CN112480478A - Preparation method and application of silver-loaded polymer microspheres - Google Patents
Preparation method and application of silver-loaded polymer microspheres Download PDFInfo
- Publication number
- CN112480478A CN112480478A CN202011171346.XA CN202011171346A CN112480478A CN 112480478 A CN112480478 A CN 112480478A CN 202011171346 A CN202011171346 A CN 202011171346A CN 112480478 A CN112480478 A CN 112480478A
- Authority
- CN
- China
- Prior art keywords
- polymer microspheres
- silver
- loaded polymer
- agno
- steps
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
-
- 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
- C08G16/00—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00
- C08G16/02—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes
- C08G16/025—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with heterocyclic organic compounds
- C08G16/0281—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with heterocyclic organic compounds containing phosphorus in the ring
-
- 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
- C08K3/02—Elements
- C08K3/08—Metals
-
- 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
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
-
- 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)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
本发明提供了一种载银聚合物微球的制备方法及其应用，方法包括如下步骤：(1)将适量氨基单体、含磷分子置于有机溶剂中超声，向上述溶液中滴加含醛基单体的溶液，反应得到聚合物微球；(2)将适量PVP、步骤(1)中的聚合物微球置于水与乙醇混合溶剂中超声，向上述溶液中加入AgNO3溶液，避光搅拌；(3)向步骤(2)中的溶液加入硼氢化钠，搅拌；(4)反应一段时间后离心得到载银聚合物微球。该聚合物微球含氮、磷元素，能够促进体系成炭；负载的银粒子能够催化体系成炭，抑制有害气体产生。The invention provides a preparation method and application of silver-loaded polymer microspheres. The method includes the following steps: (1) placing an appropriate amount of amino monomers and phosphorus-containing molecules in an organic solvent for ultrasonication, and adding dropwise to the above solution The solution of the aldehyde-based monomer is reacted to obtain polymer microspheres; (2) an appropriate amount of PVP and the polymer microspheres in step (1) are placed in a mixed solvent of water and ethanol for ultrasonication, and AgNO3 solution is added to the above solution to avoid Light stirring; (3) adding sodium borohydride to the solution in step (2), stirring; (4) centrifuging to obtain silver-loaded polymer microspheres after reacting for a period of time. The polymer microspheres contain nitrogen and phosphorus elements, which can promote the carbonization of the system; the supported silver particles can catalyze the carbonization of the system and inhibit the generation of harmful gases.
Description
Technical Field
The invention belongs to the technical field of organic flame retardants, and particularly relates to a preparation method and application of silver-loaded polymer microspheres.
Background
The polymer material has the advantages of excellent physical and chemical stability, easy processing and forming and the like, and is widely applied to the fields of buildings, coating paints, packaging and the like. However, most of polymer materials are flammable in practical application, so that flame retardant modification of polymer materials is not slow. However, when a flame retardant is added into a polymer material system, the flame retardant performance of the system is improved and the mechanical properties are reduced. How to consider the flame retardance and the mechanical property of the material is also a problem to be solved by researchers.
With the development of polymer flame retardants, the requirements of people on flame retardants are gradually developing from the original single flame retardant property to multifunctional properties, and it is expected that new functions and properties are imparted to materials while flame retardant modification is performed.
Disclosure of Invention
The invention aims to provide a preparation method of silver-loaded polymer microspheres.
The invention also aims to provide application of the silver-loaded polymer microspheres.
The technical scheme of the invention is as follows:
a preparation method of silver-loaded polymer microspheres comprises the following steps:
(1) synthesis of polymer microspheres: dissolving an amino monomer in a solvent, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), performing ultrasonic treatment at room temperature for 10-20min to obtain a mixed solution, adding an aldehyde monomer and the amino monomer into the mixed solution: aldehyde group monomer: the molar ratio of DOPO was 1: 1-6: 1-6, stirring and reacting for 15-25h to obtain the polymer microsphere.
(2) Synthesis of silver-loaded polymer microspheres: adding polyvinylpyrrolidone (PVP) and the polymer microspheres obtained in the step (1) into a mixed solvent of water and ethanol, and carrying out ultrasonic treatment for 1-2h to obtain a dispersion liquid; adding a certain amount of AgNO with a certain concentration into the dispersion liquid3Stirring the solution for 3-12h in the dark, adding sodium borohydride (NaBH)4) Continuously stirring for 1-4 h; centrifuging, washing the product with solvent, and vacuum drying at 50-70 deg.C to obtain silver-carrying polymer microsphere; wherein, AgNO3The solution concentration is 0.5-10mol/L, PVP and AgNO3The mass ratio is 0.1-10: 1, NaBH4With AgNO3The molar ratio is 2-15: 1.
in a preferred embodiment of the present invention, the amino monomer of step (1) comprises: 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine, tris (4-aminophenyl) amine, 1,3, 5-tris (4-aminophenyl) benzene.
In a preferred embodiment of the present invention, the concentration of the amino monomer in step (1) is 5-20 mg/mL.
In a preferred embodiment of the present invention, the solvent in step (1) comprises at least one of ethanol or methanol.
In a preferred embodiment of the present invention, the aldehyde-based monomer of step (1) includes at least one of terephthalaldehyde and biphenyldicarboxaldehyde.
In a preferred embodiment of the present invention, the concentration of the polymer microspheres in step (1) is 1-9 mg/mL.
In a preferred embodiment of the present invention, the volume ratio of the two solvents in the mixed solvent of water and ethanol of step (2) is 1: 2-8.
In a preferred embodiment of the present invention, the AgNO of step (2)3The solution concentration is 1-5mol/L, PVP and AgNO3The mass ratio is 0.1-4: 1, NaBH4With AgNO3The molar ratio is 5-10: 1.
the invention also provides the application of the silver-loaded polymer microspheres prepared by the preparation method in flame-retardant high polymer materials.
In a preferred embodiment of the present invention, the flame retardant polymer material includes, but is not limited to, bisphenol a epoxy resin, phenolic resin, and the like.
The silver-loaded polymer microsphere has the following characteristics:
(1) the silver-loaded polymer microsphere prepared by the invention contains elements such as phosphorus and nitrogen, and the elements of phosphorus and nitrogen can promote the system to form carbon; the supported silver particles can catalyze the carbonization of the system and inhibit the generation of harmful gases.
(2) The silver-loaded polymer microsphere prepared by the invention contains DOPO groups, can improve the compatibility of the flame retardant and a matrix, and enables the obtained flame-retardant epoxy resin to have better mechanical properties.
(3) The silver-loaded polymer microsphere prepared by the invention contains Schiff base, the C-N bond in the Schiff base is higher, the stability of the polymer microsphere is improved, and the Schiff base can be crosslinked at high temperature and forms a stable network during combustion, so that a certain self-extinguishing property is endowed to a matrix.
(4) The method has the advantages of simple operation, mild reaction conditions and simple and convenient post-treatment process.
Drawings
FIG. 1 is an infrared spectrum of the polymer microsphere prepared in example 1 of the present invention, wherein the abscissa of FIG. 1 is the absorption wavenumber (cm)-1). FIG. 2 is a Scanning Electron Micrograph (SEM) of the polymeric microspheres prepared in example 1 of the present invention, with the scale of the SEM in FIG. 2 being 300 nm.
FIG. 3 is a Transmission Electron Micrograph (TEM) of the silver-loaded polymer microspheres prepared in example 1 of the present invention, and the scale of the TEM in FIG. 3 is 100 nm.
FIG. 4 is a Scanning Electron Micrograph (SEM) of the polymeric microspheres prepared in comparative example 1 of the present invention, with the scale of the SEM in FIG. 4 being 100 nm.
FIG. 5 is a Transmission Electron Micrograph (TEM) of the silver-loaded polymer microspheres prepared in comparative example 2 of the present invention, and the scale of the TEM in FIG. 5 is 200 nm.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The invention will be further described and illustrated with reference to the following figures and examples.
Example 1
And (3) synthesizing the polymer microspheres.
(1) Weighing 200mg of 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine and 400mg of DOPO, dissolving the 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine and the DOPO in 20mL of ethanol, carrying out ultrasonic treatment in an ultrasonic machine with ultrasonic power of 45w for 10min, and then stirring;
(2) weighing 200mg of terephthalaldehyde, dissolving the terephthalaldehyde in 20mL of ethanol, dropwise adding the solution (the dropping speed is 3mL/min) into the solution in the step (1), and carrying out polymerization reaction for 20 hours at room temperature after dropwise adding;
(3) after the reaction is finished, washing the product with ethanol, and centrifuging to obtain the polymer microsphere.
And (3) synthesizing silver-loaded polymer microspheres.
(1) Weighing 3mg of PVP and 40mg of the polymer microspheres obtained in the example 1, adding the PVP and the polymer microspheres into 40mL of a mixed solvent of water and ethanol, and ultrasonically dispersing for 1h in an ultrasonic machine with the ultrasonic power of 45w to obtain a dispersion liquid;
(2) adding 10mL of AgNO with the concentration of 1mol/L into the dispersion liquid of the step (1)3Stirring the solution for 8 hours in the dark;
(3) adding 4mg of sodium borohydride into the solution obtained in the step (1), and reacting for 1-4 h;
(4) and after the reaction is finished, washing the product by using ethanol, and centrifuging to obtain the silver-loaded polymer microspheres.
The results are shown in FIGS. 1 to 3.
The silver-loaded polymer microsphere/epoxy resin system and the flame retardant test thereof are prepared by utilizing the obtained silver-loaded polymer microsphere.
(1) Weighing 20g of epoxy resin, heating to 100 ℃, adding 5 wt% of silver-loaded polymer microsphere flame retardant, and fully and uniformly stirring;
(2) weighing 5g of curing agent 4, 4-diaminodiphenylmethane (DDM), adding into the system in the step (1), and stirring until the curing agent is completely dissolved;
(3) pouring the silver-loaded polymer microspheres/epoxy resin obtained in the step (2) into a mould, and sequentially and respectively curing for 2h, 4h and 2h at the temperature of 120 ℃, 140 ℃ and 180 ℃ to finally obtain the flame-retardant epoxy resin.
The limit oxygen index of the silver-loaded polymer microspheres/epoxy resin measured according to GB/T2406-2009 was 27.6%.
Comparative example 1
And (3) synthesizing the polymer microspheres.
(1) Weighing 100mg of 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine and 200mg of DOPO, dissolving the 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine and the DOPO in 20mL of ethanol, carrying out ultrasonic treatment in an ultrasonic machine with ultrasonic power of 45w for 10min, and then stirring;
(2) weighing 100mg of terephthalaldehyde, dissolving the terephthalaldehyde in 20mL of ethanol, dropwise adding the solution (the dropping speed is 3mL/min) into the solution in the step (1), and carrying out polymerization reaction for 20 hours at room temperature after dropwise adding;
(3) after the reaction is finished, washing the product with ethanol, and centrifuging to obtain the polymer microspheres shown in figure 4. By comparing fig. 2, the polymer of fig. 4 is less spherical.
Comparative example 2
And (3) synthesizing silver-loaded polymer microspheres.
(1) Weighing 5mg of PVP and 40mg of the polymer microspheres obtained in the example 1, adding the PVP and the polymer microspheres into 40mL of a mixed solvent of water and ethanol, and ultrasonically dispersing for 1h in an ultrasonic machine with the ultrasonic power of 45w to obtain a dispersion liquid;
(2) adding 10mL of AgNO with the concentration of 3mol/L into the dispersion liquid of the step (1)3Stirring the solution for 8 hours in the dark;
(3) adding 10mg of sodium borohydride into the solution obtained in the step (1), and reacting for 1-4 h;
(4) after the reaction is finished, washing the product with ethanol, and centrifuging to obtain the silver-loaded polymer microspheres shown in figure 5. By comparing fig. 3, the polymer spheres of fig. 5 were loaded with larger silver particles and were not uniformly loaded.
Claims (10)
1. A preparation method of silver-loaded polymer microspheres is characterized by comprising the following steps: the method comprises the following steps:
(1) synthesis of polymer microspheres: dissolving an amino monomer in a solvent, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide DOPO, performing ultrasonic treatment at room temperature for 10-20min to obtain a mixed solution, adding an aldehyde monomer and the amino monomer into the mixed solution: aldehyde group monomer: the molar ratio of DOPO was 1: 1-6: 1 to 6; stirring and reacting for 15-25h to obtain polymer microspheres;
(2) synthesis of silver-loaded polymer microspheres: adding polyvinylpyrrolidone (PVP) and the polymer microspheres obtained in the step (1) into a mixed solvent of water and ethanol, and carrying out ultrasonic treatment for 1-2h to obtain a dispersion liquid; adding a certain amount of AgNO with a certain concentration into the dispersion liquid3Stirring the solution for 3 to 12 hours in the dark, and adding sodium borohydride NaBH4Continuously stirring for 1-4 h; centrifuging, washing the product with solvent, and vacuum drying at 50-70 deg.C to obtain silver-carrying polymer microsphere; wherein, AgNO3The solution concentration is 0.5-10mol/L, PVP and AgNO3The mass ratio is 0.1-10: 1, NaBH4With AgNO3The molar ratio is 2-15: 1.
2. the method for preparing silver-loaded polymer microspheres according to claim 1, wherein the method comprises the following steps: the amino monomer in the step (1) comprises at least one of 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine, tri (4-aminophenyl) amine and 1,3, 5-tri (4-aminophenyl) benzene.
3. The method for preparing silver-loaded polymer microspheres according to claim 1, wherein the method comprises the following steps: the concentration of the amino monomer is 5-20 mg/mL.
4. The method for preparing silver-loaded polymer microspheres according to claim 1, wherein the method comprises the following steps: the solvent of step (1) comprises at least one of ethanol or methanol.
5. The method for preparing silver-loaded polymer microspheres according to claim 1, wherein the method comprises the following steps: the aldehyde monomer in the step (1) comprises at least one of terephthalaldehyde and biphenyldicarboxaldehyde.
6. The method for preparing silver-loaded polymer microspheres according to claim 1, wherein the method comprises the following steps: the concentration of the polymer microspheres in the step (1) is 1-9 mg/mL.
7. The method for preparing silver-loaded polymer microspheres according to claim 1, wherein the method comprises the following steps: and (3) the volume ratio of two solvents in the mixed solvent of water and ethanol in the step (2) is 1: 2-8.
8. The method for preparing silver-loaded polymer microspheres according to any one of claims 1 to 7, wherein: AgNO of step (2)3The solution concentration is 1-5mol/L, PVP and AgNO3The mass ratio is 0.1-4: 1, NaBH4With AgNO3The molar ratio is 5-10: 1.
9. silver-loaded polymer microspheres prepared according to the preparation method of any one of claims 1 to 7.
10. The silver-loaded polymer microsphere of claim 9 is applied to the preparation of flame-retardant high polymer materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011171346.XA CN112480478B (en) | 2020-10-28 | 2020-10-28 | Preparation method and application of silver-loaded polymer microspheres |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011171346.XA CN112480478B (en) | 2020-10-28 | 2020-10-28 | Preparation method and application of silver-loaded polymer microspheres |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112480478A true CN112480478A (en) | 2021-03-12 |
| CN112480478B CN112480478B (en) | 2021-12-31 |
Family
ID=74927244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011171346.XA Expired - Fee Related CN112480478B (en) | 2020-10-28 | 2020-10-28 | Preparation method and application of silver-loaded polymer microspheres |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112480478B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118324312A (en) * | 2024-06-12 | 2024-07-12 | 西安水创新材料科技有限公司 | Solid slow-release phosphorus-free scale inhibitor and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040077825A1 (en) * | 2002-10-22 | 2004-04-22 | Chang Chun Plastics Co., Ltd. | Phosphorus-containing compound |
| US20060223921A1 (en) * | 2005-04-05 | 2006-10-05 | Monika Bauer | Prepolymers containing phosphororganic compounds and uses thereof |
| CN102974395A (en) * | 2012-12-10 | 2013-03-20 | 南京工程学院 | Eggshell noble metal-polymer ligand catalyst and preparation method thereof |
| CN103788526A (en) * | 2014-01-14 | 2014-05-14 | 鲁东大学 | Preparation method of silver-loaded polymer microspheres |
| CN105038501A (en) * | 2015-07-15 | 2015-11-11 | 厦门大学 | Conductive coating based on noble-metal-loaded polymer nanoparticle and preparation method of conductive coating |
-
2020
- 2020-10-28 CN CN202011171346.XA patent/CN112480478B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040077825A1 (en) * | 2002-10-22 | 2004-04-22 | Chang Chun Plastics Co., Ltd. | Phosphorus-containing compound |
| US20060223921A1 (en) * | 2005-04-05 | 2006-10-05 | Monika Bauer | Prepolymers containing phosphororganic compounds and uses thereof |
| CN102974395A (en) * | 2012-12-10 | 2013-03-20 | 南京工程学院 | Eggshell noble metal-polymer ligand catalyst and preparation method thereof |
| CN103788526A (en) * | 2014-01-14 | 2014-05-14 | 鲁东大学 | Preparation method of silver-loaded polymer microspheres |
| CN105038501A (en) * | 2015-07-15 | 2015-11-11 | 厦门大学 | Conductive coating based on noble-metal-loaded polymer nanoparticle and preparation method of conductive coating |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118324312A (en) * | 2024-06-12 | 2024-07-12 | 西安水创新材料科技有限公司 | Solid slow-release phosphorus-free scale inhibitor and preparation method thereof |
| CN118324312B (en) * | 2024-06-12 | 2024-09-17 | 西安水创新材料科技有限公司 | Solid slow-release phosphorus-free scale inhibitor and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112480478B (en) | 2021-12-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113462127B (en) | A kind of modified boron nitride, composite material containing it, its preparation method and application | |
| CN104826119B (en) | The preparation of the mesoporous silicon oxide@polymer drug carriers of pH and glucose doubling sensitivity | |
| Fu et al. | Epoxy nanocomposites containing mercaptopropyl polyhedral oligomeric silsesquioxane: Morphology, thermal properties, and toughening mechanism | |
| CN113004518B (en) | Phthalonitrile resin prepolymer and preparation method thereof | |
| CN110655652A (en) | A kind of metal hybrid POSS flame retardant, preparation method and application | |
| CN105254828B (en) | The preparation method of eight phenolic hydroxyl group polyhedral oligomeric silsesquioxane hybrid phenol-formaldehyde resins | |
| CN108752637A (en) | A kind of ZIF-8 encapsulation hexachlorocyclotriph,sphazene fire retardant, preparation method and application and fire retarding epoxide resin | |
| WO2018166440A1 (en) | Phosphorus-nitrogen-containing polymer-modified silica nanoparticles, preparation method therefor and use thereof | |
| CN105542229A (en) | Multi-gradient functionalized microcapsule titanium phosphate flame retardant and preparation method thereof | |
| CN112480478B (en) | Preparation method and application of silver-loaded polymer microspheres | |
| CN116041964A (en) | A kind of polymer composite flame retardant and preparation method thereof | |
| Zhou et al. | Controlled architecture of polyhedral oligomeric silsesquioxane-functionalized poly (glycidyl methacrylate)/polyester composites using surface-initiated ICAR ATRP Technique for High Flame Retardancy and Smoke Suppression | |
| CN110144046A (en) | A kind of preparation method of boron-containing phenolic resin microsphere and carbon microsphere | |
| CN110775981A (en) | Silica microspheres and process for producing the same | |
| CN114409874A (en) | Epoxy resin curing agent and preparation method thereof | |
| CN117924637A (en) | Preparation method of efficient flame-retardant phosphorus-containing benzoxazine epoxy resin copolymer | |
| CN119039590A (en) | Cage polysilsesquioxane, fibers comprising same and methods of making | |
| CN118325044A (en) | A method for preparing a DOPO-based functionalized ionic liquid and a modified epoxy resin composite material | |
| CN118702966A (en) | A phosphorus flame retardant modified carbon nanotube and its preparation method and application | |
| CN114426659B (en) | Reactive halogen-free epoxy resin flame-retardant curing agent and preparation method thereof | |
| TW202000720A (en) | Cationically curable composition and cured product production method | |
| TWI757816B (en) | Phosphorus-containing compound, manufacturing method thereof, flame-retardant unsaturated resin composition and thermoset | |
| Gao et al. | Octa (aminophenyl) polyhedral oligomeric silsesquioxane/boron‐containing phenol–formaldehyde resin nanocomposites: Synthesis, cured, and thermal properties | |
| CN111303739B (en) | A kind of hydrophobic flame retardant coating and preparation process thereof | |
| CN113769671A (en) | High-flame-retardant microsphere C60-PMMA composite 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20211231 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |