Graphene grafted phenolic resin binder composite material and preparation method thereof
By grafting and modifying graphene oxide with phenolic resin, a graphene grafted phenolic resin binder composite material is solved, and the problems of poor mechanical properties and low thermal stability of phenolic resin are achieved, and higher mechanical strength and Thermal stability.
Patent Information
- Application Number
- CN202411815654.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-11
- Publication Date
- 2025-02-14
- Estimated Expiration
- Not applicable · inactive patent
AI Technical Summary
The poor mechanical properties and low thermal stability of phenolic resins limit their application range.
By grafting the graphene oxide with phenolic resin, and modifying chemical substances such as aminoacetophenone and phenylenediamine, a graphene grafted phenolic resin binder composite material is formed.
The mechanical strength and thermal stability of the phenolic resin are improved, the agglomeration of graphene oxide is avoided, and the overall performance of the material is enhanced.
Smart Images
Figure CN119431817A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of novel plastics, in particular to a graphene-grafted phenolic resin binder composite material and a preparation method thereof. Background Art
[0002] Phenolic resin is a synthetic plastic obtained by polymerization of phenol and formaldehyde. It has excellent insulation properties and chemical stability and has been widely used in aerospace, electrical equipment, coatings, etc. However, due to its unique structural characteristics, the methyl groups in its molecules are extremely easy to break when affected by external forces or high temperatures, which greatly limits the application of phenolic resin.
[0003] In order to improve phenolic resin and obtain materials with good performance, researchers have done a lot of research, among which nano-modification is undoubtedly one of the best methods. Through nano-modification, phenolic resin can have the advantages of both nano-inorganic and polymers. Graphene is an important nano-modified material. Each vertex in its hexagonal lattice structure has an atom, which has high inherent conductivity, as well as mechanical strength and chemical stability. Its unique physical, chemical and mechanical properties enable graphene and its derivatives to improve the mechanical properties and thermal stability of phenolic resin. However, the large number of active groups on the surface of graphene oxide makes it easy to agglomerate, which limits the scope of use of graphene oxide. Summary of the Invention
[0004] In view of the deficiencies in the prior art, the present invention provides a graphene-grafted phenolic resin binder composite material and a preparation method thereof, which solves the problems of poor mechanical properties and low thermal stability of phenolic resin.
[0005] To achieve the above object, the present invention provides the following technical solution: a graphene-grafted phenolic resin binder composite material, wherein the preparation method of the graphene-grafted phenolic resin binder composite material comprises the following steps: (1) ultrasonically dispersing graphene oxide in N,N-dimethylformamide solvent, then adding aminoacetophenone and dicyclohexylcarbodiimide thereto to carry out modification reaction, and after the reaction is completed, centrifugally washing and drying to obtain aminoacetophenone-modified graphene; (2) Adding formaldehyde solution to the ethanol solution of p-phenylenediamine, adjusting the pH to 3-5, and stirring until uniform, then adding aminoacetophenone-modified graphene, refluxing and performing Mannich reaction, filtering, washing, and drying to obtain p-phenylenediamine functionalized graphene; (3) Phenol, formaldehyde solution and sodium hydroxide are added to deionized water one by one, stirred evenly, and then p-phenylenediamine functionalized graphene is added, and then transferred to a reactor for polymerization reaction. After the reaction is completed, dehydration, washing and drying are performed to obtain graphene-grafted phenolic resin; (4) Add melamine and urea to the graphene-grafted phenolic resin, react at 50-60°C for 30-60 minutes, cool to room temperature, add 3-8 wt% of ammonium sulfate, and stir evenly to obtain a graphene-grafted phenolic resin binder composite material.
[0006] Preferably, in step (1), the mass ratio of graphene oxide, aminoacetophenone and dicyclohexylcarbodiimide is 100:150-250:10-30.
[0007] Preferably, the temperature of the modification reaction in step (1) is 20-50° C., and the reaction time is 18-30 h.
[0008] Preferably, in the step (2), the mass ratio of aminoacetophenone-modified graphene, p-phenylenediamine and formaldehyde is 100:120-150:40-60.
[0009] Preferably, the temperature of the Mannich reaction in step (2) is 60-90° C., and the reaction time is 12-24 h.
[0010] Preferably, the mass ratio of phenol, formaldehyde, sodium hydroxide and p-phenylenediamine functionalized graphene in step (3) is 100:130-140:1-10:1-2.5.
[0011] Preferably, the polymerization reaction temperature in step (3) is 80-120° C., and the reaction time is 1-3 h.
[0012] Preferably, in step (4), the mass ratio of the graphene-grafted phenolic resin, melamine and urea is 10:8-12:30-50.
[0013] Compared with the prior art, the present invention has the following experimental principles and beneficial technical effects: The invention discloses a graphene-grafted phenolic resin binder composite material. Dicyclohexylcarbodiimide is used as a catalyst to react aminoacetophenone with carboxyl groups on the surface of graphene oxide to obtain aminoacetophenone-modified graphene. The carbonyl groups formed on the surface of the graphene oxide are then subjected to a Mannich reaction with p-phenylenediamine and formaldehyde to obtain p-phenylenediamine-functionalized graphene. Subsequently, under alkaline conditions, the aniline groups in the aminoacetophenone-modified graphene are used to initiate a polymerization reaction in a phenol and formaldehyde solution to obtain a graphene-grafted phenolic resin. The graphene-grafted phenolic resin binder composite material is then prepared by combining the graphene with melamine, urea, and the like. The introduction of graphene oxide into the phenolic resin can improve the mechanical strength and thermal stability of the phenolic resin. The graphene oxide is uniformly dispersed in the phenolic resin by chemical grafting, thereby avoiding the agglomeration of the graphene oxide and increasing the effect of the graphene oxide-modified phenolic resin, thereby increasing the mechanical strength and thermal stability of the graphene-grafted phenolic resin binder composite material.
[0014] The graphene-grafted phenolic resin binder composite material has better mechanical properties and thermal stability than pure phenolic resin binder. Graphene oxide itself has good mechanical properties, and the mechanical properties of phenolic resin can be improved by grafting. This is because the interaction force between graphene oxide and phenolic resin is increased by chemical bonding. At the same time, graphene oxide has a unique flaky structure. When subjected to external force, carbon atoms offset the external force by bending and deforming between the flaky layers. The mechanical properties of the composite material are improved, and the external force can be transferred to the graphene oxide through the chemical bonds formed at the interface, reducing the force on the phenolic resin. The improvement of the thermodynamic stability of the composite material is mainly due to the chemical bonds formed between graphene oxide and phenolic resin, which restricts the movement of the phenolic resin molecular chain when heated, so that it maintains good thermal stability. The agglomeration behavior of graphene oxide will reduce the improvement of mechanical properties and thermal stability. The grafting method can make the graphene oxide evenly dispersed in the phenolic resin, effectively avoiding the adverse effects caused by agglomeration. BRIEF DESCRIPTION OF THE DRAWINGS
[0015] Figure 1 is the reaction formula of aminoacetophenone and graphene oxide; Figure 2 It is aminoacetophenone modified graphene, p-phenylenediamine and formaldehyde undergo Mannich reaction; Figure 3 This is the reaction formula of p-phenylenediamine functionalized graphene, phenol and formaldehyde; DETAILED DESCRIPTION
[0016] To achieve the above objectives, the present invention provides the following specific implementation methods and examples: A graphene-grafted phenolic resin binder composite material, the preparation method of which comprises the following steps: (1) ultrasonically dispersing graphene oxide in an N,N-dimethylformamide solvent, and then adding aminoacetophenone and dicyclohexylcarbodiimide thereto, wherein the mass ratio of graphene oxide, aminoacetophenone and dicyclohexylcarbodiimide is 100:150-250:10-30, and performing a modification reaction at a temperature of 20-50°C and a reaction time of 18-30 hours. After the reaction is completed, centrifugation, washing and drying are performed to obtain aminoacetophenone-modified graphene; (2) Adding formaldehyde solution to the ethanol solution of p-phenylenediamine, adjusting the pH to 3-5, and stirring until uniform, then adding aminoacetophenone-modified graphene, wherein the mass ratio of aminoacetophenone-modified graphene, p-phenylenediamine and formaldehyde is 100:120-150:40-60, refluxing and performing Mannich reaction, the temperature is 60-90 ° C, the reaction time is 12-24 hours, filtering, washing and drying to obtain p-phenylenediamine functionalized graphene; (3) Phenol, formaldehyde solution and sodium hydroxide are added to deionized water one by one, stirred evenly, and then p-phenylenediamine functionalized graphene is added, wherein the mass ratio of phenol, formaldehyde, sodium hydroxide and p-phenylenediamine functionalized graphene is 100:130-140:1-10:1-2.5, and then transferred to a reactor for polymerization reaction at a temperature of 80-120°C and a reaction time of 1-3 hours. After the reaction is completed, dehydration and drying are performed to obtain graphene-grafted phenolic resin; (4) Adding melamine and urea to the graphene-grafted phenolic resin in a mass ratio of 10:8-12:30-50, reacting at 50-60°C for 30-60 minutes, cooling to room temperature, and then adding 3-8 wt% of ammonium sulfate. After stirring evenly, a graphene-grafted phenolic resin binder composite material is obtained. Example 1
[0017] (1) Graphene oxide is ultrasonically dispersed in N,N-dimethylformamide solvent, and then aminoacetophenone and dicyclohexylcarbodiimide are added thereto, wherein the mass ratio of graphene oxide, aminoacetophenone and dicyclohexylcarbodiimide is 100:150:10, and a modification reaction is carried out at a temperature of 20°C and a reaction time of 18 hours. After the reaction is completed, the graphene oxide is centrifuged, washed and dried to obtain aminoacetophenone-modified graphene; (2) Adding formaldehyde solution to the ethanol solution of p-phenylenediamine, adjusting the pH to 3, and stirring until uniform, then adding aminoacetophenone-modified graphene, wherein the mass ratio of aminoacetophenone-modified graphene, p-phenylenediamine and formaldehyde is 100:120:40, refluxing and performing Mannich reaction at 60°C for 12 hours, filtering, washing and drying to obtain p-phenylenediamine functionalized graphene; (3) Phenol, formaldehyde solution and sodium hydroxide were added to deionized water one by one, stirred evenly, and then p-phenylenediamine functionalized graphene was added, wherein the mass ratio of phenol, formaldehyde, sodium hydroxide and p-phenylenediamine functionalized graphene was 100:130:1:1, and then transferred to a reactor for polymerization reaction at a temperature of 80°C and a reaction time of 1 hour. After the reaction was completed, the mixture was dehydrated and dried to obtain a graphene-grafted phenolic resin; (4) Melamine and urea were added to the graphene-grafted phenolic resin in a mass ratio of 10:8:30, and the mixture was reacted at 50°C for 30 minutes. After cooling to room temperature, 3 wt% of ammonium sulfate was added and stirred evenly to obtain a graphene-grafted phenolic resin binder composite material. Example 2
[0018] (1) Graphene oxide is ultrasonically dispersed in N,N-dimethylformamide solvent, and then aminoacetophenone and dicyclohexylcarbodiimide are added thereto, wherein the mass ratio of graphene oxide, aminoacetophenone and dicyclohexylcarbodiimide is 100:180:15, and a modification reaction is carried out at a temperature of 30°C and a reaction time of 22 hours. After the reaction is completed, the graphene oxide is centrifuged, washed and dried to obtain aminoacetophenone-modified graphene; (2) Adding formaldehyde solution to the ethanol solution of p-phenylenediamine, adjusting the pH to 3.5, and stirring until uniform, then adding aminoacetophenone-modified graphene, wherein the mass ratio of aminoacetophenone-modified graphene, p-phenylenediamine and formaldehyde is 100:130:45, reflux and perform Mannich reaction, the temperature is 70 ° C, the reaction time is 16 hours, filtering, washing and drying to obtain p-phenylenediamine functionalized graphene; (3) Phenol, formaldehyde solution and sodium hydroxide were added to deionized water one by one, stirred evenly, and then p-phenylenediamine functionalized graphene was added, wherein the mass ratio of phenol, formaldehyde, sodium hydroxide and p-phenylenediamine functionalized graphene was 100:132:3:1.5, and then transferred to a reactor for polymerization reaction at a temperature of 90°C and a reaction time of 1.5 hours. After the reaction was completed, the mixture was dehydrated and dried to obtain a graphene-grafted phenolic resin; (4) Melamine and urea were added to the graphene-grafted phenolic resin in a mass ratio of 10:9:35, and the mixture was reacted at 52°C for 40 min. After cooling to room temperature, 4 wt% of ammonium sulfate was added and stirred evenly to obtain a graphene-grafted phenolic resin binder composite material. Example 3
[0019] (1) Graphene oxide is ultrasonically dispersed in N,N-dimethylformamide solvent, and then aminoacetophenone and dicyclohexylcarbodiimide are added thereto, wherein the mass ratio of graphene oxide, aminoacetophenone and dicyclohexylcarbodiimide is 100:200:24, and a modification reaction is carried out at a temperature of 4°C and a reaction time of 24 hours. After the reaction is completed, the graphene oxide is centrifuged, washed and dried to obtain aminoacetophenone-modified graphene; (2) Adding formaldehyde solution to the ethanol solution of p-phenylenediamine, adjusting the pH to 4.5, and stirring until uniform, then adding aminoacetophenone-modified graphene, wherein the mass ratio of aminoacetophenone-modified graphene, p-phenylenediamine and formaldehyde is 100:140:55, reflux and perform Mannich reaction, the temperature is 80 ° C, the reaction time is 20 h, filtering, washing and drying to obtain p-phenylenediamine functionalized graphene; (3) Phenol, formaldehyde solution and sodium hydroxide were added to deionized water one by one, stirred evenly, and then p-phenylenediamine functionalized graphene was added, wherein the mass ratio of phenol, formaldehyde, sodium hydroxide and p-phenylenediamine functionalized graphene was 100:135:8:2, and then transferred to a reactor for polymerization reaction at a temperature of 100 ° C and a reaction time of 2.4 h. After the reaction was completed, dehydration and drying were performed to obtain graphene grafted phenolic resin; (4) Melamine and urea were added to the graphene-grafted phenolic resin in a mass ratio of 10:11:45, and the mixture was reacted at 58°C for 50 min. After cooling to room temperature, 6 wt% of ammonium sulfate was added and stirred evenly to obtain a graphene-grafted phenolic resin binder composite material. Example 4
[0020] (1) Graphene oxide is ultrasonically dispersed in N,N-dimethylformamide solvent, and then aminoacetophenone and dicyclohexylcarbodiimide are added thereto, wherein the mass ratio of graphene oxide, aminoacetophenone and dicyclohexylcarbodiimide is 100:250:30, and a modification reaction is carried out at a temperature of 50°C and a reaction time of 30 hours. After the reaction is completed, the graphene oxide is centrifuged, washed and dried to obtain aminoacetophenone-modified graphene; (2) Adding formaldehyde solution to the ethanol solution of p-phenylenediamine, adjusting the pH to 5, and stirring until uniform, then adding aminoacetophenone-modified graphene, wherein the mass ratio of aminoacetophenone-modified graphene, p-phenylenediamine and formaldehyde is 100:150:60, refluxing and performing Mannich reaction at 90°C for 24 hours, filtering, washing and drying to obtain p-phenylenediamine functionalized graphene; (3) Phenol, formaldehyde solution and sodium hydroxide were added to deionized water one by one, stirred evenly, and then p-phenylenediamine functionalized graphene was added, wherein the mass ratio of phenol, formaldehyde, sodium hydroxide and p-phenylenediamine functionalized graphene was 100:140:10:2.5, and then transferred to a reactor for polymerization reaction at a temperature of 120°C and a reaction time of 3 hours. After the reaction was completed, the mixture was dehydrated and dried to obtain a graphene-grafted phenolic resin; (4) Melamine and urea were added to the graphene-grafted phenolic resin in a mass ratio of 10:12:50, and the mixture was reacted at 60°C for 60 min. After cooling to room temperature, 8 wt% of ammonium sulfate was added and stirred evenly to obtain a graphene-grafted phenolic resin binder composite material.
[0021] Comparative Example 1 (1) Graphene oxide is ultrasonically dispersed in N,N-dimethylformamide solvent, and then aminoacetophenone and dicyclohexylcarbodiimide are added thereto, wherein the mass ratio of graphene oxide, aminoacetophenone and dicyclohexylcarbodiimide is 100:120:8, and a modification reaction is carried out at a temperature of 16°C and a reaction time of 15 hours. After the reaction is completed, the graphene oxide is centrifuged, washed and dried to obtain aminoacetophenone-modified graphene; (2) Adding formaldehyde solution to the ethanol solution of p-phenylenediamine, adjusting the pH to 2.4, and stirring until uniform, then adding aminoacetophenone-modified graphene, wherein the mass ratio of aminoacetophenone-modified graphene, p-phenylenediamine and formaldehyde is 100:96:32, reflux and perform Mannich reaction, the temperature is 50 ° C, the reaction time is 9 hours, filtering, washing and drying to obtain p-phenylenediamine functionalized graphene; (3) Phenol, formaldehyde solution and sodium hydroxide were added to deionized water one by one, stirred evenly, and then p-phenylenediamine functionalized graphene was added, wherein the mass ratio of phenol, formaldehyde, sodium hydroxide and p-phenylenediamine functionalized graphene was 100:110:0.8:0.8, and then transferred to a reactor for polymerization reaction at a temperature of 60°C and a reaction time of 0.8 h. After the reaction was completed, the mixture was dehydrated and dried to obtain a graphene-grafted phenolic resin; (4) Melamine and urea were added to the graphene-grafted phenolic resin in a mass ratio of 10:6:24, and the mixture was reacted at 42°C for 24 minutes. After cooling to room temperature, 2 wt% of ammonium sulfate was added and stirred evenly to obtain a graphene-grafted phenolic resin binder composite material.
[0022] Comparative Example 2 (1) Graphene oxide was ultrasonically dispersed in N,N-dimethylformamide solvent, and then aminoacetophenone and dicyclohexylcarbodiimide were added thereto, wherein the mass ratio of graphene oxide, aminoacetophenone and dicyclohexylcarbodiimide was 100:300:36, and a modification reaction was carried out at a temperature of 60°C and a reaction time of 36 hours. After the reaction was completed, the graphene oxide was centrifuged, washed and dried to obtain aminoacetophenone-modified graphene; (2) Adding formaldehyde solution to the ethanol solution of p-phenylenediamine, adjusting the pH to 6, and stirring until uniform, then adding aminoacetophenone-modified graphene, wherein the mass ratio of aminoacetophenone-modified graphene, p-phenylenediamine and formaldehyde is 100:180:72, reflux and perform Mannich reaction, the temperature is 110 ° C, the reaction time is 30 hours, filtering, washing and drying to obtain p-phenylenediamine functionalized graphene; (3) Phenol, formaldehyde solution and sodium hydroxide were added to deionized water one by one, stirred evenly, and then p-phenylenediamine functionalized graphene was added, wherein the mass ratio of phenol, formaldehyde, sodium hydroxide and p-phenylenediamine functionalized graphene was 100:170:12:3, and then transferred to a reactor for polymerization reaction at a temperature of 150°C and a reaction time of 3.5 hours. After the reaction was completed, the mixture was dehydrated and dried to obtain a graphene-grafted phenolic resin; (4) Melamine and urea were added to the graphene-grafted phenolic resin in a mass ratio of 10:16:65, and the mixture was reacted at 90°C for 80 min. After cooling to room temperature, 11 wt% of ammonium sulfate was added and stirred evenly to obtain a graphene-grafted phenolic resin binder composite material.
[0023] The mechanical properties of graphene grafted phenolic resin were tested using an L-200A electronic universal testing machine.
[0024]
[0025] In a nitrogen atmosphere, the heat resistance index of graphene grafted phenolic resin was tested using a TGA-1150 thermogravimetric analyzer. The test parameters were: test temperature 800°C, heating rate 10°C / min.
[0026]
Claims
1. A graphene-grafted phenolic resin binder composite material, characterized in that: The preparation method of the graphene-grafted phenolic resin binder composite material comprises the following steps: (1) ultrasonically dispersing graphene oxide in an N,N-dimethylformamide solvent, then adding aminoacetophenone and dicyclohexylcarbodiimide thereto to carry out a modification reaction, and after the reaction is completed, centrifugally washing and drying to obtain aminoacetophenone-modified graphene; (2) adding formaldehyde solution to the ethanol solution of p-phenylenediamine, adjusting the pH to 3-5, and stirring until uniform, then adding aminoacetophenone-modified graphene, refluxing and performing Mannich reaction, filtering, washing, and drying to obtain p-phenylenediamine functionalized graphene; (3) adding phenol, formaldehyde solution and sodium hydroxide to deionized water one by one, stirring evenly, then adding p-phenylenediamine functionalized graphene, and then transferring to a reactor to carry out a polymerization reaction. After the reaction is completed, dehydrating, washing and drying to obtain a graphene-grafted phenolic resin; (4) Add melamine and urea to the graphene-grafted phenolic resin, react at 50-60° C. for 30-60 min, cool to room temperature, add 3-8 wt % of ammonium sulfate, stir evenly, and obtain a graphene-grafted phenolic resin binder composite material.
2. A graphene-grafted phenolic resin binder composite material according to claim 1, characterized in that: In the step (1), the mass ratio of graphene oxide, aminoacetophenone and dicyclohexylcarbodiimide is 100:150-250:10-30.
3. The graphene-grafted phenolic resin binder composite material according to claim 1, characterized in that: The temperature of the modification reaction in step (1) is 20-50° C., and the reaction time is 18-30 hours.
4. The graphene-grafted phenolic resin binder composite material according to claim 1, characterized in that: In the step (2), the mass ratio of aminoacetophenone-modified graphene, p-phenylenediamine and formaldehyde is 100:120-150:40-60.
5. The graphene-grafted phenolic resin binder composite material according to claim 1, characterized in that: The temperature of the Mannich reaction in step (2) is 60-90° C., and the reaction time is 12-24 h.
6. The graphene-grafted phenolic resin binder composite material according to claim 1, characterized in that: In the step (3), the mass ratio of phenol, formaldehyde, sodium hydroxide and p-phenylenediamine functionalized graphene is 100:130-140:1-10:1-2.
5.
7. The graphene-grafted phenolic resin binder composite material according to claim 1, characterized in that: The polymerization reaction temperature in step (3) is 80-120° C., and the reaction time is 1-3 hours.
8. The graphene-grafted phenolic resin binder composite material according to claim 1, characterized in that: In the step (4), the mass ratio of the graphene-grafted phenolic resin, melamine and urea is 10:8-12:30-50.