CN114669283A - Preparation method of polydimethylsiloxane composite sponge for continuously and efficiently filtering PM - Google Patents
Preparation method of polydimethylsiloxane composite sponge for continuously and efficiently filtering PM Download PDFInfo
- Publication number
- CN114669283A CN114669283A CN202210424793.4A CN202210424793A CN114669283A CN 114669283 A CN114669283 A CN 114669283A CN 202210424793 A CN202210424793 A CN 202210424793A CN 114669283 A CN114669283 A CN 114669283A
- Authority
- CN
- China
- Prior art keywords
- pdms
- sponge
- pda
- composite sponge
- zif
- 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
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 title claims abstract description 133
- 239000002131 composite material Substances 0.000 title claims abstract description 97
- 239000004205 dimethyl polysiloxane Substances 0.000 title claims abstract description 71
- 238000001914 filtration Methods 0.000 title claims abstract description 50
- -1 polydimethylsiloxane Polymers 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000243 solution Substances 0.000 claims abstract description 37
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229960001149 dopamine hydrochloride Drugs 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000002791 soaking Methods 0.000 claims abstract description 23
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims abstract description 20
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 17
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims description 33
- 229960002303 citric acid monohydrate Drugs 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims 7
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 claims 5
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 claims 5
- 238000002604 ultrasonography Methods 0.000 claims 1
- 229920001690 polydopamine Polymers 0.000 description 60
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 20
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 20
- 239000002245 particle Substances 0.000 description 17
- 239000002105 nanoparticle Substances 0.000 description 16
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 12
- 239000011148 porous material Substances 0.000 description 9
- 238000003760 magnetic stirring Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 6
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 5
- 239000013618 particulate matter Substances 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000007983 Tris buffer Substances 0.000 description 4
- 230000009920 chelation Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000010041 electrostatic spinning Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/30—Particle separators, e.g. dust precipitators, using loose filtering material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/024—Compounds of Zn, Cd, Hg
- B01J20/0244—Compounds of Zn
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a preparation method of Polydimethylsiloxane (PDMS) composite sponge capable of continuously and efficiently filtering PM, which comprises the steps of preparing PDMS sponge by a sacrificial template method, then placing the PDMS sponge in dopamine hydrochloride solution, preparing PDA @ PDMS composite sponge by self-polymerization, and then placing the obtained PDA @ PDMS composite sponge in a mixed solution of 2-methylimidazole and zinc nitrate hexahydrate for soaking to prepare ZIF-8@ PDA @ PDMS composite sponge. The preparation method is simple in preparation process and low in cost, the ZIF-8@ PDA @ PDMS composite sponge has extremely high filtering performance under severe environments such as high temperature, high humidity and the like due to the thermal stability and hydrophobicity, the shape of the ZIF-8@ PDA @ PDMS composite sponge is controllable, the mechanical performance of the ZIF-8@ PDA @ PDMS composite sponge is excellent, and the application range of the ZIF-8@ PDMS composite sponge is greatly widened.
Description
Technical Field
The invention belongs to the field of material chemical industry, and particularly relates to a preparation method of Polydimethylsiloxane (PDMS) composite sponge for continuously and efficiently filtering Particulate Matters (PM) in harsh environments such as high temperature, high humidity and the like.
Background
With the increasing improvement of the living standard of people, the automobile also becomes an indispensable living tool for each family. Along with the rapid increase of the number of automobiles, the emission of tail gas generated by the automobiles in the driving process is accompanied; in addition, there is a large amount of particulate-rich gas emissions from activities such as industrial production, daily power generation, and the like. The visibility is influenced by the pollution of particles in the air, so that the life quality of people is influenced; even smaller sized particles can pose a serious health hazard to the public. In order to avoid the harm caused by the fine particles, the production application of the industrial filter bag reduces the emission of the particles from the source, and the daily mask also serves as a last barrier to protect the respiratory tract of people. However, these filters have a problem of poor durability, and their filtering performance is rapidly reduced as the concentration of particulate matter increases. In addition, the application range and performance of such filter materials are also severely limited by the special particles generated under harsh environments such as high temperature and high humidity.
The prior patent CN 111905816A discloses a preparation method of a ZIF-8 functional fabric, which is characterized in that a polydopamine layer is introduced on the surface of the fabric, and the chelating effect of polydopamine active functional groups and zinc ions is utilized to induce a ZIF-8 film to uniformly grow on the surface of the fabric. The two-dimensional filter material still has poor filtering continuity, the performance is obviously reduced along with the increase of the concentration of particulate matters, a plurality of electrostatic spinning filter membranes also have the problems, and the application range of the two-dimensional filter material is greatly limited by a plurality of problems of long preparation period, high energy consumption, poor mechanical performance and the like.
Disclosure of Invention
The invention aims to overcome the defects of poor continuous performance and mechanical performance, narrow application range and the like of the existing gas filtering material, and provides a preparation method of polydimethylsiloxane composite sponge capable of continuously and efficiently filtering PM.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of polydimethylsiloxane composite sponge for continuously and efficiently filtering PM comprises the steps of firstly preparing PMDS sponge by a sacrificial template method, then placing the PMDS sponge in a dopamine hydrochloride solution, generating PDA @ PDMS composite sponge through self-polymerization, then placing the obtained PDA @ PDMS composite sponge in a mixed solution of 2-methylimidazole and zinc nitrate hexahydrate, and growing ZIF-8 nano particles on the surface of the PDA @ PDMS composite sponge in situ by utilizing the chelation of an active functional group of polydopamine and zinc ions to prepare the obtained ZIF-8@ PDA @ PDMS composite sponge; the method comprises the following specific steps:
(1) PDMS sponge prepared by sacrificial template method
Fully stirring the citric acid monohydrate powder and polydimethylsiloxane to uniformly mix the citric acid monohydrate powder and the polydimethylsiloxane, transferring the mixture into a required mould, repeatedly pressing the mould to discharge air, placing the mould in an oven at 150 ℃ to cure overnight, then placing the mould in deionized water, dissolving the citric acid monohydrate by using ultrasonic waves, and drying the mixture in the oven at 60 ℃ to obtain the three-dimensional porous PDMS sponge;
(2) preparation of PDA @ PDMS composite sponge by dopamine hydrochloride self-polymerization
Dissolving dopamine hydrochloride (DA) and Tris (hydroxymethyl) aminomethane (Tris) in deionized water to prepare dopamine hydrochloride solution, then placing the prepared PDMS sponge in the solution, soaking under magnetic stirring, then repeatedly washing with deionized water for a plurality of times, and then placing in a 60 ℃ oven for drying to obtain the PDA @ PDMS composite sponge;
(3) ZIF-8@ PDA @ PDMS composite sponge prepared by in-situ growth method
Respectively dissolving 2-methylimidazole and zinc nitrate hexahydrate in deionized water with equal mass to obtain a 17.5% 2-methylimidazole solution and a 1.1% zinc nitrate hexahydrate solution, and mixing the two prepared solutions under magnetic stirring to obtain a mixed solution of 2-methylimidazole and zinc nitrate hexahydrate; and continuously stirring and soaking the prepared PDA @ PDMS composite sponge in the mixed solution to grow ZIF-8 nano particles in situ, repeatedly cleaning the nano particles with deionized water for multiple times, and drying the nano particles in an oven at 60 ℃ overnight to obtain the ZIF-8@ PDA @ PDMS composite sponge.
Wherein the mass ratio of the citric acid monohydrate to the PDMS used in the step (1) is 3-6: 1.
The dopamine hydrochloride solution in the step (2) contains 0.2% of dopamine hydrochloride and 0.6% of tris (hydroxymethyl) aminomethane by mass; the PDMS sponge is soaked in the dopamine hydrochloride solution for 2-6 h.
And (4) soaking the PDA @ PDMS composite sponge in the mixed solution of 2-methylimidazole and zinc nitrate hexahydrate for 2-8 h in the step (3).
According to the invention, the large aperture and the high specific surface area of the PDMS sponge provide a large number of attachment sites for ZIF-8 while ensuring good air permeability, and the regular and complete sponge edge ensures the airtightness of the PDMS sponge in the gas filtration process, so that the PDMS sponge can be prepared into sponges with any shapes according to different molds, and the application range of the PDMS sponge in the gas filtration field is widened; the polydopamine layer grows through self-polymerization, the loading capacity of the ZIF-8 nano particles can be greatly increased by utilizing the chelation of active functional groups of the polydopamine layer and zinc ions, and the purpose of filtering particles in gas is further realized by utilizing a large number of polar functional groups, open metal sites and electrostatic adsorption of the ZIF-8. Meanwhile, a large number of ZIF-8 nanoparticles on the three-dimensional skeleton of the composite sponge ensure the continuity and the thermal stability of efficient filtration, the hydrophobicity of PDMS ensures that the PDMS can still have excellent filtration performance in harsh environments such as high temperature, high humidity and the like, and the potential application range of the PDMS is widened due to the characteristics of simple preparation process, adjustable pore diameter, excellent mechanical performance and the like, so that the composite sponge can obtain excellent performance in practical applications such as automobile exhaust filtration and the like.
The invention has the advantages that:
(1) the invention applies PDMS sponge to the PM filtering field for the first time. The PDMS sponge as the carrier has simple preparation process, low energy consumption and short period. Compared with a plurality of electrostatic spinning filter membranes, the PDMS sponge with more excellent mechanical properties has higher application value. The sponge has regular and controllable shape, the air tightness in the actual filtering process is ensured, and the large aperture and the high specific surface area of the three-dimensional skeleton provide enough attachment sites for ZIF-8 while the gas fluidity is ensured;
(2) in the preparation process of the composite sponge, polydopamine is used as a binder, and a large amount of active functional groups of the polydopamine and the chelation of zinc ions are utilized to ensure that a large amount of ZIF-8 nano particles grow on the surface of the sponge;
(3) according to the invention, a large amount of ZIF-8 nano-particles grow in the pore diameter and pore canal caused by the PDMS sponge three-dimensional framework, and the composite sponge has high-efficiency (> 99.8%) filtering performance of 65 h while ensuring low pressure drop. Due to the thermal stability of the composite sponge and the hydrophobicity of the PDMS material, the PDMS material still has high filtering performance (> 99%) in the environment of 250 ℃ and 90% of relative humidity, and the practical application range of the PDMS material is greatly widened.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein,
FIG. 1 is an SEM image of ZIF-8@ PDA @ PDMS composite sponges obtained by soaking in examples one-four for different time periods (wherein A, B, C, D corresponds to examples one-four in sequence).
FIG. 2 is a graph showing the loading of ZIF-8 nanoparticles on a ZIF-8@ PDA @ PDMS composite sponge obtained by soaking in one to four of the examples at different times, and the filtration performance and pressure drop of the obtained composite sponge.
FIG. 3 is a graph showing the effect of using different weight parts of citric acid monohydrate on the morphology of PDMS sponges prepared in examples five to eight (wherein A, B, C, D corresponds to examples five to eight in turn).
FIG. 4 is a graph comparing the filtration efficiency of the ZIF-8@ PDA @ PDMS composite sponges prepared in the fifth to eighth examples using different weight parts of citric acid monohydrate.
FIG. 5 is an SEM comparison of PDMS sponge and ZIF-8@ PDA @ PDMS composite sponge prepared in example three.
FIG. 6 is a graph of the initial concentration of Particulate Matter (PM) for the ZIF-8@ PDA @ PDMS composite sponge prepared in example III2.5And PM10Both greater than 20000 μ g/m) and pressure drop profile.
FIG. 7 is a graph of the change in pressure drop for the SEM before and after 4 washes and during each test for the ZIF-8@ PDA @ PDMS composite sponge prepared in example three.
FIG. 8 is a thermogravimetric analysis of the ZIF-8@ PDA @ PDMS composite sponge prepared in example three and a graph of the filtration performance under different high temperature environments.
FIG. 9 is a graph of contact angle measurements and filtration performance in a high humidity environment for a ZIF-8@ PDA @ PDMS composite sponge prepared in example three.
Detailed Description
A preparation method of polydimethylsiloxane composite sponge for continuously and efficiently filtering PM comprises the following specific steps:
(1) PDMS sponge prepared by sacrificial template method
Thoroughly grinding a proper amount of citric acid monohydrate particles into powder in a mortar, fully stirring the citric acid monohydrate powder and polydimethylsiloxane to uniformly mix the citric acid monohydrate powder and the polydimethylsiloxane, transferring the mixture into a required mold, repeatedly pressing the mold to discharge air, placing the mold in a 150 ℃ oven to cure overnight, placing the mold in deionized water, dissolving the citric acid monohydrate by using ultrasonic waves, and drying the mixture in the 60 ℃ oven to obtain the three-dimensional porous PDMS sponge; wherein the mass ratio of the citric acid monohydrate to the PDMS is 3-6: 1;
(2) preparation of PDA @ PDMS composite sponge by dopamine hydrochloride self-polymerization
Dissolving dopamine hydrochloride (DA) and Tris (hydroxymethyl) aminomethane (Tris) in deionized water to prepare dopamine hydrochloride solution, wherein the mass concentration of the dopamine hydrochloride is 0.2%, and the mass concentration of the Tris (hydroxymethyl) aminomethane is 0.6%; then placing the prepared PDMS sponge into the solution, soaking for 2-6 h under magnetic stirring, then repeatedly washing with deionized water for several times, and then placing in an oven at 60 ℃ for drying to obtain the PDA @ PDMS composite sponge;
(3) ZIF-8@ PDA @ PDMS composite sponge prepared by in-situ growth method
Respectively dissolving 2-methylimidazole and zinc nitrate hexahydrate in deionized water with equal mass to obtain a 17.5% 2-methylimidazole solution and a 1.1% zinc nitrate hexahydrate solution, and mixing the two prepared solutions under magnetic stirring to obtain a mixed solution of 2-methylimidazole and zinc nitrate hexahydrate; and continuously stirring and soaking the prepared PDA @ PDMS composite sponge in the mixed solution for 2-8 h, then repeatedly washing the mixed solution with deionized water for many times, and then drying the washed solution in an oven at 60 ℃ overnight to obtain the ZIF-8@ PDA @ PDMS composite sponge.
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, embodiments accompanying figures are described further below. The invention is not limited to the embodiments listed but also comprises any other known variations within the scope of the invention as claimed.
First, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
The present invention is described in detail by using the schematic structural diagrams, etc., and for convenience of illustration, the schematic diagrams are not enlarged partially according to the general scale when describing the embodiments of the present invention, and the schematic diagrams are only examples, which should not limit the scope of the present invention. In addition, the actual fabrication process should include three-dimensional space of length, width and depth.
Example one
The embodiment prepares the Polydimethylsiloxane (PDMS) composite sponge for continuously and efficiently filtering PM under the harsh environment such as high temperature and high humidity according to the following steps:
the method comprises the following steps: PDMS sponge prepared by sacrificial template method
Taking a proper amount of citric acid monohydrate particles, completely grinding the citric acid monohydrate particles into powder in a mortar, fully stirring 3 parts by weight of citric acid monohydrate powder and 1 part by weight of polydimethylsiloxane to uniformly mix the citric acid monohydrate powder and the polydimethylsiloxane, transferring the mixture into a required mold, repeatedly pressing the mold to discharge air, placing the mold in an oven at 150 ℃ to cure overnight, placing the mold in deionized water, dissolving the citric acid monohydrate by using ultrasonic waves, and drying the mixture in the oven at 60 ℃ to obtain the three-dimensional porous PDMS sponge;
step two: preparing PDA @ PDMS composite sponge by dopamine hydrochloride self-polymerization;
dissolving dopamine hydrochloride (DA) and Tris (hydroxymethyl) aminomethane (Tris) in deionized water to prepare dopamine hydrochloride solution, wherein the mass concentration of the dopamine hydrochloride is 0.2%, and the mass concentration of the Tris (hydroxymethyl) aminomethane is 0.6%; then placing the prepared PDMS sponge into the solution, soaking for 4h under magnetic stirring, then repeatedly cleaning with deionized water for several times, and then placing in a 60 ℃ oven for drying to obtain the PDA @ PDMS composite sponge;
step three: ZIF-8@ PDA @ PDMS composite sponge prepared by in-situ growth method
Respectively dissolving 2-methylimidazole and zinc nitrate hexahydrate in deionized water with equal mass to obtain a 17.5% mass concentration 2-methylimidazole solution and a 1.1% mass concentration zinc nitrate hexahydrate solution, and mixing the two solutions under magnetic stirring to obtain a mixed solution of 2-methylimidazole and zinc nitrate hexahydrate; and continuously stirring and soaking the prepared PDA @ PDMS composite sponge in the mixed solution for 2 h, then repeatedly washing the mixed solution with deionized water for many times, and then drying the washed solution in an oven at 60 ℃ overnight to obtain the ZIF-8@ PDA @ PDMS composite sponge.
Example two
The soaking in the third step of the first embodiment is actually replaced by 4 hours, and other operations are carried out as in the first embodiment to prepare the ZIF-8@ PDA @ PDMS composite sponge.
EXAMPLE III
The soaking in the third step of the first embodiment is actually replaced by 6 hours, and other operations are carried out as in the first embodiment to prepare the ZIF-8@ PDA @ PDMS composite sponge.
Example four
The soaking in the third step of the first embodiment is actually replaced by 8 hours, and other operations are carried out as in the first embodiment to prepare the ZIF-8@ PDA @ PDMS composite sponge.
EXAMPLE five
The embodiment prepares the Polydimethylsiloxane (PDMS) composite sponge for continuously and efficiently filtering PM under the harsh environment such as high temperature and high humidity according to the following steps:
the method comprises the following steps: PDMS sponge prepared by sacrificial template method
Taking a proper amount of citric acid monohydrate particles, completely grinding the citric acid monohydrate particles into powder in a mortar, fully stirring 3 parts by weight of citric acid monohydrate powder and 1 part by weight of polydimethylsiloxane to uniformly mix the citric acid monohydrate powder and the polydimethylsiloxane, transferring the mixture into a required mold, repeatedly pressing the mold to discharge air, placing the mold in an oven at 150 ℃ to cure overnight, placing the mold in deionized water, dissolving the citric acid monohydrate by using ultrasonic waves, and drying the mixture in the oven at 60 ℃ to obtain the three-dimensional porous PDMS sponge;
step two: preparing PDA @ PDMS composite sponge by dopamine hydrochloride self-polymerization;
dissolving dopamine hydrochloride (DA) and Tris (hydroxymethyl) aminomethane (Tris) in deionized water to prepare a dopamine hydrochloride solution, wherein the dopamine hydrochloride solution contains 0.2 mass percent of dopamine hydrochloride and 0.6 mass percent of Tris (hydroxymethyl) aminomethane; then placing the prepared PDMS sponge into the solution, soaking for 4h under magnetic stirring, then repeatedly cleaning with deionized water for several times, and then placing in a 60 ℃ oven for drying to obtain the PDA @ PDMS composite sponge;
step three: ZIF-8@ PDA @ PDMS composite sponge prepared by in-situ growth method
Respectively dissolving 2-methylimidazole and zinc nitrate hexahydrate in deionized water with equal mass to obtain a 17.5% 2-methylimidazole solution and a 1.1% zinc nitrate hexahydrate solution, and mixing the two solutions under magnetic stirring to obtain a mixed solution of 2-methylimidazole and zinc nitrate hexahydrate; and continuously stirring and soaking the prepared PDA @ PDMS composite sponge in the mixed solution for 6h, then repeatedly washing the mixed solution with deionized water for many times, and then drying the washed solution in an oven at 60 ℃ overnight to obtain the ZIF-8@ PDA @ PDMS composite sponge.
Example six
A ZIF-8@ PDA @ PDMS composite sponge was prepared as in example five, except that the amount of citric acid monohydrate powder used in step one of example five was changed to 4 parts by weight.
EXAMPLE seven
The ZIF-8@ PDA @ PDMS composite sponge was prepared by substituting 5 parts by weight of citric acid monohydrate powder in the first step of the fifth example and performing the other operations of the fifth example.
Example eight
The ZIF-8@ PDA @ PDMS composite sponge was prepared by substituting 6 parts by weight of citric acid monohydrate powder in the first step of the fifth example and performing the other operations of the fifth example.
FIG. 1 is an SEM image of ZIF-8@ PDA @ PDMS composite sponge obtained by soaking in the first to fourth examples for different time periods. As can be seen from the figure, the growth amount of the ZIF-8 nanoparticles is remarkably increased along with the time from sporadic growth for 2 hours to massive growth for 4 hours and then to dense and uniform loading for 6 hours; and when the sponge is soaked for 8 hours, the ZIF-8 nano particles grow in the sponge in a large amount and even are in a mountain peak shape.
FIG. 2 is a graph showing the loading of ZIF-8 nanoparticles on a ZIF-8@ PDA @ PDMS composite sponge obtained by soaking in the first to fourth examples for different periods of time, and the filtration performance and pressure drop of the obtained composite sponge. It can be seen from the figure that the filtration efficiency of the ZIF-8@ PDA @ PDMS composite sponge can reach 99.9% after soaking for 6 hours, if the soaking is continued, the pressure drop of the ZIF-8@ PDA @ PDMS composite sponge is rapidly increased, and the analysis is performed by referring to fig. 1, which may be because when the soaking is performed for 8 hours, the growth of ZIF-8 nanoparticles is transferred from the surface of the sponge skeleton to the stacking growth of ZIF-8 nanoparticles, which blocks the pore channels to some extent, reduces the reduction of air permeability, which may affect the subsequent filtration of particles, and therefore, the soaking is preferably performed for 6 hours.
FIG. 3 is a graph illustrating the effect of using different weight parts of citric acid monohydrate on the morphology of PDMS sponges prepared in examples V to V. As can be clearly seen from the figure, with the increase of the consumption of citric acid monohydrate, the number of holes is increased, the pore diameter is enlarged, and the size is different from dozens to three hundred micrometers, so that the PDMS sponge is loosened from compact, the air permeability is increased, and the pressure drop is reduced.
FIG. 4 is a graph comparing the filtration efficiency of the ZIF-8@ PDA @ PDMS composite sponges prepared in the fifth to eighth examples using different weight parts of citric acid monohydrate. As can be further seen from the figure, as the amount of citric acid monohydrate used as a sacrificial agent increases, the pore size of the PDMS sponge increases, the porosity increases, the sponge becomes more porous, and therefore the filtration performance for fine particles is significantly reduced, so the mass ratio of citric acid monohydrate to polydimethylsiloxane is preferably 3: 1.
FIG. 5 is an SEM comparison of PDMS sponge and ZIF-8@ PDA @ PDMS composite sponge prepared in example three. As can be seen from the pictures, compared with PDMS sponge, a large amount of ZIF-8 nano-particles grow inside the ZIF-8@ PDA @ PDMS composite sponge pore channel, and the high efficiency and the continuity of filtering are ensured.
The continuous filtration performance of the composite sponge particles was tested. The method specifically comprises the steps of utilizing PM particles generated by incense burning, discharging the generated smoke from an air outlet through an incense burning table through an air inlet under the action of a fan, detecting the particle concentration of the air outlet provided with the composite sponge by using a particle air quality detector, and further calculating the filtering efficiency of the composite sponge. FIG. 6 is a graph of the initial concentration of Particulate Matter (PM) for the ZIF-8@ PDA @ PDMS composite sponge prepared in example III2.5And PM10Both greater than 20000 μ g/m) and pressure drop profile. Under the environment of continuous high concentration and high wind speed, the composite sponge can continuously maintain higher filtering efficiency for up to 65 hours in the filtering process (>99.8%), the pressure drop also increases only by around 20 Pa.
The testing device simulates gas suction filtration under an industrial high-pressure environment through the diaphragm vacuum pump, the diaphragm vacuum pump is connected with a box body filled with smoke through a rubber tube, the smoke ignited in the box body can continuously generate the smoke, the composite sponge is fixed between the diaphragm vacuum pump and the box body, a particle concentration counter is used for testing the particle concentration in the gas at the exhaust port of the diaphragm vacuum pump, the composite sponge is taken out every 20min of testing, and the composite sponge is cleaned by deionized water and absolute ethyl alcohol and then is loaded into the device for testing. FIG. 7 is a graph of the change in pressure drop for the SEM before and after 4 washes and during each test for the ZIF-8@ PDA @ PDMS composite sponge prepared in example three. It can be seen from the figure that as the particulate matters are continuously accumulated in the sponge, the pressure drop is rapidly increased due to the blockage of the pore channels, the particulate matters fall off after repeated cleaning by the deionized water and the absolute ethyl alcohol, the air permeability of the composite sponge is recovered, and the pressure drop is also reduced.
Utilize tubular furnace simulation industry high temperature environment particulate matter's quick filtration testing arrangement. Then place compound sponge in the most intermediate position of the interior quartz capsule of tubular furnace, through rising temperature and then change the filtration ambient temperature of compound sponge to the tubular furnace, utilize diaphragm vacuum pump to carry out high pressure and bleed fast, test the concentration of particulate matter in the gas after compound sponge adsorbs under the high temperature environment, and then calculate the filtration efficiency of compound sponge under the high temperature environment. FIG. 8 is a thermogravimetric analysis and filtration performance plots of the ZIF-8@ PDA @ PDMS composite sponge prepared in example three under different high temperature environments. Compared with thermogravimetric analysis, the composite sponge still keeps extremely high filtering efficiency (> 99%) in a high-temperature environment of 250 ℃, and the application range of the composite sponge in the high-temperature environment is widened;
the relative humidity of the environment in the closed environment is adjusted through the humidifier, and then the continuous filtering performance of the composite sponge in different humidity environments is tested. FIG. 9 is a graph of contact angle measurements and filtration performance in a high humidity environment for a ZIF-8@ PDA @ PDMS composite sponge prepared in example three. As can be seen from the figure, since the hydrophobic property of PDMS endows the composite sponge with a higher water contact angle, the filtration efficiency (> 99%) can be maintained in a high-humidity environment with a relative humidity of 90%, which shows the potential applications of the composite sponge in different humidity environments.
In conclusion, the invention discloses a preparation method of polydimethylsiloxane composite sponge capable of continuously and efficiently filtering PM under harsh environments such as high temperature, high humidity and the like, the method comprises the steps of preparing PDMS sponge with a certain pore size by a sacrificial template method, growing a polydopamine layer on a sponge framework through dopamine hydrochloride autopolymerization, and growing a large number of ZIF-8 nanoparticles on the sponge framework by utilizing the chelation of active functional groups of the polydopamine and zinc ions, thereby preparing the ZIF-8@ PDA @ PDMS composite sponge. The invention has simple preparation industry, low energy consumption and short period, and the PDMS sponge as a carrier has regular and controllable shape, thereby ensuring the air tightness in the gas filtering process; the large aperture and the high specific surface area ensure the air permeability of the composite sponge and simultaneously provide a large number of attachment sites for ZIF-8, thereby ensuring the high efficiency and the continuity of filtration. The excellent mechanical property, thermal stability and hydrophobicity of the composite sponge broaden the application range of the composite sponge, so that the composite sponge still has excellent filtering performance under harsh environments such as high temperature, high humidity and the like.
It should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting, and although the present invention is described in detail with reference to the preferred embodiments, those skilled in the art can make modifications or adjustments to the technical solutions of the present invention without departing from the essential scope of the technical solutions of the present invention, and all should be covered in the scope of the claims of the present invention.
Claims (6)
1. A preparation method of polydimethylsiloxane composite sponge for continuously and efficiently filtering PM is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing PDMS sponge by a sacrificial template method by taking citric acid monohydrate as a sacrificial agent;
(2) soaking the PDMS sponge obtained in the step (1) in dopamine hydrochloride solution, and preparing the PDA @ PDMS composite sponge through self-polymerization;
(3) and (3) placing the PDA @ PDMS composite sponge obtained in the step (2) into a mixed solution of 2-methylimidazole and zinc nitrate hexahydrate for stirring and soaking, then cleaning with deionized water, and drying to obtain the ZIF-8@ PDA @ PDMS composite sponge.
2. The production method according to claim 1, characterized in that: the step (1) is specifically that citric acid monohydrate powder and polydimethylsiloxane are fully stirred to be uniformly mixed, then the mixture is transferred to a needed mold, air is discharged through repeated pressing, the mixture is solidified overnight at 150 ℃, then the mixture is placed in deionized water, citric acid monohydrate is dissolved by utilizing ultrasound, and then the mixture is dried at 60 ℃ to obtain the three-dimensional porous PDMS sponge.
3. The method of claim 2, wherein: the mass ratio of the citric acid monohydrate to the PDMS is 3-6: 1.
4. The method of claim 1, wherein: in the step (2), the PDMS sponge is soaked in the dopamine hydrochloride solution for 2-6 h.
5. The method of claim 1, wherein: in the step (3), the PDA @ PDMS composite sponge is soaked in the mixed solution of 2-methylimidazole and zinc nitrate hexahydrate for 2-8 h.
6. The production method according to claim 1 or 5, characterized in that: the mixed solution of the 2-methylimidazole and the zinc nitrate hexahydrate is prepared by respectively dissolving the 2-methylimidazole and the zinc nitrate hexahydrate in deionized water with equal mass to obtain a 17.5% 2-methylimidazole solution and a 1.1% zinc nitrate hexahydrate solution, and mixing the two solutions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210424793.4A CN114669283A (en) | 2022-04-22 | 2022-04-22 | Preparation method of polydimethylsiloxane composite sponge for continuously and efficiently filtering PM |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210424793.4A CN114669283A (en) | 2022-04-22 | 2022-04-22 | Preparation method of polydimethylsiloxane composite sponge for continuously and efficiently filtering PM |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114669283A true CN114669283A (en) | 2022-06-28 |
Family
ID=82079505
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210424793.4A Pending CN114669283A (en) | 2022-04-22 | 2022-04-22 | Preparation method of polydimethylsiloxane composite sponge for continuously and efficiently filtering PM |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114669283A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115746392A (en) * | 2022-11-25 | 2023-03-07 | 中国科学院海洋研究所 | Modified friction power generation sponge, single-electrode sponge friction power generation device, and preparation and application thereof |
| CN116510706A (en) * | 2023-05-23 | 2023-08-01 | 中北大学 | Preparation method and application of porous nano-sponge loaded MOF material |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103394336A (en) * | 2013-07-31 | 2013-11-20 | 武汉大学 | Metal organic framework compound sol-gel coating stirring rod and preparation method and application thereof |
| WO2019207475A1 (en) * | 2018-04-24 | 2019-10-31 | Ecole Polytechnique Federale De Lausanne (Epfl) | Method for synthesis of a metal organic framework composite. |
| CN110394062A (en) * | 2019-01-28 | 2019-11-01 | 北京理工大学 | A kind of mixed-matrix plate membrane preparation method of MOF particle modification nanotube filled silicon rubber |
| CN111905816A (en) * | 2020-07-08 | 2020-11-10 | 武汉纺织大学 | ZIF-8 functional fabric and preparation method thereof |
| CN111939678A (en) * | 2014-05-15 | 2020-11-17 | 霍林斯沃思和沃斯有限公司 | Pre-coalesced multi-layer filter media |
| CN113388155A (en) * | 2021-06-15 | 2021-09-14 | 安徽大学 | Preparation method of super-hydrophobic sponge for efficient oil-water separation |
| CN114288993A (en) * | 2022-03-07 | 2022-04-08 | 农业农村部环境保护科研监测所 | Hetero-pore covalent organic framework integral material and preparation method and application thereof |
-
2022
- 2022-04-22 CN CN202210424793.4A patent/CN114669283A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103394336A (en) * | 2013-07-31 | 2013-11-20 | 武汉大学 | Metal organic framework compound sol-gel coating stirring rod and preparation method and application thereof |
| CN111939678A (en) * | 2014-05-15 | 2020-11-17 | 霍林斯沃思和沃斯有限公司 | Pre-coalesced multi-layer filter media |
| WO2019207475A1 (en) * | 2018-04-24 | 2019-10-31 | Ecole Polytechnique Federale De Lausanne (Epfl) | Method for synthesis of a metal organic framework composite. |
| CN110394062A (en) * | 2019-01-28 | 2019-11-01 | 北京理工大学 | A kind of mixed-matrix plate membrane preparation method of MOF particle modification nanotube filled silicon rubber |
| CN111905816A (en) * | 2020-07-08 | 2020-11-10 | 武汉纺织大学 | ZIF-8 functional fabric and preparation method thereof |
| CN113388155A (en) * | 2021-06-15 | 2021-09-14 | 安徽大学 | Preparation method of super-hydrophobic sponge for efficient oil-water separation |
| CN114288993A (en) * | 2022-03-07 | 2022-04-08 | 农业农村部环境保护科研监测所 | Hetero-pore covalent organic framework integral material and preparation method and application thereof |
Non-Patent Citations (8)
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115746392A (en) * | 2022-11-25 | 2023-03-07 | 中国科学院海洋研究所 | Modified friction power generation sponge, single-electrode sponge friction power generation device, and preparation and application thereof |
| CN115746392B (en) * | 2022-11-25 | 2023-12-19 | 中国科学院海洋研究所 | Modified friction power generation sponge, single-electrode sponge friction power generation device, and preparation and application thereof |
| CN116510706A (en) * | 2023-05-23 | 2023-08-01 | 中北大学 | Preparation method and application of porous nano-sponge loaded MOF material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114669283A (en) | Preparation method of polydimethylsiloxane composite sponge for continuously and efficiently filtering PM | |
| Liu et al. | Efficient and reusable polyamide-56 nanofiber/nets membrane with bimodal structures for air filtration | |
| CN111569665B (en) | Preparation method of flexible graphene oxide/metal organic framework composite filtering membrane | |
| CN109235044A (en) | A kind of polyvinylidene fluoride nanometer tunica fibrosa and its preparation method and application loading ZIF-8 | |
| CN106995531A (en) | The synthesizing preparation method in situ of cellulose/metal organic frame compound and its application | |
| CN113047050B (en) | TiO 2 2 -SiO 2 Preparation method of @ PDMS composite super-hydrophobic filter material | |
| CN112316743B (en) | Preparation method of low-cost low-density catalytic functional ceramic membrane | |
| CN113750968A (en) | Water-insoluble cyclodextrin-based metal organic framework material and preparation method thereof | |
| CN110412087A (en) | One kind being based on NiCoxFe2-xO4Isopropanol gas sensor of nanocube material and preparation method thereof | |
| CN113019137A (en) | Preparation and application of MXene @ COF composite film | |
| CN108970581A (en) | A kind of air cleaning antibiotic property three dimensional stress graphene adsorbent and preparation method | |
| CN106986898B (en) | Preparation method of flower-like nickel metal organic framework nano material and application of flower-like nickel metal organic framework nano material in sensor | |
| CN108735523A (en) | A kind of preparation method and applications with its derivative carbon material of the Zn-MOF of window girder construction | |
| Wu et al. | Research progress on the cleaning and regeneration of PM2. 5 filter media | |
| Shao et al. | Electrospun PS/PAN nanofiber membranes formed from doped carbon nanotubes with a fluffy and multi-scale construction for air-filtration materials | |
| CN104312578A (en) | Fluorescent material with high thermal stability and stable to organic solvent | |
| CN113325036A (en) | GO-MOF composite material and dimethylamine QCM sensor and preparation method thereof | |
| Gou et al. | Rational designed ZIF-8@ PDA@ PDMS composite sponge for efficient and sustainable particulate matter filtering under harsh environment | |
| CN110302766B (en) | Application of organic aerogel as air purification material | |
| CN108854960B (en) | Water filter rod | |
| CN114345301A (en) | Preparation and application of Bi @ chrysotile aerogel for removing radioactive iodine gas and aerosol | |
| CN105401240A (en) | Nano-fiber preparation method capable of catalyzing exhaust gas and absorbing dust particles and based on static spinning technology | |
| CN110787658A (en) | Preparation method of Pebax/ATP mixed matrix membrane | |
| Li et al. | Synergistic enhancement of external electrical energy in PM filtration with Cu-HHTP@ CuO nanowire arrays coated copper mesh | |
| CN109453734A (en) | A kind of MnO2Modified ferrihydrite adsorbing material and preparation method thereof |
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 |
Application publication date: 20220628 |