CN109180952B - Nitrogen-phosphorus-silicon synergistic halogen-free flame retardant grafted with graphene and preparation method thereof - Google Patents
Nitrogen-phosphorus-silicon synergistic halogen-free flame retardant grafted with graphene and preparation method thereof Download PDFInfo
- Publication number
- CN109180952B CN109180952B CN201810783112.7A CN201810783112A CN109180952B CN 109180952 B CN109180952 B CN 109180952B CN 201810783112 A CN201810783112 A CN 201810783112A CN 109180952 B CN109180952 B CN 109180952B
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- nitrogen
- graphene
- phosphorus
- free flame
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
Abstract
The invention belongs to the technical field of flame retardants, and mainly relates to a nitrogen-phosphorus-silicon synergistic halogen-free flame retardant grafted with graphene and a preparation method thereof, wherein 3-aminopropyl-triethoxysilane is synthesized into octaaminopropyl cage-type silsesquioxane through a hydrolytic condensation polymerization method; preparing graphene oxide by carrying out chemical oxidation and stripping on graphene through an improved hummers method; synthesizing a grafted product 1 with a reactive functional group by using 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and graphene oxide through an in-situ polymerization method; the octa-aminopropyl cage-type silsesquioxane and the grafted product 1 are synthesized into the nitrogen-phosphorus-silicon synergistic halogen-free flame retardant of the grafted graphene through an in-situ polymerization method. The preparation method of the nitrogen-phosphorus-silicon synergistic halogen-free flame retardant grafted with the graphene has the advantages of simple preparation process, safety, environmental friendliness and the like, can be widely applied to flame retardance in the fields of electronic appliances, automobiles, cables, packaging, aviation and the like, and has a wide development prospect.
Description
Technical Field
The invention belongs to the technical field of flame retardants, and mainly relates to a nitrogen-phosphorus-silicon synergistic halogen-free flame retardant grafted with graphene and a preparation method thereof.
Background
The cage type oligomeric silsesquioxane (POSS) is a nano organic silicon material and has a unique polyhedral cage type structure, a cage type framework consists of Si-O-Si bonds, and Si atoms at the vertex angles of a polyhedron can be connected with different organic functional groups. The special structure enables POSS to have unique physicochemical properties, namely an organic-inorganic hybrid structure formed by an inorganic core and an organic functional group endows the cage-type oligomeric silsesquioxane with excellent heat resistance and higher reaction activity; the nanometer size endows the material with special thermodynamic, magnetic and optical properties; by molecular design, various functionalized cage type oligomeric silsesquioxanes are prepared, and different reactivities and functionalities can be endowed to the functionalized cage type oligomeric silsesquioxanes. Compared with other polymers, the organic silicon polymer and the cage type oligomeric silsesquioxane have better compatibility, and the functionalized cage type oligomeric silsesquioxane is applied to the preparation and modification of high molecular materials by a physical or chemical method, so that the physical and chemical properties of the materials can be obviously improved, and the application field of the materials is widened.
9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) contains active P-H bonds, can react with alkenyl, alkynyl, epoxy group, carbonyl, imine, cyano, amine and the like, and the phosphaphenanthrene group has the characteristics of non-coplanarity, interactivity with intramolecular or intermolecular groups, large volume structure, molecular polarity and the like, it is used as a modifying group for constructing micromolecules and polymers, can ensure that the molecules respectively obtain flame retardant property, unique aggregation state structure, luminescent property and good organic solubility, therefore, the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative as an environment-friendly flame retardant has the characteristics of no halogen, low toxicity, no smoke and the like and also has high flame retardant efficiency. Therefore, the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide based flame retardant system has obvious advantages and good application prospect no matter from the consideration of environmental protection or cost reduction.
Graphene Oxide (GO) is an intermediate product for preparing graphene by using a redox method, and can improve the mechanical property, the thermal property and the like of a polymer by compounding with the polymer, so that the Graphene Oxide (GO) is well applied to the field of composite materials. However, researches find that graphene oxide is a precursor for preparing graphene in the field of materials, and has good application prospects in other fields such as chemistry, chemical engineering and the like. The graphene oxide has a special two-dimensional lamellar structure, and the surface of the graphene oxide also contains a large number of oxygen-containing functional groups, so that the graphene oxide is endowed with good dispersion performance in a polar solvent and good surface reactivity, and a structural basis is laid for the functionalization and the chemical reaction participating in the synthesis of a new compound.
The chemical composition of the high polymer material is mainly composed of elements such as carbon, hydrogen, oxygen and the like, most of the elements have low limiting oxygen index, and are easy to burn to cause fire, so that great loss is caused to lives and properties of people, and therefore the high polymer material needs to be subjected to flame retardance, and a high-performance halogen-free flame retardant is researched and developed. The flame retardant for the high polymer material mainly comprises a halogen flame retardant, an inorganic flame retardant, a halogen-free flame retardant and the like. The traditional halogen flame retardant has the advantages of higher flame retardant efficiency and less addition amount, but the halogen flame retardant can release a large amount of toxic and harmful gases and smoke when a flame-retardant product is burnt, and the personal safety and the property safety are seriously damaged. Inorganic flame retardant such as magnesium hydroxide in the halogen-free flame retardant has the advantages of high safety, smoke suppression, no toxicity, low price and the like, but has the defect of large addition amount (generally 50-60%), great influence on mechanical and electrical properties of materials and easy generation of molten drops during combustion. In addition to inorganic flame retardants, other halogen-free flame retardants such as nitrogen and phosphorus systems are receiving attention from people in terms of better flame retardant effect, low smoke, no toxicity and relatively small addition amount, and particularly have incomparable advantages with other types of flame retardants in solving the problem of melt dripping of flame retardancy of composite materials. Therefore, with the increasing concern of people on health and environmental protection, the use of halogen flame retardants is gradually forbidden, and the development of environment-friendly intrinsic or additive multi-element synergistic intumescent halogen-free flame retardant compounds has very important scientific significance and broad market prospects and is also very necessary.
The development direction of the future flame retardant is as follows: the halogen flame retardant such as decabromodiphenyl ether is developed to replace halogen flame retardant such as certain halogen-free flame retardant and intumescent flame retardant with unique performance, so that the flame retardant high polymer material has good fluidity, low permeability, compatibility, easy recovery and good dimensional stability.
In order to better utilize the effects of high thermal stability, smoke suppression and combustion suppression of POSS, DOPO and GO and the catalytic carbonization of the POSS, DOPO and GO on the surface of a polymer to form a high-quality protective carbon layer, a nitrogen-phosphorus-silicon synergistic halogen-free flame retardant with both POSS and DOPO grafted on a GO lamellar structure is prepared by utilizing the reaction among functional groups with strong reaction activity among the POSS, DOPO and GO. The flame retardant has high stability and structural controllability, so that the high-efficiency flame retardance of a system is realized, and the flame retardant is not reported at home and abroad.
Disclosure of Invention
The invention mainly solves the technical problems that: at present, a halogen flame retardant generates a large amount of smoke and releases toxic and corrosive hydrogen halide gas during combustion, thereby causing secondary pollution; although halogen-free flame retardant systems such as aluminum hydroxide, magnesium hydroxide and the like do not generate toxic hydrogen halide gas, the flame retardant efficiency is low, and the halogen-free flame retardant systems need large filling amount to have flame retardancy, so that the processing performance and the mechanical property of the material are influenced; on the other hand, the general flame-retardant nanocomposite material has problems of dispersibility and compatibility with a polymer matrix, and the use of the flame-retardant nanocomposite material is limited. Therefore, the invention provides a preparation method of the nitrogen-phosphorus-silicon synergistic halogen-free flame retardant grafted with graphene, and the preparation method is simple in preparation process and environment-friendly.
The invention provides a nitrogen-phosphorus-silicon synergistic halogen-free flame retardant grafted with graphene, which is formed by in-situ grafting octaaminopropyl cage-type silsesquioxane, graphene oxide and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.
The preparation method of the nitrogen-phosphorus-silicon synergistic halogen-free flame retardant grafted with graphene comprises the following steps:
step 1: hydrolyzing, condensing and polymerizing 3-aminopropyl-triethoxysilane under the catalysis of acetonitrile and tetraethylammonium hydroxide to synthesize a reaction intermediate product 1, namely the octaaminopropyl cage-type silsesquioxane; the reaction temperature for synthesizing the octaaminopropyl cage-type silsesquioxane is 50-70 ℃, preferably 55-65 ℃, and the reaction catalyst is at least one of triethylamine, acetonitrile and tetraethylammonium hydroxide solution which are volatile and can regulate and control the pH value of the solution. The reaction product was washed with acetone solution and extracted with methanol.
Step 2: preparing graphene oxide by chemically oxidizing and stripping graphene under the action of concentrated sulfuric acid, concentrated phosphoric acid and potassium permanganate through an improved hummers method; the reaction temperature for synthesizing the graphene oxide is not more than 95 ℃. The oxidant metering ratio in the synthesized graphene oxide solution is concentrated sulfuric acid and concentrated phosphoric acid which is 9/1.
And step 3: synthesizing a reaction intermediate product 2 with a reactive functional group by using 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and the graphene oxide synthesized in the step 2 in a tetrahydrofuran solution through an in-situ polymerization method under the protection of nitrogen;
and 4, step 4: synthesizing a nitrogen-phosphorus-silicon synergistic halogen-free flame retardant grafted with graphene by an in-situ polymerization method in tetrahydrofuran solution under the catalysis of dicyclohexylcarbodiimide and under the protection of nitrogen by using the reaction intermediate product 1 synthesized in the step 1 and the reaction intermediate product 2 synthesized in the step 3, wherein the halogen-free flame retardant is a compound grafted by octaaminopropyl cage-type silsesquioxane, graphene oxide and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.
The washing solvents required by the present invention are anhydrous methanol and tetrahydrofuran.
The catalyst required in step 4 is dicyclohexylcarbodiimide.
The synthesis of the reactive intermediate 2 and the nitrogen-phosphorus-silicon-containing synergistic halogen-free flame retardant needs to be carried out in tetrahydrofuran solution under the protection of nitrogen and filtered by a 0.2-0.45 micron polytetrafluoroethylene film.
The nitrogen-phosphorus-silicon synergistic halogen-free flame retardant grafted with graphene and the preparation method thereof have the following advantages:
1. the non-halogenation synthesis of the nitrogen-phosphorus-silicon-containing flame-retardant element on the surface of the graphene is realized for the first time, the multi-element synergistic flame-retardant effect of the three flame-retardant elements and the barrier effect of the graphene can be fully exerted, and the method has important scientific and practical innovative significance.
2. No harmful pollutants are generated in the combustion process, the smoke yield is low, the environment is protected, the efficiency is high, and the application value and the application prospect are high.
3. Under long-term high-temperature conditions, the stability and the flame-retardant effect are still remarkable, and the flame-retardant coating can be suitable for more extreme environments.
4. The flame retardant can be compounded with common intumescent flame retardants, metal flame retardants and biomass flame retardants to play a synergistic flame retardant role, so that the addition amount of the flame retardants is reduced, the flame retardant effect is improved, and the application of the flame retardant in the flame retardant field is widened.
5. The prepared graphene oxide, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and octaaminopropyl cage-type silsesquioxane with low cost and environmental friendliness are used as halogen-free flame retardants to synthesize the three-in-one nitrogen-containing phosphorus-silicon synergistic halogen-free flame retardant, and the halogen-free flame retardant has the advantages of environmental friendliness, low price and sustainable development.
Detailed Description
The present invention is described in detail below by way of examples, it being necessary here to point out that the following examples are only intended to illustrate the invention further and are not to be construed as limiting the scope of protection of the invention, which is susceptible to numerous insubstantial modifications and adaptations by those skilled in the art.
Example 1
A500 ml three-necked flask was placed in a 50 ℃ constant temperature water bath, and then 40ml of distilled water, 10ml of isopropyl alcohol, 2ml of acetonitrile, 10ml of triethylamine and 2ml of tetraethylammonium hydroxide were sequentially added to the three-necked flask, and stirred at a medium speed to mix them uniformly. 80g of 3-aminopropyltriethoxysilane was added dropwise to the mixture, and the mixture was refluxed at a constant temperature of 50 ℃ for 12 hours. After the reaction, the reaction solution was distilled under reduced pressure, and a large amount of white solid was precipitated by standing. Vacuum filtering, washing with acetone, and extracting with methanol. Vacuum drying to obtain yellow solid product octaaminopropyl cage type silsesquioxane, namely reaction intermediate 1.
And adding 500mg of graphene oxide into 500ml of tetrahydrofuran, and performing ultrasonic dispersion for 1 h. The dispersion was transferred into a three-necked flask charged with nitrogen, and 100ml of a tetrahydrofuran solution containing 5g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was added thereto and stirred. The mixture was heated to 50 ℃ and refluxed under nitrogen for 12 h. After the functionalization process is complete, the mixture is filtered through a 0.2 μm teflon membrane to remove the product. Then, the reaction intermediate 2 is obtained by thoroughly washing and removing the residual reactant with anhydrous tetrahydrofuran and acetone, and finally, drying in vacuum at 80-90 ℃ to remove the reaction solvent.
The prepared reaction intermediate 2 was initially dispersed in 500ml of tetrahydrofuran and sonicated for 2h to give a suspension, and then reaction intermediate 1 and N, N-dicyclohexylcarbodiimide were added to the above-obtained suspension and sonicated for 1 h. The mixture was magnetically stirred at 65 ℃ under nitrogen and refluxed for 24 h. After the reaction was completed, the solution was vacuum filtered through a 0.2 μm polytetrafluoroethylene membrane and washed three times with sufficient amounts of anhydrous methanol and anhydrous tetrahydrofuran. Finally, the solid obtained is dried in a vacuum oven at 80 ℃ and 0.1MPa overnight to remove the solvent, thus obtaining the product.
Example 2
A500 ml three-necked flask was placed in a constant temperature water bath of 60 ℃ and then 60ml of distilled water, 20ml of isopropyl alcohol, 2ml of acetonitrile, 10ml of triethylamine and 2ml of tetraethylammonium hydroxide were sequentially added to the three-necked flask and stirred at a medium speed to mix them uniformly. 100g of 3-aminopropyltriethoxysilane was added dropwise to the mixture, and the mixture was refluxed at a constant temperature of 60 ℃ for 24 hours. After the reaction, the reaction solution was distilled under reduced pressure, and a large amount of white solid was precipitated by standing. Vacuum filtering, washing with acetone, and extracting with methanol. Vacuum drying to obtain yellow solid product octaaminopropyl cage type silsesquioxane, namely reaction intermediate 1.
And adding 500mg of graphene oxide into 500ml of tetrahydrofuran, and performing ultrasonic dispersion for 1 h. The dispersion was transferred into a three-necked flask charged with nitrogen, and 100ml of a tetrahydrofuran solution containing 10g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was added thereto and stirred. The mixture was heated to 60 ℃ and reacted under nitrogen at reflux for 24 h. After the functionalization process is complete, the mixture is filtered through a 0.45 μm teflon membrane to remove the product. Then, the reaction intermediate 2 is obtained by thoroughly washing and removing the residual reactant with anhydrous tetrahydrofuran and acetone, and finally, drying in vacuum at 80-90 ℃ to remove the reaction solvent.
The prepared reaction intermediate 2 was initially dispersed in 500ml of tetrahydrofuran and sonicated for 2h to give a suspension, and then reaction intermediate 1 and N, N-dicyclohexylcarbodiimide were added to the above-obtained suspension and sonicated for 1 h. The mixture was magnetically stirred at 75 ℃ under nitrogen and refluxed for 36 h. After the reaction was completed, the solution was vacuum filtered through a 0.45 μm polytetrafluoroethylene membrane and washed three times with sufficient amounts of anhydrous methanol and anhydrous tetrahydrofuran. Finally, the solid obtained is dried in a vacuum oven at 80 ℃ and 0.1MPa overnight to remove the solvent, thus obtaining the product.
Example 3
A500 ml three-necked flask was placed in a constant temperature water bath of 65 ℃ and then 80ml of distilled water, 30ml of isopropyl alcohol, 2ml of acetonitrile, 10ml of triethylamine and 2ml of tetraethylammonium hydroxide were sequentially added to the three-necked flask and stirred at a medium speed to mix them uniformly. 120g of 3-aminopropyltriethoxysilane was added dropwise to the mixture, and the mixture was refluxed at a constant temperature of 65 ℃ for 36 hours. After the reaction, the reaction solution was distilled under reduced pressure, and a large amount of white solid was precipitated by standing. Vacuum filtering, washing with acetone, and extracting with methanol. Vacuum drying to obtain yellow solid product octaaminopropyl cage type silsesquioxane, namely reaction intermediate 1.
And adding 1g of graphene oxide into 500ml of tetrahydrofuran, and performing ultrasonic dispersion for 1 h. The dispersion was transferred into a three-necked flask charged with nitrogen, and 100ml of a tetrahydrofuran solution containing 15g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was added thereto and stirred. The mixture was heated to 65 ℃ and refluxed under nitrogen for 36 h. After the functionalization process is complete, the mixture is filtered through a 0.22 μm teflon membrane to remove the product. Then, the reaction intermediate 2 is obtained by thoroughly washing and removing the residual reactant with anhydrous tetrahydrofuran and acetone, and finally, drying in vacuum at 80-90 ℃ to remove the reaction solvent.
The prepared reaction intermediate 2 was initially dispersed in 500ml of tetrahydrofuran and sonicated for 2h to give a suspension, and then reaction intermediate 1 and N, N-dicyclohexylcarbodiimide were added to the above-obtained suspension and sonicated for 1 h. The mixture was magnetically stirred at 80 ℃ under nitrogen and refluxed for 48 h. After the reaction was completed, the solution was vacuum filtered through a 0.22 μm polytetrafluoroethylene membrane and washed three times with sufficient amounts of anhydrous methanol and anhydrous tetrahydrofuran. Finally, the solid obtained is dried in a vacuum oven at 80 ℃ and 0.1MPa overnight to remove the solvent, thus obtaining the product.
Example 4
A500 ml three-necked flask was placed in a constant temperature water bath of 65 ℃ and then 80ml of distilled water, 30ml of isopropyl alcohol, 2ml of acetonitrile, and 2ml of tetraethylammonium hydroxide were sequentially added to the three-necked flask, and stirred at a medium speed to mix them uniformly. 120g of 3-aminopropyltriethoxysilane was added dropwise to the mixture, and the reaction was refluxed at a constant temperature of 65 ℃ for 36 hours. After the reaction, the reaction solution was distilled under reduced pressure, and a large amount of white solid was precipitated by standing. Vacuum filtering, washing with acetone, and extracting with methanol. Vacuum drying to obtain yellow solid product octaaminopropyl cage type silsesquioxane, namely reaction intermediate 1.
And adding 1g of graphene oxide into 500ml of tetrahydrofuran, and performing ultrasonic dispersion for 1 h. The dispersion was transferred into a three-necked flask charged with nitrogen, and 100ml of a tetrahydrofuran solution containing 20g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was added thereto, and stirred. The mixture was heated to 70 ℃ and reacted under nitrogen at reflux for 36 h. After the functionalization process is complete, the mixture is filtered through a 0.3 μm teflon membrane to remove the product. Then, the reaction intermediate 2 is obtained by thoroughly washing and removing the residual reactant with anhydrous tetrahydrofuran and acetone, and finally, drying in vacuum at 80-90 ℃ to remove the reaction solvent.
The prepared reaction intermediate 2 was initially dispersed in 500ml of tetrahydrofuran and sonicated for 2h to give a suspension, and then reaction intermediate 1 and N, N-dicyclohexylcarbodiimide were added to the above-obtained suspension and sonicated for 1 h. The mixture was magnetically stirred at 80 ℃ under nitrogen and refluxed for 48 h. After the reaction was completed, the solution was vacuum filtered through a 0.3 μm polytetrafluoroethylene membrane and washed three times with sufficient amounts of anhydrous methanol and anhydrous tetrahydrofuran. Finally, the solid obtained is dried in a vacuum oven at 80 ℃ and 0.1MPa overnight to remove the solvent, thus obtaining the product.
Example 5
A500 ml three-necked flask is placed in a constant temperature water area of 65 ℃, and then 80ml of distilled water, 20ml of isopropanol, 2ml of acetonitrile and 10ml of triethylamine are sequentially added into the three-necked flask, and stirred at a medium speed to mix uniformly. 120g of 3-aminopropyltriethoxysilane was added dropwise to the mixture, and the mixture was refluxed at a constant temperature of 65 ℃ for 24 hours. After the reaction, the reaction solution was distilled under reduced pressure, and a white solid was precipitated by standing. Vacuum filtering, washing with acetone, and extracting with methanol. Vacuum drying to obtain yellow solid product octaaminopropyl cage type silsesquioxane, namely reaction intermediate 1.
And 2g of graphene oxide is added into 500ml of tetrahydrofuran, and ultrasonic dispersion is carried out for 1 h. The dispersion was transferred into a three-necked flask charged with nitrogen, and 100ml of a tetrahydrofuran solution containing 20g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was added thereto, and stirred. The mixture was heated to 70 ℃ and reacted under nitrogen at reflux for 36 h. After the functionalization process is complete, the mixture is filtered through a 0.4 μm teflon membrane to remove the product. Then, the reaction intermediate 2 is obtained by thoroughly washing and removing the residual reactant with anhydrous tetrahydrofuran and acetone, and finally, drying in vacuum at 80-90 ℃ to remove the reaction solvent.
Prepared reaction intermediate 2 was initially dispersed in 500ml of tetrahydrofuran and sonicated for 2h to give a suspension, and then reaction intermediate 1 was added to the above-obtained suspension and sonicated for 1 h. The mixture was magnetically stirred at 80 ℃ under nitrogen and refluxed for 48 h. After the reaction was completed, the solution was vacuum filtered through a 0.4 μm polytetrafluoroethylene membrane and washed three times with sufficient amounts of anhydrous methanol and anhydrous tetrahydrofuran. Finally, the solid was dried in a vacuum oven at 80 ℃ and 0.1MPA overnight to remove the solvent to give the product.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (8)
1. The preparation method of the nitrogen-phosphorus-silicon synergistic halogen-free flame retardant grafted with the graphene is characterized in that the flame retardant is formed by in-situ grafting octaaminopropyl cage-type silsesquioxane, graphene oxide and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and comprises the following steps:
(1) synthesizing a reactive intermediate 1 from 3-aminopropyl-triethoxysilane by a hydrolytic condensation polymerization method: octaaminopropyl cage silsesquioxane;
(2) preparing graphene oxide by carrying out chemical oxidation and stripping on graphene through an improved hummers method;
(3) synthesizing a reaction active intermediate 2 by using 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and graphene oxide through an in-situ polymerization method;
(4) and (3) synthesizing the nitrogen-phosphorus-silicon-containing synergistic halogen-free flame retardant by the reactive intermediate 1 and the reactive intermediate 2 through an in-situ polymerization method.
2. The preparation method of the nitrogen-phosphorus-silicon synergistic halogen-free flame retardant grafted with the graphene according to claim 1, wherein in the step (1), the 3-aminopropyl-triethoxysilane is used for synthesizing the octaaminopropyl cage-type silsesquioxane, and the catalyst is a triethylamine solution, an acetonitrile solution and a tetraethylammonium hydroxide solution which are volatile and can regulate and control the solution p H.
3. The preparation method of the nitrogen-phosphorus-silicon synergistic halogen-free flame retardant grafted with graphene according to claim 2, wherein the reaction time for synthesizing the octaaminopropyl cage-type silsesquioxane in the step (1) is 1-3 days, the reaction temperature is 50-70 ℃, the reaction product is washed by acetone solution, and finally, methanol is used for extraction.
4. The preparation method of the nitrogen-phosphorus-silicon synergistic halogen-free flame retardant grafted with graphene according to claim 1, wherein the reaction temperature for preparing graphene oxide in the step (2) is not more than 95 ℃; the oxidant metering ratio in the synthesized graphene oxide solution is concentrated sulfuric acid: the concentrated phosphoric acid is 9/1, the potassium permanganate is added in batches slowly, and the hydrogen peroxide is added finally.
5. The preparation method of the nitrogen-phosphorus-silicon synergistic halogen-free flame retardant grafted with graphene according to claim 1, wherein the reaction time for preparing the reactive intermediate 2 in the step (3) is 1-5 days, the reactive intermediate is synthesized in a tetrahydrofuran solution under the protection of nitrogen, and a product is subjected to vacuum filtration by using a polytetrafluoroethylene film with the thickness of 0.2-0.45 microns.
6. The preparation method of the nitrogen-phosphorus-silicon synergistic halogen-free flame retardant grafted with graphene according to claim 1, wherein the nitrogen-phosphorus-silicon synergistic halogen-free flame retardant synthesized in the step (4) is catalyzed by dicyclohexylcarbodiimide and synthesized in tetrahydrofuran solution under the protection of nitrogen.
7. The preparation method of the nitrogen-phosphorus-silicon synergistic halogen-free flame retardant grafted with graphene according to claim 1, wherein the step (4) further comprises washing the product with anhydrous methanol and tetrahydrofuran for several times, and performing vacuum filtration with a 0.2-0.45 micrometer polytetrafluoroethylene film.
8. The nitrogen-phosphorus-silicon synergistic halogen-free flame retardant grafted with graphene is characterized by being prepared by the preparation method of any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810783112.7A CN109180952B (en) | 2018-07-17 | 2018-07-17 | Nitrogen-phosphorus-silicon synergistic halogen-free flame retardant grafted with graphene and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810783112.7A CN109180952B (en) | 2018-07-17 | 2018-07-17 | Nitrogen-phosphorus-silicon synergistic halogen-free flame retardant grafted with graphene and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109180952A CN109180952A (en) | 2019-01-11 |
| CN109180952B true CN109180952B (en) | 2020-08-04 |
Family
ID=64936766
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810783112.7A Active CN109180952B (en) | 2018-07-17 | 2018-07-17 | Nitrogen-phosphorus-silicon synergistic halogen-free flame retardant grafted with graphene and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109180952B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110041612B (en) * | 2019-04-01 | 2021-03-30 | 四川大学 | Halogen-free flame-retardant polypropylene composite material compatibilized by oligomeric silsesquioxane and synergistic effect and preparation method thereof |
| CN111269461A (en) * | 2020-03-09 | 2020-06-12 | 贵州民族大学 | Phosphaphenanthrene silane grafted and modified graphene and preparation method thereof |
| CN111662475B (en) * | 2020-06-17 | 2022-12-23 | 山东师范大学 | Intelligent early warning flame-retardant material prepared from modified high-molecular polymer, and preparation method and application thereof |
| CN112341825A (en) * | 2020-11-06 | 2021-02-09 | 陕西科技大学 | Environment-friendly flame-retardant ternary composite material POSS/GO/ZIF-8 and preparation method thereof |
| CN112938955B (en) * | 2021-04-02 | 2022-11-08 | 青岛量子元基环保科技有限公司 | Chemical preparation method of single-layer porous graphene |
| CN115536910B (en) * | 2022-09-29 | 2023-06-30 | 南京鸿瑞塑料制品有限公司 | Preparation method of DOPO derivative grafted graphene oxide/layered double hydroxide composite flame retardant |
| CN115477827B (en) * | 2022-10-18 | 2023-09-26 | 北京服装学院 | Preparation method and application of phosphorus-nitrogen-silicon composite intumescent flame retardant |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101503419A (en) * | 2009-03-20 | 2009-08-12 | 北京化工大学 | Octa-aminopropyl cage type sesquialter siloxane and preparation thereof |
-
2018
- 2018-07-17 CN CN201810783112.7A patent/CN109180952B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101503419A (en) * | 2009-03-20 | 2009-08-12 | 北京化工大学 | Octa-aminopropyl cage type sesquialter siloxane and preparation thereof |
Non-Patent Citations (3)
| Title |
|---|
| Deposition of amino-functionalized polyhedral oligomeric silsesquioxanes on graphene oxide sheets immobilized onto an amino-silane modified silicon surface;Luca Valentini，Silvia Bittolo Bon etl.;《Journal of Materials Chemistry》;20120217;第6213-6217页 * |
| 侯培鑫，何锴慰 等.磷硅元素改性氧化石墨烯的制备及其阻燃改性环氧树脂的应用.《厦门大学学报（自然科学版）》.2017, * |
| 磷硅元素改性氧化石墨烯的制备及其阻燃改性环氧树脂的应用;侯培鑫，何锴慰 等;《厦门大学学报（自然科学版）》;20170915;第186-192页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109180952A (en) | 2019-01-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109180952B (en) | Nitrogen-phosphorus-silicon synergistic halogen-free flame retardant grafted with graphene and preparation method thereof | |
| CN111072973B (en) | Phosphorus-containing POSS, preparation method thereof and application thereof in flame retardant | |
| CN107090083B (en) | Nitrogen-phosphorus-silicon copolymer with double-layer silsesquioxane as main chain and preparation method and application thereof | |
| CN111793090A (en) | DOPO silicon phosphorus synergistic flame retardant and preparation method and application thereof | |
| CN106700078A (en) | Hybridization structured polysiloxane flame retardant and preparation method thereof | |
| CN110511431B (en) | Application of nitrogen-phosphorus efficient flame retardant containing benzoguanamine structure | |
| CN105001451A (en) | Graphene containing DOPO group and preparation method thereof | |
| CN110643018B (en) | Bio-based flame-retardant epoxy resin containing nitrogen and phosphorus structures and preparation method thereof | |
| CN109135189A (en) | A kind of epoxy resin poly- phosphorus silazane fire retardant of multielement containing P/N/Si and preparation method thereof | |
| CN115010993A (en) | Preparation method and application of graphene oxide hybrid flame retardant | |
| CN108586807B (en) | Flame-retardant functionalized graphene and preparation and application thereof | |
| CN111253437A (en) | P/N/Si-containing multi-element reactive epoxy resin flame retardant and preparation method thereof | |
| CN101659677B (en) | Triphosphazene epoxy resin and preparation method thereof | |
| CN108424617B (en) | Preparation method and application of ferric oxide hydroxide loaded graphene oxide flame retardant | |
| CN109082017B (en) | Phosphorus-doped carbon nanotube/organic modified layered double hydroxide/polyolefin flame-retardant material 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 | |
| CN105801867B (en) | A kind of expansion type flame retardant and preparation method thereof based on biomass structure | |
| CN107501526B (en) | DOPO type epoxy resin curing agent and preparation method thereof | |
| CN110591388A (en) | Flame-retardant smoke suppressant containing cobalt, nitrogen and silicon and preparation method thereof | |
| CN113174057B (en) | Nitrogen-phosphorus synergistic Al-based MOFs flame retardant and preparation method and application thereof | |
| CN112521660B (en) | Titanium dioxide hybrid nano particle flame retardant containing phosphorus, nitrogen and silicon and preparation method and application thereof | |
| CN115594943A (en) | Modified carbon nanotube flame-retardant reinforced epoxy resin and preparation method thereof | |
| CN113121882B (en) | Functionalized graphene oxide-aluminum hypophosphite flame retardant and preparation method and application thereof | |
| CN112625064B (en) | Cyclotriphosphazene modified graphene and preparation method and application thereof | |
| CN114685937A (en) | Flame-retardant epoxy resin 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 |