CN111534042A - Anti-yellowing heat insulation material for wall - Google Patents
Anti-yellowing heat insulation material for wall Download PDFInfo
- Publication number
- CN111534042A CN111534042A CN202010471800.7A CN202010471800A CN111534042A CN 111534042 A CN111534042 A CN 111534042A CN 202010471800 A CN202010471800 A CN 202010471800A CN 111534042 A CN111534042 A CN 111534042A
- Authority
- CN
- China
- Prior art keywords
- phenolic resin
- parts
- yellowing
- insulating material
- modifier
- 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.)
- Pending
Links
- 238000004383 yellowing Methods 0.000 title claims abstract description 24
- 239000012774 insulation material Substances 0.000 title description 10
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000011810 insulating material Substances 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 239000005011 phenolic resin Substances 0.000 claims abstract description 18
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 18
- 239000003607 modifier Substances 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229910000024 caesium carbonate Inorganic materials 0.000 claims abstract description 9
- 239000004793 Polystyrene Substances 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920002223 polystyrene Polymers 0.000 claims abstract description 6
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims abstract description 6
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims abstract description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000007792 addition Methods 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 238000006266 etherification reaction Methods 0.000 abstract description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 abstract description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005727 Friedel-Crafts reaction Methods 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract 1
- -1 phenolic aldehyde Chemical class 0.000 description 8
- 239000000463 material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 230000006750 UV protection Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08L61/14—Modified phenol-aldehyde condensates
-
- 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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
- C08G8/36—Chemically modified polycondensates by etherifying
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses a yellowing-resistant heat-insulating material for a wall, which comprises the following raw materials in parts by weight: 100-150 parts of modified phenolic resin, 18-25 parts of diatomite, 15-20 parts of polystyrene and 6-10 parts of sodium dodecyl benzene sulfonate; the modified phenolic resin is used as a matrix, and is modified by a modifier, and the method specifically comprises the following steps: firstly, cyanuric chloride and m-naphthalenediol are used as raw materials, and are put into AlCl3Under the catalysis of the alkali catalyst cesium carbonate, a Friedel-crafts reaction is carried out to obtain a modifier shown as a formula M1, and then under the catalysis of the alkali catalyst cesium carbonate, the modifier and the phenolic resin are subjected to an etherification reaction to obtain a modified phenolic resin, wherein the etherification reduces the acidity of the phenolic resin, and the toughness of the phenolic resin is improved; in addition, on phenolic resinsThe triazine uvioresistant functional structure is connected in a chemical bond mode, so that the uvioresistant performance of the phenolic resin can be maintained for a long time, and the yellowing resistance of the phenolic resin heat-insulating material is improved.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a yellowing-resistant heat-insulating material for a wall.
Background
The phenolic resin thermal insulation material belongs to an organic thermosetting efficient thermal insulation material, and particularly, the technical performance of the applied thermal insulation material is higher and the market demand is larger and larger as the energy saving rate of buildings is gradually improved in recent years. In the application of heat-insulating materials for building, not only the physical and technical properties are required to be high, but also the fire-proof performance must be achieved. The phenolic insulation material produced by the phenolic resin has good fire penetration resistance, high temperature resistance and low smoke performance, but the phenolic insulation material has the biggest defects of high brittleness and high acidity. Due to the fact that the phenolic aldehyde heat-insulating material is high in brittleness, the problems that the phenolic aldehyde heat-insulating material is prone to powder falling, low in elasticity, low in compression strength, unqualified in heat conductivity coefficient and the like exist when the phenolic aldehyde heat-insulating material is used, inherent excellent fireproof performance cannot be well utilized, and therefore expansion of application technology of the phenolic aldehyde heat-insulating material is affected, and meanwhile inconvenience is brought to transportation and construction. Because of large acidity, the phenolic aldehyde heat-insulating material can have certain corrosivity when contacting with metal and cement-based materials, and the application range of the phenolic aldehyde heat-insulating material is limited; in addition, when the phenolic aldehyde heat-insulating material is used in an external environment, the phenolic aldehyde heat-insulating material is exposed to wind and sunlight for a long time, and the heat-insulating board is easy to age, so that the phenomena of fading, yellowing, pulverization and the like are generated.
Disclosure of Invention
The invention aims to provide a yellowing-resistant heat-insulating material for a wall.
The purpose of the invention can be realized by the following technical scheme:
a yellowing-resistant heat-insulating material for a wall comprises the following raw materials in parts by weight: 100-150 parts of modified phenolic resin, 18-25 parts of diatomite, 15-20 parts of polystyrene and 6-10 parts of sodium dodecyl benzene sulfonate.
Further, the preparation method of the modified phenolic resin specifically comprises the following steps:
the reaction process is as follows:
s1 preparation of modifier
Weighing 100mmol of cyanuric chloride, a catalyst and 500ml of solvent toluene, adding 205-210mmol of M-naphthalenediol while stirring, heating to 85-90 ℃, reacting for 3-5h under heat preservation, adding 500ml of deionized water, removing the solvent by using a rotary evaporator, and washing the obtained solid with water to obtain the modifier shown in the formula M1;
s2 preparation of modified phenolic resin
Weighing 12-14.5g of modifier A1, 105-125g of solid phenolic resin powder and 1.5-2L of solvent isopropanol, adding into a reaction kettle, stirring and dissolving completely, adding an alkali catalyst cesium carbonate, stirring and heating to 75-85 ℃ after adding, preserving heat for reaction for 3-5h, naturally cooling to room temperature after reaction, carrying out suction filtration, washing with water, and drying to obtain the modified phenolic resin shown in the formula M.
Further, in step S1, the catalyst is AlCl3The amount of catalyst added was 102-105 mmol.
Further, in step S1, the alkali catalyst is cesium carbonate, and the amount of the alkali catalyst added is 6 to 9 g.
The invention has the beneficial effects that:
the invention provides a yellowing-resistant heat-insulating material for a wall, which takes modified phenolic resin as a matrix and adopts a modifier to modify the phenolic resin, and specifically comprises the following steps: firstly, cyanuric chloride and m-naphthalenediol are used as raw materials, and are put into AlCl3Under the catalysis of the alkali catalyst cesium carbonate, a Friedel-crafts reaction is carried out to obtain a modifier shown as a formula M1, and then under the catalysis of the alkali catalyst cesium carbonate, the modifier and the phenolic resin are subjected to an etherification reaction to obtain a modified phenolic resin, wherein the etherification reduces the acidity of the phenolic resin, and the toughness of the phenolic resin is improved; in addition, the phenolic resin is connected with a triazine uvioresistant functional structure in a chemical bond mode, so that the uvioresistant performance of the phenolic resin can be maintained for a long time, and the yellowing resistance of the phenolic resin thermal insulation material is improved.
Of course, it is not necessary for any product in which the invention is practiced to achieve all of the above-described advantages at the same time.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of the modified phenolic resin specifically comprises the following steps:
s1 preparation of modifier
Weighing 100mmol of cyanuric chloride and 104mmol of AlCl serving as a catalyst3Adding toluene solvent 500ml, adding 205mmol of M-naphthalenediol while stirring, heating to 85 ℃, keeping the temperature for reaction for 4 hours, adding deionized water 500ml, removing the solvent by adopting a rotary evaporator, and washing the obtained solid with water to obtain the modifier shown in the formula M1;
s2 preparation of modified phenolic resin
Weighing 13.5g of modifier A1, 117g of solid phenolic resin powder and 2L of solvent isopropanol, adding into a reaction kettle, stirring and dissolving completely, adding 9g of alkali catalyst cesium carbonate, stirring and heating to 84 ℃, keeping the temperature for reaction for 4 hours, naturally cooling to room temperature after the reaction is finished, performing suction filtration, washing with water, and drying to obtain the modified phenolic resin shown in the formula M;
the reaction process is as follows:
the infrared characterization of the modified phenolic resin is as follows: IR (KBr):
(-OH),3023/3008 (benzene ring), 2864 (-CH)2-, 1520 (triazine Ring) cm-1。
Example 2
A yellowing-resistant heat-insulating material for a wall comprises the following raw materials in parts by weight: 100 parts of modified phenolic resin, 20 parts of diatomite, 18 parts of polystyrene and 7 parts of sodium dodecyl benzene sulfonate;
the preparation method of the yellowing-resistant heat-insulating material comprises the following steps: adding the raw materials into a ball mill, grinding and crushing for 1.5h, placing the mixture into a mold after crushing, and finally placing the mold into a heating furnace to be heated, sintered, shaped, annealed, taken out of the furnace and cooled to obtain the yellowing-resistant heat-insulating material for the wall.
Example 3
A yellowing-resistant heat-insulating material for a wall comprises the following raw materials in parts by weight: 130 parts of modified phenolic resin, 25 parts of diatomite, 16 parts of polystyrene and 10 parts of sodium dodecyl benzene sulfonate;
the preparation method of the yellowing-resistant heat-insulating material comprises the following steps: adding the raw materials into a ball mill, grinding and crushing for 2h, placing the materials into a mold after crushing, and finally placing the materials into a heating furnace to be heated, sintered, shaped, annealed, taken out of the furnace and cooled to obtain the yellowing-resistant heat-insulating material for the wall.
Example 4
A yellowing-resistant heat-insulating material for a wall comprises the following raw materials in parts by weight: 150 parts of modified phenolic resin, 22 parts of diatomite, 19 parts of polystyrene and 6 parts of sodium dodecyl benzene sulfonate;
the preparation method of the yellowing-resistant heat-insulating material comprises the following steps: adding the raw materials into a ball mill, grinding and crushing for 1.5h, placing the mixture into a mold after crushing, and finally placing the mold into a heating furnace to be heated, sintered, shaped, annealed, taken out of the furnace and cooled to obtain the yellowing-resistant heat-insulating material for the wall.
Comparative example 1
The modified phenolic resin was replaced with a phenolic resin as in example 4.
The prepared thermal insulation material is subjected to ultraviolet resistance test
As can be seen from the above table, the thermal insulation material prepared by the invention has good ultraviolet resistance, can be used in an external wall, can maintain thermal insulation for a long time, prevents the wall from yellowing, and has good practicability.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (4)
1. A yellowing-resistant heat-insulating material for a wall body is characterized in that: the feed comprises the following raw materials in parts by weight: 100-150 parts of modified phenolic resin, 18-25 parts of diatomite, 15-20 parts of polystyrene and 6-10 parts of sodium dodecyl benzene sulfonate.
2. The yellowing-resistant heat-insulating material for the wall body as claimed in claim 1, wherein: the preparation method of the modified phenolic resin specifically comprises the following steps:
the reaction process is as follows:
s1 preparation of modifier
Weighing 100mmol of cyanuric chloride, a catalyst and 500ml of solvent toluene, adding 205-210mmol of M-naphthalenediol while stirring, heating to 85-90 ℃, reacting for 3-5h under heat preservation, adding 500ml of deionized water, removing the solvent by using a rotary evaporator, and washing the obtained solid with water to obtain the modifier shown in the formula M1;
s2 preparation of modified phenolic resin
Weighing 12-14.5g of modifier A1, 105-125g of solid phenolic resin powder and 1.5-2L of solvent isopropanol, adding into a reaction kettle, stirring and dissolving completely, adding an alkali catalyst cesium carbonate, stirring and heating to 75-85 ℃ after adding, preserving heat for reaction for 3-5h, naturally cooling to room temperature after reaction, carrying out suction filtration, washing with water, and drying to obtain the modified phenolic resin shown in the formula M.
3. The yellowing-resistant heat-insulating material for the wall body as claimed in claim 2, wherein: in step S1, the catalyst is AlCl3The amount of catalyst added was 102-105 mmol.
4. The yellowing-resistant heat-insulating material for the wall body as claimed in claim 2, wherein: in step S1, the alkali catalyst is cesium carbonate, and the addition amount of the alkali catalyst is 6-9 g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010471800.7A CN111534042A (en) | 2020-05-29 | 2020-05-29 | Anti-yellowing heat insulation material for wall |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010471800.7A CN111534042A (en) | 2020-05-29 | 2020-05-29 | Anti-yellowing heat insulation material for wall |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111534042A true CN111534042A (en) | 2020-08-14 |
Family
ID=71972530
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010471800.7A Pending CN111534042A (en) | 2020-05-29 | 2020-05-29 | Anti-yellowing heat insulation material for wall |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111534042A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150284638A1 (en) * | 2011-10-31 | 2015-10-08 | Asia Cuanon Technology (Shanghai) Co., Ltd. | Fireproof composition and fireproof thermal insulation board |
| CN107446305A (en) * | 2017-07-18 | 2017-12-08 | 合肥广能新材料科技有限公司 | Phenolic resin warming plate and preparation method thereof |
-
2020
- 2020-05-29 CN CN202010471800.7A patent/CN111534042A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150284638A1 (en) * | 2011-10-31 | 2015-10-08 | Asia Cuanon Technology (Shanghai) Co., Ltd. | Fireproof composition and fireproof thermal insulation board |
| CN107446305A (en) * | 2017-07-18 | 2017-12-08 | 合肥广能新材料科技有限公司 | Phenolic resin warming plate and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107324776A (en) | A kind of thermal-insulation energy-conservation material and preparation method thereof | |
| CN109761633B (en) | Baking-free boron mud PVC ceramsite and preparation method thereof | |
| CN107399992A (en) | A kind of wall insulating sheet materials and preparation method thereof | |
| CN108409349A (en) | A kind of thermal-insulation energy-conservation material and preparation method thereof | |
| CN111592733B (en) | Anti-aging heat insulation board | |
| CN105368466A (en) | Preparation method of hydroxide compound fire retardant with surface of diisocyanate in bridge joint with graphene oxide | |
| CN104497554A (en) | Preparation method of weatherproof polyurethane thermal insulation wall material | |
| CN111892353A (en) | Fireproof flame-retardant thermal insulation mortar and preparation method thereof | |
| CN102295821B (en) | Production method of phenolic foam wall insulation material | |
| WO2019104817A1 (en) | Preparation method for lignin phenolic resin foam material | |
| CN102877556B (en) | Novel wall body heat preservation core plate and production method thereof | |
| CN103881231B (en) | A kind of thermal storage and energy accumulation spacer bar based on ethylene-vinyl acetate copolymer and preparation method thereof | |
| CN111534042A (en) | Anti-yellowing heat insulation material for wall | |
| CN103351575B (en) | Production method of inorganic soil graft modified phenolic resin foam | |
| CN107474204A (en) | A kind of modified phenolic foam insulation material and preparation method thereof | |
| CN104262898A (en) | Organic-inorganic composite modified flame-retardant phenolic foam | |
| CN112028554A (en) | Graphene oxide modified diatomite fireproof insulation board | |
| CN111574809A (en) | High-temperature-resistant modified phenolic resin thermal insulation material | |
| CN111534043A (en) | Thermal insulation board with good thermal stability | |
| CN105385126A (en) | Polylactic acid / porous geopolymer composite material preparation method | |
| CN111662558B (en) | High-strength flame-retardant heat-insulation composite door and window | |
| CN111620567B (en) | Light microcrystalline foaming thermal insulation material prepared from molybdenum tailings and preparation method thereof | |
| CN105315481B (en) | A method of preparing flame retardant type phenolic resin low temp expanded material | |
| CN110482950B (en) | Low-cost high-strength insulation board and preparation method thereof | |
| CN104311868A (en) | Preparation method of cellulose modified phenolic foams |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200814 |