CN112552526A - Preparation method and application of functionalized graphene grafted modified polyurethane material - Google Patents
Preparation method and application of functionalized graphene grafted modified polyurethane material Download PDFInfo
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Abstract
The invention relates to the technical field of polyurethane flame retardance, and discloses a functionalized graphene grafted modified polyurethane material, wherein in a catalytic system of diethylenetriamine and cuprous bromide, alkynyl of functionalized graphene and azide groups of polyurethane are subjected to click reaction to generate 1,2, 3-triazole groups, the graphene and the polyurethane are subjected to chemical covalent grafting, the interface affinity and the dispersity of the graphene and the polyurethane are improved, the agglomeration of the graphene is avoided, the tensile strength and the elongation at break of the polyurethane are enhanced, the 1,2, 3-triazole groups with high nitrogen content are modified on the surface, a large amount of non-combustible gas is generated by thermal decomposition of the 1,2, 3-triazole groups under high-temperature combustion of the graphene with high nitrogen content, the foaming effect of the polyurethane material in the combustion process is promoted, and the uniformly dispersed graphene is carbonized at high temperature to form a continuous and compact foam carbon layer, the combustion process of polyurethane is inhibited, so that the excellent flame retardant effect is achieved.
Description
Technical Field
The invention relates to the technical field of polyurethane flame retardance, in particular to a preparation method and application of a functionalized graphene grafted modified polyurethane material.
Background
The flame retardant mainly comprises a nitrogen flame retardant, a nitrogen-phosphorus flame retardant, a silicon flame retardant, a halogen-containing flame retardant and the like, and can be divided into an additive flame retardant and a reactive flame retardant, wherein the reactive flame retardant is added into a polymer molecular chain as a reaction monomer, and the additive flame retardant is directly physically or mechanically mixed with a high polymer, so that the flame retardant property of high polymer materials such as epoxy resin, phenolic resin, polyurethane and the like can be obviously improved, but the additive flame retardant is generally used in large amount, the flame retardant property is not lasting, and if the additive flame retardant is not well compatible with the high polymer material, the mechanical properties such as strength, toughness and the like of the material can be influenced.
The polyurethane is a common high molecular material, has good rebound resilience, toughness and mechanical property, chemical resistance, easy processing and good film forming property, can be made into polyurethane plastics, polyurethane paint, polyurethane film, polyurethane elastomer and the like, has wide application in the aspects of furniture and household appliances, mechanical manufacturing, aerospace and the like, so that the comprehensive properties of the polyurethane material such as mechanical strength, mechanical property, flame retardance, thermodynamic stability and the like need to be improved so as to meet the requirement of industrial development, the graphene has unique mechanical, thermal and electrical properties, can be used as a nano filler and an auxiliary agent, is widely applied to high polymer materials such as polyurethane and the like, generally, a dispersant such as polyvinylpyrrolidone and a silane coupling agent is required to improve the dispersibility of graphene in a polyurethane material, but the graphene agglomeration phenomenon is still serious, and the introduction of the dispersant can influence the comprehensive performance of the polyurethane.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a preparation method and application of a functionalized graphene grafted modified polyurethane material, solves the problems of poor dispersibility and interface affinity of graphene in a polyurethane material, and simultaneously solves the problem of poor flame retardant property of polyurethane.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a functionalized graphene grafted modified polyurethane material comprises the following steps:
(1) adding a toluene solvent, graphene oxide and 4-ethynylaniline into a reaction beaker, placing the reaction beaker in an atmosphere regulation reaction device, heating and reacting in a nitrogen atmosphere, cooling, distilling under reduced pressure, washing and removing impurities to obtain the alkynyl functionalized graphene.
(2) Adding an acetone solvent, polyether glycol, toluene diisocyanate, 2-dihydroxybutyric acid and dibutyltin dilaurate into a reaction beaker, heating to 65-75 ℃, reacting for 2-4h, distilling under reduced pressure, washing and removing impurities to obtain the carboxyl-containing polyurethane.
(3) Adding thionyl chloride and polyurethane prepolymer into a reaction beaker, placing the reaction beaker in an atmosphere regulation reaction device, adding N, N-dimethylformamide as a catalyst under the nitrogen atmosphere, heating the reaction beaker to 75-85 ℃, carrying out reflux reaction for 3-6h, carrying out reduced pressure distillation, washing and removing impurities to obtain the acyl chloride polyurethane.
(4) Adding distilled water and an acetone solvent into a reaction beaker, adding sodium azide, stirring for dissolving, adding an acetone solution of acyl chlorinated polyurethane at 0-5 ℃, reacting for 3-8h, adding acetone and distilled water for extraction, taking an acetone organic phase, distilling under reduced pressure, washing and drying to obtain the azido polyurethane.
(5) Adding an N, N-dimethylformamide solvent, polyurethane azide, alkynyl functionalized graphene, an accelerant divinyl triamine and a catalyst cuprous bromide into a reaction beaker, placing the reaction beaker into an atmosphere regulation reaction device, reacting for 12-24h in a nitrogen atmosphere, carrying out vacuum drying, washing and doping, dissolving a solid product in an acetone solvent, pouring the acetone solvent on a polytetrafluoroethylene plate, carrying out vacuum defoaming and film forming to obtain the functionalized graphene grafted modified polyurethane material, and applying the functionalized graphene grafted modified polyurethane material to a flame-retardant polyurethane material.
Preferably, the atmosphere adjusting reaction device in the step (1) comprises an air inlet pipe and an air outlet pipe, the air inlet pipe and the air outlet pipe are movably connected with an air inlet valve and an air outlet valve, air holes are formed in the surfaces of the air inlet pipe and the air outlet pipe, an oil bath groove is formed in the atmosphere adjusting reaction device, a heating plate is arranged below the oil bath groove, an objective table is fixedly connected to the inside of the oil bath groove, and a reaction beaker is arranged above the objective table.
Preferably, the mass ratio of the polyether polyol, the toluene diisocyanate, the 2, 2-dihydroxybutyric acid and the dibutyltin dilaurate in the step (2) is 100:10-20:0.5-2: 0.02-0.05.
Preferably, the mass ratio of the thionyl chloride, the polyurethane prepolymer and the N, N-dimethylformamide as the catalyst in the step (3) is 100:5-15: 0.1-0.3.
Preferably, the mass ratio of the sodium azide to the acyl chloride polyurethane in the step (4) is 1-4: 100.
Preferably, the mass ratio of the polyurethane azide, the alkynyl functionalized graphene, the divinyl triamine and the cuprous bromide in the step (5) is 100:0.5-3:0.15-0.5: 0.1-0.4.
Drawings
FIG. 1 is a schematic view of the structure of an atmosphere control reaction apparatus;
fig. 2 is a schematic view of the structure of the intake pipe.
1-atmosphere adjusting reaction device; 2, an air inlet pipe; 3-air outlet pipe; 4-an air inlet valve; 5-an air outlet valve; 6-air holes; 7-oil bath groove; 8-heating plate; 9-an object stage; 10-reaction beaker.
(III) advantageous technical effects
Compared with the prior art, the invention has the following chemical experiment principle and beneficial technical effects:
according to the functional graphene graft modification polyurethane material, amino of 4-ethynylaniline is easy to react with carboxyl and epoxy of graphene oxide to obtain alkynyl functional graphene, 2, 2-dihydroxybutyric acid participates in the polymerization process of polyurethane, so that carboxyl groups are introduced into a polyurethane molecular chain, the carboxyl groups are reacted with thionyl chloride to obtain acylchlorinated polyurethane, and further the acyl chloride groups are reacted with sodium azide to obtain azide polyurethane, so that the azide groups are introduced into the polyurethane molecular chain.
According to the functionalized graphene grafted modified polyurethane material, in a catalytic system of divinyl triamine and cuprous bromide, alkynyl of functionalized graphene and azide groups of polyurethane generate simple and efficient click reaction, 1, 3-dipolar cycloaddition is performed to generate 1,2, 3-triazole groups, so that graphene and polyurethane are chemically and covalently grafted, the graphene and the polyurethane are organically combined through the connection of chemical covalent bonds, the interface affinity and the dispersity of the graphene and the polyurethane are remarkably improved, the agglomeration of the graphene is avoided, and the highly dispersed graphene has mechanical properties such as tensile strength, elongation at break and the like to the polyurethane.
According to the functionalized graphene graft modification polyurethane material, the 1,2, 3-triazole group modified graphene has high nitrogen content in the 1,2, 3-triazole group under high-temperature combustion, a large amount of non-combustible gas is generated by thermal decomposition, the foaming effect of the polyurethane material in the combustion process is promoted, and the uniformly dispersed graphene is carbonized at high temperature to form a continuous and compact foam carbon layer, so that the combustion process of polyurethane is inhibited, and the 1,2, 3-triazole group modified graphene can be used as an intumescent flame retardant to achieve an excellent flame retardant effect.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a preparation method of a functionalized graphene grafted modified polyurethane material comprises the following steps:
(1) adding toluene solvent, graphene oxide and 4-ethynylaniline into a reaction beaker, placing the mixture in an atmosphere adjusting reaction device, wherein the atmosphere adjusting reaction device comprises an air inlet pipe and an air outlet pipe, the air inlet pipe and the air outlet pipe are movably connected with an air inlet valve and an air outlet valve, air inlet pipe and air outlet pipe are provided with air holes on the surfaces, an oil bath groove is arranged inside the atmosphere adjusting reaction device, a heating plate is arranged below the oil bath groove, an objective table is fixedly connected inside the oil bath groove, the reaction beaker is arranged above the objective table, and in a nitrogen atmosphere, heating reaction is carried out, cooling, reduced pressure distillation and washing impurity removal are carried out, so that alkynyl functionalized graphene is prepared.
(2) Adding an acetone solvent, polyether polyol, toluene diisocyanate, 2-dihydroxybutyric acid and dibutyltin dilaurate in a mass ratio of 100:10-20:0.5-2:0.02-0.05 into a reaction beaker, heating to 65-75 ℃, reacting for 2-4h, distilling under reduced pressure, washing to remove impurities, and thus obtaining the carboxyl-containing polyurethane.
(3) Adding thionyl chloride and polyurethane prepolymer into a reaction beaker, adding N, N-dimethylformamide serving as a catalyst in a nitrogen atmosphere at a mass ratio of 100:5-15:0.1-0.3, heating to 75-85 ℃, carrying out reflux reaction for 3-6h, carrying out reduced pressure distillation, washing and impurity removal to obtain the acyl chloride polyurethane.
(4) Adding distilled water and an acetone solvent into a reaction beaker, adding sodium azide, stirring for dissolving, adding an acetone solution of acyl chloride polyurethane at 0-5 ℃, reacting for 3-8 hours, adding acetone and distilled water for extraction, taking an acetone organic phase, distilling under reduced pressure, washing and drying to obtain the azide polyurethane, wherein the mass ratio of the sodium azide to the acyl chloride polyurethane is 1-4: 100.
(5) Adding N, N-dimethylformamide solvent, polyurethane azide, alkynyl functional graphene, promoter divinyl triamine and catalyst cuprous bromide in a mass ratio of 100:0.5-3:0.15-0.5:0.1-0.4 into a reaction beaker, placing the reaction beaker in an atmosphere regulation reaction device, reacting for 12-24 hours in a nitrogen atmosphere, carrying out vacuum drying and washing doping, dissolving a solid product in acetone solvent, pouring the acetone solvent on a polytetrafluoroethylene plate, and carrying out vacuum defoaming and film forming to obtain the functional graphene grafted modified polyurethane material.
Example 1
(1) Adding toluene solvent, graphene oxide and 4-ethynylaniline into a reaction beaker, placing the mixture in an atmosphere adjusting reaction device, wherein the atmosphere adjusting reaction device comprises an air inlet pipe and an air outlet pipe, the air inlet pipe and the air outlet pipe are movably connected with an air inlet valve and an air outlet valve, air inlet pipe and air outlet pipe are provided with air holes on the surfaces, an oil bath groove is arranged inside the atmosphere adjusting reaction device, a heating plate is arranged below the oil bath groove, an objective table is fixedly connected inside the oil bath groove, the reaction beaker is arranged above the objective table, and in a nitrogen atmosphere, heating reaction is carried out, cooling, reduced pressure distillation and washing impurity removal are carried out, so that alkynyl functionalized graphene is prepared.
(2) Adding an acetone solvent, polyether polyol, toluene diisocyanate, 2-dihydroxybutyric acid and dibutyltin dilaurate in a mass ratio of 100:10:0.5:0.02 into a reaction beaker, heating to 65 ℃, reacting for 2 hours, distilling under reduced pressure, washing and removing impurities to obtain the carboxyl-containing polyurethane.
(3) Adding thionyl chloride and polyurethane prepolymer into a reaction beaker, adding N, N-dimethylformamide as a catalyst in a nitrogen atmosphere at a mass ratio of 100:5:0.1, heating to 75 ℃, carrying out reflux reaction for 3 hours, carrying out reduced pressure distillation, washing and removing impurities to obtain the acyl chloride polyurethane.
(4) Adding distilled water and an acetone solvent into a reaction beaker, adding sodium azide, stirring for dissolving, adding an acetone solution of acyl chloride polyurethane at 0 ℃, wherein the mass ratio of the sodium azide to the acyl chloride polyurethane is 1:100, reacting for 3 hours, adding acetone and distilled water for extraction, taking an acetone organic phase, distilling under reduced pressure, washing and drying to obtain the azide polyurethane.
(5) Adding N, N-dimethylformamide solvent, nitridized polyurethane with the mass ratio of 100:0.5:0.15:0.1, alkynyl functionalized graphene, accelerant divinyl triamine and catalyst cuprous bromide into a reaction beaker, placing the reaction beaker in an atmosphere regulation reaction device, reacting for 12 hours in a nitrogen atmosphere, carrying out vacuum drying, washing and doping, dissolving a solid product in acetone solvent, pouring the acetone solvent on a polytetrafluoroethylene plate, carrying out vacuum defoaming and film forming to obtain the functionalized graphene grafted modified polyurethane material, and applying the functionalized graphene grafted modified polyurethane material to a flame-retardant polyurethane material.
Example 2
(1) Adding toluene solvent, graphene oxide and 4-ethynylaniline into a reaction beaker, placing the mixture in an atmosphere adjusting reaction device, wherein the atmosphere adjusting reaction device comprises an air inlet pipe and an air outlet pipe, the air inlet pipe and the air outlet pipe are movably connected with an air inlet valve and an air outlet valve, air inlet pipe and air outlet pipe are provided with air holes on the surfaces, an oil bath groove is arranged inside the atmosphere adjusting reaction device, a heating plate is arranged below the oil bath groove, an objective table is fixedly connected inside the oil bath groove, the reaction beaker is arranged above the objective table, and in a nitrogen atmosphere, heating reaction is carried out, cooling, reduced pressure distillation and washing impurity removal are carried out, so that alkynyl functionalized graphene is prepared.
(2) Adding an acetone solvent, polyether polyol, toluene diisocyanate, 2-dihydroxybutyric acid and dibutyltin dilaurate in a mass ratio of 100:14:1:0.03 into a reaction beaker, heating to 70 ℃, reacting for 4 hours, distilling under reduced pressure, washing and removing impurities to obtain the carboxyl-containing polyurethane.
(3) Adding thionyl chloride and polyurethane prepolymer into a reaction beaker, adding N, N-dimethylformamide as a catalyst in a nitrogen atmosphere, heating to 85 ℃, carrying out reflux reaction for 4 hours, carrying out reduced pressure distillation, washing and impurity removal to obtain the acyl chloride polyurethane.
(4) Adding distilled water and an acetone solvent into a reaction beaker, adding sodium azide, stirring for dissolving, adding an acetone solution of acyl chloride polyurethane at the temperature of 2 ℃, reacting for 8 hours, adding acetone and distilled water for extraction, taking an acetone organic phase, distilling under reduced pressure, washing and drying to obtain the acyl chloride polyurethane.
(5) Adding N, N-dimethylformamide solvent, nitridized polyurethane with the mass ratio of 100:1.5:0.3:0.25, alkynyl functionalized graphene, promoter divinyl triamine and catalyst cuprous bromide into a reaction beaker, placing the reaction beaker in an atmosphere regulation reaction device, reacting for 18 hours in a nitrogen atmosphere, carrying out vacuum drying and washing doping, dissolving a solid product in acetone solvent, pouring the acetone solvent on a polytetrafluoroethylene plate, carrying out vacuum defoaming and film forming to obtain the functionalized graphene grafted modified polyurethane material, and applying the functionalized graphene grafted modified polyurethane material to a flame-retardant polyurethane material.
Example 3
(1) Adding toluene solvent, graphene oxide and 4-ethynylaniline into a reaction beaker, placing the mixture in an atmosphere adjusting reaction device, wherein the atmosphere adjusting reaction device comprises an air inlet pipe and an air outlet pipe, the air inlet pipe and the air outlet pipe are movably connected with an air inlet valve and an air outlet valve, air inlet pipe and air outlet pipe are provided with air holes on the surfaces, an oil bath groove is arranged inside the atmosphere adjusting reaction device, a heating plate is arranged below the oil bath groove, an objective table is fixedly connected inside the oil bath groove, the reaction beaker is arranged above the objective table, and in a nitrogen atmosphere, heating reaction is carried out, cooling, reduced pressure distillation and washing impurity removal are carried out, so that alkynyl functionalized graphene is prepared.
(2) Adding an acetone solvent, polyether polyol, toluene diisocyanate, 2-dihydroxybutyric acid and dibutyltin dilaurate in a mass ratio of 100:20:2:0.05 into a reaction beaker, heating to 75 ℃, reacting for 4 hours, distilling under reduced pressure, washing and removing impurities to obtain the carboxyl-containing polyurethane.
(3) Adding thionyl chloride and polyurethane prepolymer into a reaction beaker, adding N, N-dimethylformamide as a catalyst in a nitrogen atmosphere at a mass ratio of 100:15:0.3, heating to 85 ℃, carrying out reflux reaction for 6 hours, carrying out reduced pressure distillation, washing and removing impurities to obtain the acyl chloride polyurethane.
(4) Adding distilled water and an acetone solvent into a reaction beaker, adding sodium azide, stirring for dissolving, adding an acetone solution of acyl chloride polyurethane at 5 ℃, wherein the mass ratio of the sodium azide to the acyl chloride polyurethane is 4:100, reacting for 8 hours, adding acetone and distilled water for extraction, taking an acetone organic phase, distilling under reduced pressure, washing and drying to obtain the azide polyurethane.
(5) Adding N, N-dimethylformamide solvent, nitridized polyurethane with the mass ratio of 100:3:0.5:0.4, alkynyl functionalized graphene, promoter divinyl triamine and catalyst cuprous bromide into a reaction beaker, placing the reaction beaker in an atmosphere regulation reaction device, reacting for 24 hours in a nitrogen atmosphere, vacuum drying, washing and doping, dissolving a solid product in acetone solvent, pouring the acetone solvent on a polytetrafluoroethylene plate, and carrying out vacuum defoaming and film forming to obtain the functionalized graphene graft modified polyurethane material which is applied to the flame-retardant polyurethane material.
Comparative example 1
(1) Adding toluene solvent, graphene oxide and 4-ethynylaniline into a reaction beaker, placing the mixture in an atmosphere adjusting reaction device, wherein the atmosphere adjusting reaction device comprises an air inlet pipe and an air outlet pipe, the air inlet pipe and the air outlet pipe are movably connected with an air inlet valve and an air outlet valve, air inlet pipe and air outlet pipe are provided with air holes on the surfaces, an oil bath groove is arranged inside the atmosphere adjusting reaction device, a heating plate is arranged below the oil bath groove, an objective table is fixedly connected inside the oil bath groove, the reaction beaker is arranged above the objective table, and in a nitrogen atmosphere, heating reaction is carried out, cooling, reduced pressure distillation and washing impurity removal are carried out, so that alkynyl functionalized graphene is prepared.
(2) Adding an acetone solvent, polyether polyol, toluene diisocyanate, 2-dihydroxybutyric acid and dibutyltin dilaurate in a mass ratio of 100:4:0.2:0.008 into a reaction beaker, heating to 75 ℃, reacting for 4 hours, distilling under reduced pressure, washing and removing impurities to obtain carboxyl-containing polyurethane.
(3) Adding thionyl chloride and polyurethane prepolymer into a reaction beaker, adding N, N-dimethylformamide as a catalyst in a nitrogen atmosphere, heating to 85 ℃, carrying out reflux reaction for 4 hours, carrying out reduced pressure distillation, washing and impurity removal to obtain the acyl chloride polyurethane.
(4) Adding distilled water and an acetone solvent into a reaction beaker, adding sodium azide, stirring for dissolving, adding an acetone solution of acyl chloride polyurethane at 0 ℃, wherein the mass ratio of the sodium azide to the acyl chloride polyurethane is 0.5:100, reacting for 8 hours, adding acetone and distilled water for extraction, taking an acetone organic phase, carrying out reduced pressure distillation, washing and drying to obtain the azide polyurethane.
(5) Adding N, N-dimethylformamide solvent, nitridized polyurethane with the mass ratio of 100:0.2:0.1:0.05, alkynyl functionalized graphene, promoter divinyl triamine and catalyst cuprous bromide into a reaction beaker, placing the reaction beaker in an atmosphere regulation reaction device, reacting for 24 hours in a nitrogen atmosphere, carrying out vacuum drying and washing doping, dissolving a solid product in acetone solvent, pouring the acetone solvent on a polytetrafluoroethylene plate, carrying out vacuum defoaming and film forming to obtain the functionalized graphene grafted modified polyurethane material, and applying the functionalized graphene grafted modified polyurethane material to a flame-retardant polyurethane material.
Comparative example 2
(1) Adding toluene solvent, graphene oxide and 4-ethynylaniline into a reaction beaker, placing the mixture in an atmosphere adjusting reaction device, wherein the atmosphere adjusting reaction device comprises an air inlet pipe and an air outlet pipe, the air inlet pipe and the air outlet pipe are movably connected with an air inlet valve and an air outlet valve, air inlet pipe and air outlet pipe are provided with air holes on the surfaces, an oil bath groove is arranged inside the atmosphere adjusting reaction device, a heating plate is arranged below the oil bath groove, an objective table is fixedly connected inside the oil bath groove, the reaction beaker is arranged above the objective table, and in a nitrogen atmosphere, heating reaction is carried out, cooling, reduced pressure distillation and washing impurity removal are carried out, so that alkynyl functionalized graphene is prepared.
(2) Adding an acetone solvent, polyether polyol, toluene diisocyanate, 2-dihydroxybutyric acid and dibutyltin dilaurate in a mass ratio of 100:25:3:0.06 into a reaction beaker, heating to 75 ℃, reacting for 3h, distilling under reduced pressure, washing and removing impurities to obtain the carboxyl-containing polyurethane.
(3) Adding thionyl chloride and polyurethane prepolymer into a reaction beaker, adding N, N-dimethylformamide as a catalyst in a nitrogen atmosphere, heating to 85 ℃, carrying out reflux reaction for 6 hours, carrying out reduced pressure distillation, washing and impurity removal to obtain the acyl chloride polyurethane.
(4) Adding distilled water and an acetone solvent into a reaction beaker, adding sodium azide, stirring for dissolving, adding an acetone solution of acyl chloride polyurethane at the temperature of 2 ℃, reacting for 8 hours, adding acetone and distilled water for extraction, taking an acetone organic phase, distilling under reduced pressure, washing and drying to obtain the azide polyurethane, wherein the mass ratio of the sodium azide to the acyl chloride polyurethane is 6: 100.
(5) Adding N, N-dimethylformamide solvent, polyurethane azide with the mass ratio of 100:4:0.65:0.5, alkynyl functionalized graphene, promoter divinyl triamine and catalyst cuprous bromide into a reaction beaker, placing the reaction beaker in an atmosphere regulation reaction device, reacting for 18 hours in a nitrogen atmosphere, vacuum drying, washing and doping, dissolving a solid product in acetone solvent, pouring the acetone solvent on a polytetrafluoroethylene plate, and carrying out vacuum defoaming and film forming to obtain the functionalized graphene graft modified polyurethane material.
An LTAO-73 limiting oxygen index tester is used for testing the limiting oxygen index and the flame retardant property of the functionalized graphene grafted modified polyurethane material, and the test standard is GB/T2406.2-2009.
And testing the tensile strength and the elongation at break of the functionalized graphene grafted modified polyurethane material by using an MX-2T double-column tensile machine, wherein the test standard is GB/T1040.3-2006.
Claims (6)
1. A functionalized graphene grafted modified polyurethane material is characterized in that: the preparation method of the functionalized graphene grafted modified polyurethane material comprises the following steps:
(1) adding a toluene solvent, graphene oxide and 4-ethynylaniline into a reaction beaker, placing the reaction beaker in an atmosphere regulation reaction device, and heating and reacting in a nitrogen atmosphere to obtain alkynyl functionalized graphene;
(2) adding an acetone solvent, polyether glycol, toluene diisocyanate, 2-dihydroxybutyric acid and dibutyltin dilaurate into a reaction beaker, heating to 65-75 ℃, and reacting for 2-4h to obtain carboxyl-containing polyurethane;
(3) adding thionyl chloride and polyurethane prepolymer into a reaction beaker, placing the reaction beaker in an atmosphere regulation reaction device, adding N, N-dimethylformamide as a catalyst under the nitrogen atmosphere, heating the reaction beaker to 75-85 ℃, and carrying out reflux reaction for 3-6 hours to obtain acyl chloride polyurethane;
(4) adding distilled water and an acetone solvent into a reaction beaker, adding sodium azide, stirring for dissolving, adding an acetone solution of acyl chlorinated polyurethane at 0-5 ℃, and reacting for 3-8 hours to obtain azido polyurethane;
(5) adding an N, N-dimethylformamide solvent, polyurethane azide, alkynyl functionalized graphene, an accelerant divinyl triamine and a catalyst cuprous bromide into a reaction beaker, placing the reaction beaker into an atmosphere regulation reaction device, reacting for 12-24h in a nitrogen atmosphere, dissolving a solid product in an acetone solvent, pouring the mixture on a polytetrafluoroethylene plate, and defoaming in vacuum to form a film so as to obtain the functionalized graphene grafted modified polyurethane material which is applied to the flame-retardant polyurethane material.
2. The functionalized graphene grafted modified polyurethane material according to claim 1, wherein: the atmosphere adjusting reaction device in the step (1) comprises an air inlet pipe and an air outlet pipe, the air inlet pipe and the air outlet pipe are movably connected with an air inlet valve and an air outlet valve, air holes are formed in the surfaces of the air inlet pipe and the air outlet pipe, an oil bath groove is formed in the atmosphere adjusting reaction device, a heating plate is arranged below the oil bath groove, an objective table is fixedly connected to the inner portion of the oil bath groove, and a reaction beaker is arranged above the objective table.
3. The functionalized graphene grafted modified polyurethane material according to claim 1, wherein: the mass ratio of the polyether polyol, the toluene diisocyanate, the 2, 2-dihydroxybutyric acid and the dibutyltin dilaurate in the step (2) is 100:10-20:0.5-2: 0.02-0.05.
4. The functionalized graphene grafted modified polyurethane material according to claim 1, wherein: the mass ratio of the thionyl chloride, the polyurethane prepolymer and the N, N-dimethylformamide serving as the catalyst in the step (3) is 100:5-15: 0.1-0.3.
5. The functionalized graphene grafted modified polyurethane material according to claim 1, wherein: the mass ratio of the sodium azide to the acyl chloride polyurethane in the step (4) is 1-4: 100.
6. The functionalized graphene grafted modified polyurethane material according to claim 1, wherein: the mass ratio of the polyurethane azide, the alkynyl functionalized graphene, the divinyl triamine and the cuprous bromide in the step (5) is 100:0.5-3:0.15-0.5: 0.1-0.4.
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| CN115458713A (en) * | 2022-10-21 | 2022-12-09 | 深圳市山木新能源科技股份有限公司 | Polyanion sodium ion battery electrode |
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