剂的制备及其阻燃应用"", 《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅰ辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022263228A1 (en) | 2021-06-17 | 2022-12-22 | Basf Se | Method for preparing melamine resin foams using grinded melamine foam particles |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112795053B (en) | 2022-03-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101544783B (en) | Composite heat stabilizer for hydrophobic nano-hydrotalcite PVC and preparation method thereof | |
| Rocha et al. | Kinetics and mechanistic analysis of caustic magnesia hydration | |
| CN101280142B (en) | Preparation method of environment-friendly aqueous nanometer fireproof flame-retardant coating | |
| Pan et al. | Hierarchical nanoporous silica doped with tin as novel multifunctional hybrid material to flexible poly (vinyl chloride) with greatly improved flame retardancy and mechanical properties | |
| CN112795053B (en) | Method for recycling melamine formaldehyde resin foam waste and flame retardant prepared by method | |
| Wang et al. | Phosphorylated cellulose applied for the exfoliation of LDH: An advanced reinforcement for polyvinyl alcohol | |
| CN109897273B (en) | Composite flame retardant graft-modified EVA (ethylene-vinyl acetate) foam material and preparation method thereof | |
| CN101538019A (en) | Method for preparing hydrophobic nanometer hydrotalcite | |
| CN110256759B (en) | Environment-friendly wear-resistant anti-slip foam composite material for shoes and preparation method thereof | |
| CN104195589A (en) | Preparation method and application of nano barium sulphate | |
| CN110577708A (en) | Modified floating bead/graphene oxide flame-retardant runway particle material | |
| CN111094196A (en) | Method for recycling solar cell module glass | |
| CN1807314A (en) | Preparation method of crystallite foam glass | |
| CN114163713A (en) | High-buffering flame-retardant high-viscosity foam and preparation method thereof | |
| He et al. | Reduction in smoke emitted and fire hazard presented by flexible poly (vinyl chloride) through novel synthesis of SnO2 supported by activated carbon spheres | |
| Kisku et al. | Study of oxygen permeability and flame retardancy properties of biodegradable polymethylmethacrylate/starch composites | |
| CN106587119A (en) | Method for preparing hexagonal flake magnesium hydroxide with dominant growth on (001) crystal face | |
| Qiu et al. | Reutilization of melamine‐formaldehyde foam wastes: Removing Sn2+ in simulated tin‐containing wastewater to transform a fire hazard suppressant of flexible poly (vinyl chloride) | |
| Kong et al. | Low‐temperature synthesis of Mg (OH) 2 nanoparticles from MgO as halogen‐free flame retardant for polypropylene | |
| CN104262875A (en) | Intumescent flame-retardant cable material taking plant-based active carbon as synergist and preparation method thereof | |
| CN111592741B (en) | Melt blending modification method of solar aged fluorine-containing back plate membrane material and product thereof | |
| Jiao et al. | Flame‐retardant properties of magnesium hydroxystannate and strontium hydroxystannate coated calcium carbonate on soft poly (vinyl chloride) | |
| Xu et al. | Application of nanometer antimony trioxide modified by dioctyl phthalate in polyvinyl chloride flame retardant materials | |
| Meng et al. | Biotemplated facile synthesis of three‐dimensional micro/nanoporous tin oxide: improving the flammable and mechanical properties of flexible PVC | |
| TW201609895A (en) | Liquid stabilizer and resin composition containing said liquid stabilizer |
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 |