CN114316366B - Preparation method and application of phosphorus-grafted titanium hydroxide/graphene flame retardant - Google Patents
Preparation method and application of phosphorus-grafted titanium hydroxide/graphene flame retardant Download PDFInfo
- Publication number
- CN114316366B CN114316366B CN202111582643.8A CN202111582643A CN114316366B CN 114316366 B CN114316366 B CN 114316366B CN 202111582643 A CN202111582643 A CN 202111582643A CN 114316366 B CN114316366 B CN 114316366B
- Authority
- CN
- China
- Prior art keywords
- graphene
- titanium hydroxide
- phosphorus
- flame retardant
- grafted
- 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
Images
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method and application of a phosphorus grafted titanium hydroxide/graphene flame retardant, which comprises the steps of dispersing graphene nano sheets in a suspension by ultrasonic waves, depositing titanium hydroxide on graphene nano sheet layers by using a chemical precipitation method to obtain titanium hydroxide/graphene, grafting a silane coupling agent on the titanium hydroxide/graphene by using a dehydration reaction principle, and finally hydrolyzing-NH carried by the silane coupling agent and a-P-Cl group in diphenyl chlorophosphate 2 The groups are subjected to substitution reaction, so that organic phosphorus groups are grafted to the inorganic titanium hydroxide/graphene. The phosphorus-containing grafted titanium hydroxide/graphene composite flame retardant disclosed by the invention has a good flame retardant property and can play a role in the synergistic flame retardance of inorganic titanium hydroxide/graphene and organic phosphorus.
Description
Technical Field
The invention relates to the technical field of environment-friendly flame retardants, and particularly relates to a preparation method and application of a phosphorus-grafted titanium hydroxide/graphene flame retardant.
Background
Epoxy resin (EP) is an important thermosetting polymer having good chemical stability, low curing shrinkage, excellent adhesion and excellent processability, and has been widely used in composite materials, anticorrosive coatings, adhesives and decorative materials. However, the Limited Oxygen Index (LOI) of epoxy resin is only about 20%, and its combustion process is accompanied by a large amount of smoke and toxic gases, which severely limits its wide application. In recent years, various types of flame retardants have been added to epoxy resins to improve their flame retardant properties and reduce toxic fumes from combustion. In recent years, flame retardants are generally added to epoxy resins to improve the flame retardancy and reduce the combustion smoke yield, wherein the modified graphene oxide flame retardants not only can enhance the flame retardancy and mechanical properties of the epoxy resins, but also have no adverse effect of serious environmental pollution when halogen flame retardants are combusted. Therefore, flame retardant epoxy resins of graphene and derivatives thereof have been widely studied.
Graphene is a two-dimensional flaky nano material, is formed by connecting benzene six-membered rings consisting of carbon atoms, and has high mechanical strength and specific surface area (2600 m) 2 In terms of/g). The layered graphene may be dispersed in the polymer matrix to form a "tortuous path" effect to slow the rate of decomposition and thermal diffusion of the epoxy matrix. Therefore, it is often used as a flame retardant or a flame retardant carrier, not only to enhance the flame retardancy of the substrate, but also to enhance the mechanical properties of the substrate. In recent years, graphene has attracted extensive attention and research in the field of flame retardants. However, graphene tends to aggregate irreversibly due to strong van der waals forces and pi-pi stacking interactions, resulting in a decrease in its flame retardant properties. To solve this problem, it is generally used to modify graphene by covalent or non-covalent bonds to improve the dispersibility of graphene in a polymer matrix. In addition, graphene is often used in combination with other flame retardants to achieve synergy.
Titanium hydroxide Ti (OH) 4 Decomposing and absorbing heat at a certain temperature to consume energy and reduce temperature of condensed phase and dilute combustible gas in gas phase, so as to reduce temperature rise of polymer material, slow or prevent combustion, and thermally decompose TiO 2 Has the functions of promoting the catalytic oxidation of carbon monoxide and promoting the carbon formation.
Therefore, the research and development of the novel flame retardant aim to improve the flame retardant property of the epoxy resin, and the novel flame retardant has important significance for reducing the fire hazard of the epoxy composite material of the civil aircraft and widening the application prospect.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method and application of a phosphorus grafted titanium hydroxide/graphene flame retardant, which play a role in the synergistic flame retardance of inorganic titanium hydroxide/graphene and organic phosphorus, prepare a novel inorganic-organic hybrid flame retardant, improve the flame retardant property of epoxy resin and solve the problems in the background art.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a phosphorus grafted titanium hydroxide/graphene flame retardant comprises the following steps: preparing titanium hydroxide/graphene by using a chemical precipitation method, and grafting a phosphorus-containing group to the titanium hydroxide/graphene through a two-step method to obtain the phosphorus-containing grafted titanium hydroxide/graphene composite flame retardant.
Preferably, the preparation of the titanium hydroxide/graphene by using the chemical precipitation method specifically comprises the following steps: adding graphene nanosheets and a dispersing agent sodium hexametaphosphate into deionized water, ultrasonically dispersing for a period of time, dropwise adding concentrated hydrochloric acid until the pH of the system is = 1-2, and moving the system to an ice bath condition to stir for 30 minutes;
slowly adding titanium tetrachloride dropwise into the system, stirring for 30 minutes, then adding an ammonia water solution dropwise until the pH value of the system is reached, continuously stirring for 12 hours, centrifugally washing the reaction product by using deionized water and absolute ethyl alcohol for a plurality of times, and drying the reaction product in vacuum to obtain titanium hydroxide/graphene powder.
Preferably, the grafting of the phosphorus-containing group to the titanium hydroxide/graphene through a two-step process specifically includes: adding a titanium hydroxide/graphene suspension with the concentration of 2.7g/L into a container, adjusting the pH of the solution to be 2-3 by glacial acetic acid, dropwise adding a silane coupling agent, stirring and heating under the conditions of nitrogen protection and condensation reflux for reaction, and washing with deionized water for several times to obtain titanium hydroxide/graphene modified by the silane coupling agent;
adding titanium hydroxide/graphene modified by a silane coupling agent into a container, dropwise adding diphenyl chlorophosphate, stirring and heating for reaction under the conditions of nitrogen protection and condensation reflux, centrifugally washing and vacuum drying a reaction product by deionized water and absolute ethyl alcohol to obtain a gray solid product, namely the phosphorus-containing grafted titanium hydroxide/graphene composite flame retardant.
Preferably, the ultrasonic dispersion is carried out for 1 hour.
Preferably, the mass ratio of the graphene nanosheet to the dispersing agent sodium hexametaphosphate is 16.
Preferably, the ammonia water solution is dripped until the pH value of the system is specifically: an aqueous ammonia solution was added dropwise until the system pH =8.
Preferably, the stirring and heating reaction under the conditions of nitrogen protection and condensation reflux is carried out for 2 hours at 80 ℃ under the conditions of nitrogen protection and condensation reflux, and the stirring speed is 350-400 r/min.
Preferably, the vacuum drying is carried out at 80 ℃ for 12 hours.
Preferably, the silane coupling agent is 3-aminopropyltrimethoxysilane.
In addition, in order to achieve the purpose, the invention also provides an application of the phosphorus-grafted titanium hydroxide/graphene flame retardant, and the application of the phosphorus-grafted titanium hydroxide/graphene flame retardant in a flame-retardant epoxy resin composite material, wherein the flame-retardant epoxy resin composite material comprises 10wt% of the phosphorus-grafted titanium hydroxide/graphene flame retardant and 90wt% of epoxy resin.
The invention has the beneficial effects that: compared with pure epoxy resin, the flame-retardant epoxy resin added with the phosphorus-grafted titanium hydroxide/graphene composite flame retardant has the advantages that the UL 94 vertical burning grade of the flame-retardant epoxy resin is improved from no grade to V-1 grade, and the peak heat release rate is 539.0kW/m 2 Reduced to 488.7kW/m 2 The total heat release amount is 102.9MJ/m 2 Reduced to 80.3MJ/m 2 Total smoke yield is from 31.4m 2 Slightly reduced to 31.0m 2 . The prepared phosphorus-containing grafted titanium hydroxide/graphene composite flame retardant exerts the synergy of inorganic titanium hydroxide/graphene and organic phosphorusHas good flame-retardant performance.
Drawings
FIG. 1 is a flow chart of the preparation of phosphorus grafted titanium hydroxide/graphene according to the present invention;
FIG. 2 shows Graphene (GNS) and titanium hydroxide (Ti (OH) 4 ) X-ray diffraction (XRD) pattern of phosphorus-grafted titanium hydroxide/graphene (PTiG);
FIG. 3 is a Fourier Transform Infrared (FTIR) spectrum of phosphorus grafted titanium hydroxide/graphene (PTiG).
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The inventor finds that the flame retardant containing the phosphorus element can be pyrolyzed to generate phosphorus-oxygen groups so as to capture free radicals for maintaining combustion reaction in a gas phase to play a gas phase flame retardant role, and the phosphorus-containing flame retardant can promote the carbonization of a polymer matrix at high temperature, so that the flame retardant has lower smoke yield and toxic gas generation compared with a halogen flame retardant.
The method comprises the steps of dispersing graphene nanosheets in a suspension by ultrasonic waves, depositing titanium hydroxide on graphene nanosheets by a chemical precipitation method to obtain titanium hydroxide/graphene, grafting a silane coupling agent on the titanium hydroxide/graphene by a dehydration reaction principle, and hydrolyzing-NH carried by the silane coupling agent and a-P-Cl group in diphenyl chlorophosphate 2 The group is subjected to substitution reaction, so that an organic phosphorus group is grafted to inorganic titanium hydroxide/graphene, and the phosphorus-containing grafted titanium hydroxide/graphene composite flame retardant is obtained, and the molecular structural formula of the flame retardant is as follows:
further, as shown in fig. 1, as can be seen from fig. 1, in the preparation process of phosphorus-grafted titanium hydroxide/graphene, firstly, titanium tetrachloride is used as a raw material, and nano titanium hydroxide generated by hydrolysis of titanium tetrachloride is deposited on a graphene sheet layer; then, carrying out dehydration reaction on silanol groups hydrolyzed by using a silane coupling agent and titanium hydroxide deposited on the graphene sheet layer, and grafting the silane coupling agent to the surface of the titanium hydroxide/graphene; and finally, carrying out substitution reaction on a P-C l bond in the diphenyl chlorophosphate and an amino group on the surface of the silane coupling agent to prepare the phosphorus-containing grafted titanium hydroxide/graphene.
The flame retardant principle of the phosphorus grafted titanium hydroxide/graphene flame retardant is as follows:
(1) The nano-sheet structure of the graphene can play a role in blocking the pyrolysis of the matrix in the epoxy resin matrix, and the residual carbon content of the epoxy resin is increased; (2) The titanium hydroxide can decompose water vapor in the pyrolysis process, so that the pyrolysis gas and free radicals are diluted, and the combustion reaction is inhibited; (3) The phosphorus-oxygen free radicals generated by the pyrolysis of the phosphorus-containing groups can quench hydrogen free radicals and hydroxyl free radicals in a gas phase in the combustion reaction process, and the content of the free radicals in a combustion area is reduced; (4) The phosphorus-containing group forms inorganic phosphorus-containing acid in the matrix, and can promote the thermal decomposition of the polymer to generate a compact carbon layer.
Example 1
Preparing titanium hydroxide/graphene by using a chemical precipitation method: adding graphene nanosheets and a dispersing agent sodium hexametaphosphate into deionized water until the concentrations of the graphene nanosheets and the dispersing agent sodium hexametaphosphate reach 8g/L and 0.5g/L respectively, ultrasonically dispersing for 1 hour, dropwise adding concentrated hydrochloric acid until the pH of the system is = 1-2, and moving the system to an ice bath condition to stir for 30 minutes. Slowly adding titanium tetrachloride (the concentration reaches 0.3 mol/L), stirring for 30 minutes, then adding ammonia water solution until the pH of the system is = 7-8, and continuing stirring for 3-12 hours. And finally, carrying out centrifugal washing on the reaction product for several times by using deionized water and absolute ethyl alcohol, and carrying out vacuum drying on the reaction product for 12 hours at the temperature of 80 ℃ to obtain titanium hydroxide/graphene powder.
Grafting a phosphorus-containing group to titanium hydroxide/graphene by a two-step process: firstly, adding a titanium hydroxide/graphene suspension with the concentration of 2.7g/L into a three-neck flask, adjusting the pH of the solution to be = 2-3 by glacial acetic acid, dropwise adding 10mL of silane coupling agent 3-aminopropyltrimethoxysilane, reacting for 2 hours under the conditions of nitrogen protection and condensation reflux at the stirring speed of 350-400 r/min and the temperature of 80 ℃, and washing for several times by deionized water to obtain the silane coupling agent modified titanium hydroxide/graphene. Then, adding the titanium hydroxide/graphene modified by the silane coupling agent into a three-neck flask containing 300mL of deionized water, dropwise adding 10mL of diphenyl chlorophosphate, and reacting for 2 hours at the stirring speed of 400-600 r/min and the temperature of 80 ℃ under the conditions of nitrogen protection and condensation reflux. And (3) centrifugally washing the reaction product by using deionized water and absolute ethyl alcohol, and drying the reaction product for 12 hours in vacuum at 80 ℃ to obtain 14g of gray solid product, namely the phosphorus-containing grafted titanium hydroxide/graphene composite flame retardant.
Example 2
Preparing titanium hydroxide/graphene by using a chemical precipitation method: adding 6g of graphene nanosheet and 0.375g of dispersant sodium hexametaphosphate into 750mL of deionized water, stirring and ultrasonically treating for 1 hour, and dropwise adding concentrated hydrochloric acid until the pH of the system is =1. The system was moved to ice bath conditions and stirring was continued for 30 minutes. 24.72mL of titanium tetrachloride was slowly added dropwise to the system, stirring was continued for 30 minutes, and the aqueous ammonia solution was added dropwise until the system pH =8, and stirring was continued for 12 hours. And finally, washing the solution for several times by using deionized water and absolute ethyl alcohol, and drying the washing product for 12 hours in vacuum at the temperature of 80 ℃ to obtain 28.6g of titanium hydroxide/graphene powder.
Grafting an organophosphorus group onto the titanium hydroxide/graphene sheet layer by using a silane coupling agent as a bridge: first 8g of titanium hydroxide/graphene powder was added to a three-necked flask containing 300mL of deionized water and stirred (350 r/min), and the solution pH =3 was adjusted with glacial acetic acid, 10mL of 3-aminopropyltrimethoxysilane was added dropwise to the three-necked flask at room temperature and stirred at 80 ℃ for 2 hours under nitrogen protection and condensation reflux. And (2) centrifugally washing the solution with deionized water and absolute ethyl alcohol for several times to obtain a solid, adding the solid into a three-necked flask containing 300mL of deionized water, stirring (400 r/min), dropwise adding 10mL of diphenyl chlorophosphate at room temperature, stirring for 2 hours at 80 ℃ under the conditions of nitrogen protection and condensation reflux, centrifugally washing the reaction product with deionized water and absolute ethyl alcohol, and carrying out vacuum drying at 80 ℃ for 12 hours to obtain 16g of gray solid product phosphorus-grafted titanium hydroxide/graphene.
Example 3
Preparing titanium hydroxide/graphene by using a chemical precipitation method: adding 4g of graphene nanosheet and 0.25g of dispersant sodium hexametaphosphate into 500mL of deionized water, stirring and ultrasonically treating for 1 hour, and dropwise adding concentrated hydrochloric acid into the solution until the pH of the system is =1. The system was moved to ice bath conditions and stirring was continued for 30 minutes. 16.48mL of titanium tetrachloride was slowly added dropwise to the system, stirring was continued for 30 minutes, and then the aqueous ammonia solution was added dropwise until the system pH =8, and stirring was continued for 3 hours. And finally, carrying out centrifugal washing on the solution for several times by using deionized water and absolute ethyl alcohol, and carrying out vacuum drying on the washing product for 12 hours at the temperature of 80 ℃ to obtain 29g of titanium hydroxide/graphene powder.
Grafting an organophosphorus group onto the titanium hydroxide/graphene sheet layer by using a silane coupling agent as a bridge: first, 8g of titanium hydroxide/graphene powder was added to a three-necked flask containing 300mL of deionized water, stirred (350 r/min), and the solution pH =3 was adjusted with glacial acetic acid, 10mL of 3-aminopropyltrimethoxysilane solution was added dropwise to the three-necked flask at room temperature, and stirred in an 80 ℃ oil bath for 3 hours under nitrogen protection and reflux condensation conditions. And (2) centrifugally washing the solution with deionized water and absolute ethyl alcohol for several times to obtain a powder product, adding the powder product into a three-necked flask containing 300mL of deionized water, stirring (600 r/min), dropwise adding 10mL of diphenyl chlorophosphate at room temperature, stirring for 3 hours in an oil bath at 80 ℃ under the conditions of nitrogen protection and condensation reflux, centrifugally washing the reaction product with deionized water and absolute ethyl alcohol, and drying by air blowing at 80 ℃ for 12 hours to obtain 15g of gray solid product, namely the phosphorus-grafted titanium hydroxide/graphene composite flame retardant.
Example 4
Preparing titanium hydroxide/graphene by using a chemical precipitation method: 2g of graphene nanosheet and 0.125g of dispersant sodium hexametaphosphate are added into 250mL of deionized water, ultrasonic dispersion is carried out for 1 hour, and hydrochloric acid is dropwise added until the pH of the system is =2. The system was moved to ice bath conditions and stirring was continued for 30 minutes. 8.25mL of titanium tetrachloride was slowly added dropwise to the system, stirring was continued for 30 minutes, and then the aqueous ammonia solution was added dropwise until the system pH =7, and stirring was continued for 12 hours. And finally, carrying out centrifugal washing on the solution for several times by using deionized water and absolute ethyl alcohol, and carrying out vacuum drying on the washing product for 3 hours at the temperature of 80 ℃ to obtain 9.9g of titanium hydroxide/graphene powder.
Grafting an organophosphorus group onto the titanium hydroxide/graphene sheet layer by using a silane coupling agent as a bridge: first, 8g of titanium hydroxide/graphene powder was added to a three-necked flask containing 300mL of deionized water, stirred (400 r/min), and the solution pH =2 was adjusted with glacial acetic acid, 10mL of 3-aminopropyltrimethoxysilane solution was added dropwise to the three-necked flask at room temperature, and stirred in an 80 ℃ oil bath for 2 hours under nitrogen protection and reflux condensation conditions. Washing the solution with deionized water and absolute ethyl alcohol for several times to obtain a solid, adding the solid into a three-necked flask containing 300mL of deionized water, dropwise adding 10mL of diphenyl chlorophosphate while stirring (600 r/min), stirring in an oil bath at 80 ℃ for 2 hours under the conditions of nitrogen protection and condensation reflux, centrifugally washing the reaction product with deionized water and absolute ethyl alcohol for several times, and drying by air blowing at 80 ℃ for 12 hours to obtain 14g of gray phosphorus grafted titanium hydroxide/graphene powder.
Example 5
Application of the prepared phosphorus grafted titanium hydroxide/graphene composite flame retardant.
The flame-retardant epoxy resin composite material is prepared by a blending method. In the process of preparing the flame-retardant epoxy resin, 100g of epoxy resin is firstly placed in a beaker to be preheated at 80 ℃ for 20 minutes, the epoxy resin is placed in an 80 ℃ oil bath condition for magnetic stirring (250 r/min), 10g of phosphorus grafted titanium hydroxide/graphene powder is slowly added into the epoxy resin (AG 80 type) under the stirring state to be continuously stirred for 1 hour, 41g of diaminodiphenylmethane (DDM) particles are added into the epoxy resin to be continuously stirred for 25 minutes until the DDM particles are completely melted, the epoxy resin is placed in a 79 ℃ vacuum drying box to be subjected to bubble removal operation, then the epoxy resin is poured into a 80 ℃ preheated polytetrafluoroethylene mould for solidification, and the solidification procedures are 80 ℃ (2 h), 120 ℃ (2 h), 150 ℃ (2 h) and 180 ℃ (2 h), so that the flame-retardant epoxy resin composite material is prepared.
The pure epoxy resin material is prepared by adopting the same preparation process under the condition of not adding a flame retardant. The flame retardant properties of the samples were tested using a UL 94 vertical burn tester and a cone calorimeter. The results show that compared with pure epoxy resin, the UL 94 vertical burning grade of the flame-retardant epoxy resin is improved from no grade to V-1 grade, and the peak heat release rate is 539.0kW/m 2 Reduced to 488.7kW/m 2 The total heat release amount is 102.9MJ/m 2 Reduced to 80.3MJ/m 2 Total smoke yield is from 31.4m 2 Slightly reduced to 31.0m 2 . The results show that the prepared phosphorus-containing grafted titanium hydroxide/graphene composite flame retardant has good flame retardant performance.
As shown in FIG. 2, FIG. 2 shows Graphene (GNS) and titanium hydroxide (Ti (OH) 4 ) And phosphorus grafted titanium hydroxide/graphene (PTiG), wherein the X-ray diffraction (XRD) pattern shows that GNS has a sharp 001 diffraction peak at 26.4 degrees, which indicates that the GNS has higher crystallization degree, and Ti (OH) 4 The diffraction peak near 25.5 ° was broad and weak indicating low crystallinity, PTiG had a slight broad peak at 26.5 ° and a weak broad peak around 25 °, indicating that titanium hydroxide was deposited on the graphene surface.
As shown in FIG. 3, FIG. 3 is a Fourier Infrared Spectroscopy (IR) chart of phosphorus grafted titanium hydroxide/graphene (PT iG), in which 1050cm can be seen -1 、943cm -1 The vibration absorption peaks respectively belong to Si-O-Si and Ti-O-Si, and the silane coupling agent is grafted to the titanium hydroxide/graphene through a dehydration reaction. 1605cm -1 、1455cm -1 The vibration absorption peaks respectively attributed to N-H and P-N indicate-P-Cl and-NH in diphenyl chlorophosphate 2 And (3) carrying out substitution reaction, so that diphenyl chlorophosphate is grafted to the silane coupling agent modified titanium hydroxide/graphene, and obtaining the phosphorus-containing grafted titanium hydroxide/graphene.
The phosphorus-containing grafted titanium hydroxide/graphene composite flame retardant disclosed by the invention has a good flame retardant property and can play a role in the synergistic flame retardance of inorganic titanium hydroxide/graphene and organic phosphorus.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described in the foregoing embodiments, or equivalents may be substituted for elements thereof.
Claims (7)
1. A preparation method of a phosphorus grafted titanium hydroxide/graphene flame retardant is characterized by comprising the following steps: preparing titanium hydroxide/graphene by using a chemical precipitation method, and grafting a phosphorus-containing group to the titanium hydroxide/graphene through a two-step method to obtain a phosphorus-containing grafted titanium hydroxide/graphene composite flame retardant;
the preparation of the titanium hydroxide/graphene by using the chemical precipitation method specifically comprises the following steps: adding graphene nanosheets and a dispersing agent sodium hexametaphosphate into deionized water, ultrasonically dispersing for a period of time, dropwise adding concentrated hydrochloric acid until the pH of the system is = 1-2, and moving the system to an ice bath condition to stir for 30 minutes;
slowly dripping titanium tetrachloride into the system, stirring for 30 minutes, dripping an ammonia water solution, continuously stirring for 12 hours, carrying out centrifugal washing on a reaction product for a plurality of times by using deionized water and absolute ethyl alcohol, and drying the reaction product in vacuum to obtain titanium hydroxide/graphene powder;
the grafting of the phosphorus-containing group to the titanium hydroxide/graphene through a two-step method specifically comprises the following steps: adding a titanium hydroxide/graphene suspension with the concentration of 2.7g/L into a container, adjusting the pH of the solution to be 2-3 by glacial acetic acid, dropwise adding a silane coupling agent, stirring and heating under the conditions of nitrogen protection and condensation reflux for reaction, and washing with deionized water for several times to obtain titanium hydroxide/graphene modified by the silane coupling agent;
adding titanium hydroxide/graphene modified by a silane coupling agent into a container, dropwise adding diphenyl chlorophosphate, stirring and heating for reaction under the conditions of nitrogen protection and condensation reflux, centrifugally washing and vacuum drying a reaction product by using deionized water and absolute ethyl alcohol to obtain a gray solid product, namely the phosphorus-containing grafted titanium hydroxide/graphene composite flame retardant;
the silane coupling agent is 3-aminopropyl trimethoxy silane.
2. The method for preparing phosphorus-grafted titanium hydroxide/graphene flame retardant according to claim 1, characterized in that: the ultrasonic dispersion is carried out for 1h.
3. The method for preparing phosphorus-grafted titanium hydroxide/graphene flame retardant according to claim 1, characterized in that: the mass ratio of the graphene nanosheet to the dispersing agent sodium hexametaphosphate is 16.
4. The method for preparing phosphorus-grafted titanium hydroxide/graphene flame retardant according to claim 1, characterized in that: the dropwise addition of the ammonia water solution is specifically as follows: an aqueous ammonia solution was added dropwise until the system pH =8.
5. The method for preparing phosphorus-grafted titanium hydroxide/graphene flame retardant according to claim 1, characterized in that: the stirring and heating reaction under the conditions of nitrogen protection and condensation reflux is carried out for 2 hours at 80 ℃ under the conditions of nitrogen protection and condensation reflux, and the stirring speed is 350-400 r/min.
6. The method for preparing the phosphorus-grafted titanium hydroxide/graphene flame retardant according to claim 1, characterized in that: the vacuum drying is carried out at 80 ℃ for 12 hours.
7. The application of the phosphorus grafted titanium hydroxide/graphene flame retardant prepared by the preparation method of any one of claims 1 to 6 is characterized in that: the application of the phosphorus grafted titanium hydroxide/graphene flame retardant in the flame-retardant epoxy resin composite material comprises 10wt% of the phosphorus grafted titanium hydroxide/graphene flame retardant and 90wt% of epoxy resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111582643.8A CN114316366B (en) | 2021-12-22 | 2021-12-22 | Preparation method and application of phosphorus-grafted titanium hydroxide/graphene flame retardant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111582643.8A CN114316366B (en) | 2021-12-22 | 2021-12-22 | Preparation method and application of phosphorus-grafted titanium hydroxide/graphene flame retardant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114316366A CN114316366A (en) | 2022-04-12 |
| CN114316366B true CN114316366B (en) | 2023-04-11 |
Family
ID=81054083
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111582643.8A Active CN114316366B (en) | 2021-12-22 | 2021-12-22 | Preparation method and application of phosphorus-grafted titanium hydroxide/graphene flame retardant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114316366B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117816145A (en) * | 2024-03-04 | 2024-04-05 | 成都先进金属材料产业技术研究院股份有限公司 | Method for uniformly loading nano titanium dioxide on graphene oxide surface and photocatalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102324505A (en) * | 2011-07-27 | 2012-01-18 | 天津大学 | Preparation method of graphene loaded with anatase type nano titanium dioxide and application 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 |
| CN113512274A (en) * | 2021-08-22 | 2021-10-19 | 华北科技学院(中国煤矿安全技术培训中心) | Modified graphene oxide and preparation method and application thereof |
-
2021
- 2021-12-22 CN CN202111582643.8A patent/CN114316366B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102324505A (en) * | 2011-07-27 | 2012-01-18 | 天津大学 | Preparation method of graphene loaded with anatase type nano titanium dioxide and application 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 |
| CN113512274A (en) * | 2021-08-22 | 2021-10-19 | 华北科技学院(中国煤矿安全技术培训中心) | Modified graphene oxide and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| Quanxiao Dong等.Investigation of Flame Retardant Flexible Polyurethane Foams Containing DOPO Immobilized Titanium Dioxide Nanoparticles.《POLYMERS》.2019,第11卷(第1期),1-11. * |
| 董全霄 等.表面接枝磷杂菲的二氧化钛制备及对聚氨酯阻燃性能影响.《高分子材料科学与工程》.2019,第35卷(第7期),38-43. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114316366A (en) | 2022-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chen et al. | Recent advances in Two-dimensional Ti3C2Tx MXene for flame retardant polymer materials | |
| Yang et al. | Synergistic decoration of organic titanium and polydopamine on boron nitride to enhance fire resistance of intumescent waterborne epoxy coating | |
| CN112225985B (en) | Flame-retardant PP composite material and preparation method thereof | |
| CN106883450A (en) | A kind of rich phosphatization Graphene fire retardant and preparation method thereof | |
| CN102850905B (en) | Aqueous expansion-type steel structure fireproof paint and preparation method thereof | |
| CN111793090A (en) | DOPO silicon phosphorus synergistic flame retardant and preparation method and application thereof | |
| CN109180952B (en) | Nitrogen-phosphorus-silicon synergistic halogen-free flame retardant grafted with graphene and preparation method thereof | |
| CN106008742A (en) | Marine biomass based flame retardant with cellulose-like structure | |
| CN114316366B (en) | Preparation method and application of phosphorus-grafted titanium hydroxide/graphene flame retardant | |
| CN109517220B (en) | Preparation method of nano tin-based intumescent flame retardant | |
| CN112745610A (en) | Modified Mxene/PVA flame-retardant composite material and preparation method thereof | |
| CN110396202B (en) | ZIF-67 nanocrystalline surface modified hexa-imidazole cyclotriphosphazene flame retardant and preparation method thereof | |
| TW200904909A (en) | Modified expansible graphite by silane modifying agent and producing method thereof | |
| CN110606990A (en) | Hyperbranched polysiloxane-coated ammonium polyphosphate flame retardant and preparation method thereof | |
| CN115260899A (en) | Hydrophobic coating and preparation method and application thereof | |
| Shen et al. | Color adjustable, mechanically robust, flame-retardant and weather-resistant TiO2/MMT/CNF hierarchical nanocomposite coatings toward intelligent fire cyclic warning and protection | |
| Ma et al. | Construction of green versatile coating integrating fireproof, electric-conduction and self-cleaning performance for cotton fabrics | |
| KR100846998B1 (en) | Method for preparation of high dielectric inorganic-organic hybrid films containing crystalline barium titanate nanoparticles | |
| CN114058225A (en) | Basalt/aluminum hypophosphite flame-retardant water-resistant coating and preparation method and application thereof | |
| CN106854370B (en) | A kind of supermolecule flame-proof silicon rubber and preparation method thereof | |
| CN116285675B (en) | Novel POSS functionalized hydrophobic silane coating and preparation method and application thereof | |
| CN112194822A (en) | Phosphorus-containing flame retardant, preparation method and modified epoxy resin | |
| WO2024036756A1 (en) | Multifunctional phosphorus and nickel doped graphite-like carbon nitride nanosheet, preparation method therefor, and abs material | |
| CN113150440B (en) | Preparation method of flame-retardant polypropylene | |
| CN113121882B (en) | Functionalized graphene oxide-aluminum hypophosphite flame retardant and preparation method and application 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 |