CN104693463A - Thermosetting polymer compound, thin film and preparation method thereof - Google Patents
Thermosetting polymer compound, thin film and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of thermosetting polymer materials, and particularly relates to a thermosetting polymer compound, a thin film and a preparation method thereof. The preparation method comprises the following steps: 1) preparing an amino graphene aqueous solution; 2) preparing paraformaldehyde and aprotic/water mixed solvent into suspension, depolymerizing, and cooling to the room temperature to obtain formaldehyde reaction liquid; 3) dissolving aromatic diamine and/or aromatic triamine in an aprotic solvent to obtain arylamine reaction liquid; 4) uniformly mixing the formaldehyde reaction liquid and the arylamine reaction liquid with the amino graphene aqueous solution, pre-polymerizing, horizontally paving a film, and curing at a high temperature to prepare the thin film. The thickness of the thin film is adjustable, the mechanical properties of the thin film are excellent, and the Young modulus, the tensile strength, the elongation at break and the tensile failure can respectively reach 3-6 GPa, 90-140 MPa, 3-6% and 2.0-3.0 MJ/m<3>. The main raw materials, namely arylamine and functional graphene of the composite thin film can be recycled, and the recovery rate is higher than 90%.
Description
Technical field
The present invention relates to thermoset macromolecule material field, thermosetting polymer laminated film of specifically a kind of recycling capable of circulation and preparation method thereof.
Background technology
Thermosetting polymer matrix material has specific tenacity and the feature such as specific rigidity is high, corrosion resistance nature is good, scantlings of the structure is stable, is widely used in the high and new technology fields such as electronic information, aerospace, wind-power electricity generation, communications and transportation.But, compared with thermoplastic macromolecule material, thermosetting polymer matrices of composite material generally first forms prepolymer, functional group wherein potential time shaping continues reaction and forms crosslinked three dimensional structure and solidify, this transformation is irreversible, can not fusion plastification during heating, be also insoluble to solvent, cannot recycle.Composite scrap thing (as circuit card), usually used as garbage bury or burning disposal, not only causes huge waste to resource, also brings serious environmental pollution simultaneously.
Summary of the invention
The object of the invention is the thermosetting polymer composite film material proposing a kind of recycling capable of circulation, dry the excellent laminated film of after fixing processability by formaldehyde, aromatic amine and amination Graphene in non-proton/water mixed solvent situ pre-polymerization, further horizontal plastic film mulch.Utilize Hexahydrotriazine structure the feature of depolymerization can realize the object of main raw material recycling in strong acid dilute solution.
Object of the present invention is achieved through the following technical solutions:
A preparation method for the thermosetting polymer laminated film of recycling capable of circulation, comprises the steps:
1) amination modification is carried out to graphene oxide, preparation amination graphene aqueous solution;
2) paraformaldehyde and non-proton/water mixed solvent are made into suspension, within 0.1 ~ 2 hour, carry out depolymerization, cool to room temperature at 60 ~ 100 DEG C of stirring reactions, obtain formaldehyde reaction liquid;
3) aromatic diamines and/or fragrant triamine are dissolved in aprotic solvent, obtain aromatic amine reaction solution;
4) formaldehyde, aromatic amine reaction solution are mixed with amination graphene aqueous solution, ultrasonic disperse 0 ~ 60 minute under room temperature, be warmed up to 30 ~ 80 DEG C of stirring reactions and carry out pre-polymerization in 1 ~ 60 minute, plastic film mulch on horizontal glass plate further, first dry 0.5 ~ 6 hour for 60 ~ 120 DEG C, dry 2 ~ 6 hours for 160 ~ 200 DEG C again, obtain tawny film object product.
The structure of described aromatic diamines, fragrant triamine is as follows:
Described formaldehyde strictly follows the principle of measuring than 1:1 with the primary amino mol ratio in aromatic amine and amination Graphene; In the mixed solvent of end reaction system, the volume content of water is 0.5% ~ 60%, and the volume adding mixed solvent in every gram of reactant is 3 ~ 20ml.
The preparation of described amination graphene aqueous solution:
In graphene oxide water solution, add aprotic solvent, aromatic amine and catalyzer, chemically modified is carried out to graphene oxide, further by centrifugal, washing, obtained amination graphene aqueous solution.
Described catalyzer is methyldiethanolamine, trolamine, diethyl amino propylamine, m-xylylene two (dimethylamine), N, N '-dimethyl piperazine, N-crassitude, N-methylhydroxy piperidines, N, N, N ', N '-tetramethyl-diaminoethanes, N, N, N ', N ', N '-five methyl diethylentriamine, triethylamine, Tributylamine, Trimethylamine, triethylenediamine, N-methylmorpholine, N-methyl piperidine or pyridine, Isosorbide-5-Nitrae-diazabicyclo [2.2.2]-octane, 1,8-diazo bicyclic [5,4,0] 11 carbon-7-alkene, 1,8-diazabicyclo [2,2,2] octane, 4-dimethylaminopyridine, 4-(N-pyrrolidino) pyridine, benzyl dimethyl amine, benzyldiethylamine, dimethylaminomethyl phenol, 2,6-bis-(dimethylaminomethyl) phenol, 2,4,6-tri-(dimethylaminomethyl) phenol, N-N xylidine, N-N dimethyl benzylamine, one or more in triphenylphosphine, every gram of graphene oxide correspondence 0.01 ~ 1g aromatic amine, 0.01 ~ 0.1g catalyzer, 20 ~ 200ml aprotic solvent.
Described paraformaldehyde be the polymerization degree lower than 100 lower molecular weight formaldehyde white crystalline powder.
Described aprotic solvent is one or more in N-Methyl pyrrolidone, dimethyl formamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), 2,5-dimethyl furans, hexamethylphosphoramide.
The recoverying and utilizing method of above-mentioned film, every gram of film is after the strong acid that 5 ~ 20ml concentration is 0.1 ~ 1mol/L soaks 1 ~ 24 hour at 50 ~ 95 DEG C, cool to room temperature, washed by centrifugal, washing, alkaline solution, wash the rear recyclable amination Graphene of process, by centrifugate further across after alkaline solution neutralization, precipitation, filtration, washing, drying and processing, obtain aromatic amine.Preferably, described strong acid is sulfuric acid, hydrochloric acid; Alkaline solution is the saturated solution of sodium carbonate or sodium bicarbonate.
A kind of thermosetting polymer composite, this mixture has following structure:
Described thermosetting polymer laminated film preparation process representative reactions formula is as follows:
Compared with prior art, tool of the present invention has the following advantages and beneficial effect:
(1) the present invention adopts non-proton/water mixed solvent, by improving the dispersiveness of functionalization graphene in position in polymeric reaction solution and stability, effectively improves the dispersiveness of Graphene in laminated film product and reinforced effects; Adopting mixed solvent effectively can reduce consumption of organic solvent simultaneously, realizing the Effective Regulation of PARA FORMALDEHYDE PRILLS(91,95) and fragrant one hundred amine speed of response and degree by regulating water-content in solvent; Adopting formaldehyde strictly to follow the principle of measure than 1:1 with the primary amino mol ratio in aromatic amine and amination Graphene, effectively avoiding passingly improving product structure complexity that speed of response causes, the wasting of resources and problem of environmental pollution by adding excess formaldehyde; Synthesis for such thermosetting polymer matrix material provides a green new way.
(2) the thermosetting polymer laminated film prepared of the present invention, thickness is adjustable, film thickness scope is 0.1-300 μm, and there is excellent mechanical property, Young's modulus, tensile strength, elongation at break and tension fracture can reach 3-6GPa, 90-140MPa, 3%-6%, 2.0-3.2MJ/m respectively
3.Main raw material aromatic amine and functionalization graphene can recyclings after strong acid and mild alkaline treatment for film, and the rate of recovery reaches more than 90%.
Accompanying drawing explanation
Fig. 1 is thermosetting polymer laminated film dumbbell shape tension specimen and representative stress-strain curve.
Fig. 2 is the infrared spectrogram that the embodiment of the present invention 2 obtains laminated film.
Embodiment
Be described further of the present invention below in conjunction with specific embodiment, but content of the present invention is not limited to following embodiment.
Embodiment 1
Aromatic diamines MDA is adopted to modify graphene oxide (Product Labeling is MDA-GO, primary amino content 0.31mmol/g), the MDA-GO aqueous solution of preparation 2mg/ml.20.01mmol paraformaldehyde and 10ml dimethyl formamide/water mixed solvent are made into suspension, within 0.1 hour, carry out depolymerization, cool to room temperature at 100 DEG C of stirring reactions, obtain water white transparency formaldehyde reaction liquid.10mmol aromatic diamines MDA is dissolved in 8ml dimethyl formamide, obtains transparent aromatic amine reaction solution.By formaldehyde, aromatic amine reaction solution and 2ml MDA-GO aqueous solution evenly (in end reaction system mixed solvent, the volume content of water is 10%), ultrasonic disperse 10 minutes under room temperature, within 60 minutes, pre-polymerization is carried out at 30 DEG C of stirring reactions, plastic film mulch on horizontal glass plate further, dry for 120 DEG C and dry 4 hours for 0.5 hour, 180, obtain tawny translucent laminated film object product.MDA-GO content 0.16wt% in film, Young's modulus, tensile strength, elongation at break and tension fracture can reach respectively 4.9GPa, 138.9MPa, 4.4%, 3.1MJ/m
3(see Fig. 1, film dumbbell shape tension specimen and representative stress-strain curve (a)).Every gram of film, after the hydrochloric acid of 5ml, 1mol/L soaks 24 hours at 50 DEG C, is washed by centrifugal, washing, saturated solution of sodium carbonate, is washed, reclaims MDA-GO 3.90mg, the rate of recovery 97.5% after drying and processing; Centrifugate is reclaimed MDA 1.89g further across after the saturated neutralization of sodium carbonate, precipitation, filtration, washing, drying and processing, the rate of recovery 95.3%.
Embodiment 2
Aromatic diamines SDA is adopted to modify graphene oxide (Product Labeling is SDA-GO, primary amino content 0.63mmol/g), the SDA-GO aqueous solution of preparation 20mg/ml.14.13mmol paraformaldehyde and 7ml 2,5-dimethyl furans/water mixed solvent are made into suspension, within 0.8 hour, carry out depolymerization, cool to room temperature at 80 DEG C of stirring reactions, obtain formaldehyde reaction liquid.7mmol aromatic diamines ODA is dissolved in 3ml 2,5-dimethyl furan, obtains aromatic amine reaction solution.By formaldehyde, aromatic amine reaction solution and 10ml SDA-GO aqueous solution evenly (in end reaction system mixed solvent, the volume content of water is 50%), ultrasonic disperse 60 minutes under room temperature, within 5 minutes, pre-polymerization is carried out at 50 DEG C of stirring reactions, plastic film mulch on horizontal glass plate further, dry for 70 DEG C and dry 3 hours for 5 hours, 190, obtain brown laminated film object product.SDA-GO content 9.87wt% in film, Young's modulus, tensile strength, elongation at break and tension fracture can reach respectively 3.8GPa, 100.8MPa, 5.6%, 2.8MJ/m
3(see Fig. 1, representative stress-strain curve (b).Fig. 2 is laminated film infrared spectra.Every gram of film, after the hydrochloric acid of 20ml, 0.2mol/L soaks 12 hours at 70 DEG C, is washed by centrifugal, washing, saturated solution of sodium carbonate, is washed, reclaims SDA-GO 191.62mg, the rate of recovery 95.8% after drying and processing; Centrifugate is reclaimed ODA 1.37g further across after the saturated neutralization of sodium carbonate, precipitation, filtration, washing, drying and processing, the rate of recovery 97.7%.
Embodiment 3
Aromatic diamines APB is adopted to modify graphene oxide (Product Labeling is APB-GO, primary amino content 0.27mmol/g), the APB-GO aqueous solution of preparation 3mg/ml.16.01mmol paraformaldehyde and 6ml dimethyl sulfoxide (DMSO)/water mixed solvent are made into suspension, within 2 hours, carry out depolymerization, cool to room temperature at 60 DEG C of stirring reactions, obtain formaldehyde reaction liquid.8mmol aromatic diamines BDAO is dissolved in 2ml N-Methyl pyrrolidone, obtains aromatic amine reaction solution.By formaldehyde, aromatic amine reaction solution and 12mlAPB-GO aqueous solution evenly (in end reaction system mixed solvent, the volume content of water is 60%), ultrasonic disperse 30 minutes under room temperature, within 3 minutes, pre-polymerization is carried out at 40 DEG C of stirring reactions, plastic film mulch on horizontal glass plate further, dry for 80 DEG C and dry 2 hours for 3 hours, 200, obtain tawny translucent laminated film object product.APB-GO content 1.00wt% in film, Young's modulus, tensile strength, elongation at break and tension fracture can reach respectively 5.8GPa, 129.7MPa, 3.2%, 2.1MJ/m
3.Every gram of film, after the sulfuric acid of 15ml, 0.5mol/L soaks 6 hours at 80 DEG C, is washed by centrifugal, washing, saturated solution of sodium bicarbonate, is washed, reclaims APB-GO 35.05mg, the rate of recovery 97.4% after drying and processing; Centrifugate is reclaimed BDAO 2.83g further across after the saturated neutralization of sodium bicarbonate, precipitation, filtration, washing, drying and processing, the rate of recovery 92.0%.
Embodiment 4
Aromatic diamines ODA is adopted to modify graphene oxide (Product Labeling is ODA-GO, primary amino content 0.85mmol/g), the ODA-GO aqueous solution of preparation 2mg/ml.16.01mmol paraformaldehyde and 10mlN-methyl-2-pyrrolidone/water mixed solvent are made into suspension, within 1 hour, carry out depolymerization, cool to room temperature at 80 DEG C of stirring reactions, obtain formaldehyde reaction liquid.8mmol aromatic diamines BAPP is dissolved in 9ml N-Methyl pyrrolidone, obtains aromatic amine reaction solution.By formaldehyde, aromatic amine reaction solution and 1ml ODA-GO aqueous solution evenly (in end reaction system mixed solvent, the volume content of water is 5%), ultrasonic disperse 5 minutes under room temperature, within 30 minutes, pre-polymerization is carried out at 50 DEG C of stirring reactions, plastic film mulch on horizontal glass plate further, dry for 60 DEG C and dry 6 hours for 6 hours, 160, obtain tawny translucent laminated film object product.ODA-GO content 0.05wt% in film, Young's modulus, tensile strength, elongation at break and tension fracture can reach respectively 4.6GPa, 108.1MPa, 4.3%, 2.3MJ/m
3.Every gram of film, after the sulfuric acid of 10ml, 0.1mol/L soaks 2 hours at 95 DEG C, is washed by centrifugal, washing, saturated solution of sodium bicarbonate, is washed, reclaims ODA-GO 1.92mg, the rate of recovery 96.0% after drying and processing; Centrifugate is reclaimed BAPP 3.24g further across after the saturated neutralization of sodium bicarbonate, precipitation, filtration, washing, drying and processing, the rate of recovery 98.8%.
Embodiment 5
Fragrant triamine TAPOB is adopted to modify graphene oxide (Product Labeling is TAPOB-GO, primary amino content 0.14mmol/g), the TAPOB-GO aqueous solution of preparation 15mg/ml.16.02mmol paraformaldehyde and 6ml dimethyl sulfoxide (DMSO)/water mixed solvent are made into suspension, within 0.3 hour, carry out depolymerization, cool to room temperature at 90 DEG C of stirring reactions, obtain formaldehyde reaction liquid.4mmol aromatic diamines DDS and 4mmol ODA is dissolved in 4ml dimethyl sulfoxide (DMSO), obtains aromatic amine reaction solution.By formaldehyde, aromatic amine reaction solution and 8mlTAPOB-GO aqueous solution evenly (in end reaction system mixed solvent, the volume content of water is 40%), ultrasonic disperse 10 minutes under room temperature, within 20 minutes, pre-polymerization is carried out at 40 DEG C of stirring reactions, plastic film mulch on horizontal glass plate further, dry for 100 DEG C and dry 3 hours for 2 hours, 180, obtain tawny laminated film object product.TAPOB-GO content 5.01wt% in every gram of film, Young's modulus, tensile strength, elongation at break and tension fracture can reach respectively 3.2GPa, 95.1MPa, 5.9%, 2.8MJ/m
3.Film, after the hydrochloric acid of 15ml, 0.5mol/L soaks 8 hours at 60 DEG C, is washed by centrifugal, washing, saturated solution of sodium bicarbonate, is washed, reclaims TAPOB-GO 113.69mg, the rate of recovery 94.7% after drying and processing; Centrifugate is reclaimed DDS and ODA mixture 1.71g further across after the saturated neutralization of sodium bicarbonate, precipitation, filtration, washing, drying and processing, the rate of recovery 95.5%.
Embodiment 6
Aromatic diamines DMB is adopted to modify graphene oxide (Product Labeling is DMB-GO, primary amino content 1.28mmol/g), the DMB-GO aqueous solution of preparation 5mg/ml.22.03mmol paraformaldehyde and 10ml N-Methyl pyrrolidone/water mixed solvent are made into suspension, within 1 hour, carry out depolymerization, cool to room temperature at 80 DEG C of stirring reactions, obtain formaldehyde reaction liquid.8mmol aromatic diamines ODA and 2mmol TAPOB is dissolved in 6ml hexamethylphosphoramide, obtains aromatic amine reaction solution.By formaldehyde, aromatic amine reaction solution and 4ml DMB-GO aqueous solution evenly (in end reaction system mixed solvent, the volume content of water is 20%), ultrasonic disperse 5 minutes under room temperature, within 30 minutes, pre-polymerization is carried out at 35 DEG C of stirring reactions, plastic film mulch on horizontal glass plate further, dry for 60 DEG C and dry 4 hours for 12 hours, 170, obtain tawny translucent laminated film object product.DMB-GO content 0.65wt% in film, Young's modulus, tensile strength, elongation at break and tension fracture can reach respectively 4.5GPa, 124.6MPa, 3.9%, 2.4MJ/m
3.Every gram of film, after the hydrochloric acid of 10ml, 0.8mol/L soaks 5 hours at 70 DEG C, is washed by centrifugal, washing, saturated solution of sodium carbonate, is washed, reclaims DMB-GO 18.69mg, the rate of recovery 93.4% after drying and processing; Centrifugate is reclaimed ODA and TAPOB mixture 2.31g further across after the saturated neutralization of sodium carbonate, precipitation, filtration, washing, drying and processing, the rate of recovery 96.1%.
Embodiment 7
Aromatic diamines ODA is adopted to modify graphene oxide (Product Labeling is ODA-GO, primary amino content 0.85mmol/g), the ODA-GO aqueous solution of preparation 1mg/ml.14.01mmol paraformaldehyde and 8mlN-methyl-2-pyrrolidone/water mixed solvent are made into suspension, within 1.5 hours, carry out depolymerization, cool to room temperature at 65 DEG C of stirring reactions, obtain formaldehyde reaction liquid.2mmol SDA, 2mmol DDS, 2mmol TAPB are dissolved in 6mlN-methyl-2-pyrrolidone, obtain aromatic amine reaction solution.By formaldehyde, aromatic amine reaction solution and 6ml ODA-GO aqueous solution evenly (in end reaction system mixed solvent, the volume content of water is 30%), within 60 minutes, pre-polymerization is carried out at 30 DEG C of stirring reactions, plastic film mulch on horizontal glass plate further, dry for 90 DEG C and dry 2.5 hours for 3 hours, 200, obtain tawny translucent laminated film object product.ODA-GO content 0.29wt% in film, Young's modulus, tensile strength, elongation at break and tension fracture can reach respectively 5.3GPa, 133.3MPa, 4.1%, 2.7MJ/m
3.Every gram of film, after the sulfuric acid of 18ml, 0.3mol/L soaks 3 hours at 80 DEG C, is washed by centrifugal, washing, saturated solution of sodium bicarbonate, is washed, reclaims ODA-GO 5.87mg, the rate of recovery 97.8% after drying and processing; Centrifugate is reclaimed SDA, DDS, TAPB mixture 1.53g further across after the saturated neutralization of sodium bicarbonate, precipitation, filtration, washing, drying and processing, the rate of recovery 93.9%.
Embodiment 8
Fragrant triamine TAPOB is adopted to modify graphene oxide (Product Labeling is TAPOB-GO, primary amino content 0.14mmol/g), the TAPOB-GO aqueous solution of preparation 10mg/ml.18.01mmol paraformaldehyde and 8ml dimethyl sulfoxide (DMSO)/water mixed solvent are made into suspension, within 0.3 hour, carry out depolymerization, cool to room temperature at 90 DEG C of stirring reactions, obtain formaldehyde reaction liquid.6mmol fragrance triamine TAPOB is dissolved in 4ml N,N-dimethylacetamide, obtains aromatic amine reaction solution.By formaldehyde, aromatic amine reaction solution and 8mlTAPOB-GO aqueous solution evenly (in end reaction system mixed solvent, the volume content of water is 40%), ultrasonic disperse 15 minutes under room temperature, within 8 minutes, pre-polymerization is carried out at 50 DEG C of stirring reactions, plastic film mulch on horizontal glass plate further, dry 4 hours, 200 DEG C for 80 DEG C to dry 2 hours, obtain tawny laminated film object product.TAPOB-GO content 2.65wt% in every gram of film, Young's modulus, tensile strength, elongation at break and tension fracture can reach respectively 4.4GPa, 136.4MPa, 3.7%, 2.5MJ/m
3.Film, after the hydrochloric acid of 20ml, 0.5mol/L soaks 10 hours at 80 DEG C, is washed by centrifugal, washing, saturated solution of sodium bicarbonate, is washed, reclaims TAPOB-GO 76.32mg, the rate of recovery 95.4% after drying and processing; Centrifugate is reclaimed TAPOB 2.24g further across after the saturated neutralization of sodium bicarbonate, precipitation, filtration, washing, drying and processing, the rate of recovery 93.6%.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. a preparation method for the thermosetting polymer laminated film of recycling capable of circulation, is characterized in that, comprise the steps:
1) amination modification is carried out to graphene oxide, preparation amination graphene aqueous solution;
2) paraformaldehyde and non-proton/water mixed solvent are made into suspension, within 0.1 ~ 2 hour, carry out depolymerization, cool to room temperature at 60 ~ 100 DEG C of stirring reactions, obtain formaldehyde reaction liquid;
3) aromatic diamines and/or fragrant triamine are dissolved in aprotic solvent, obtain aromatic amine reaction solution;
4) formaldehyde, aromatic amine reaction solution are mixed with amination graphene aqueous solution, ultrasonic disperse 0 ~ 60 minute under room temperature, be warmed up to 30 ~ 80 DEG C of stirring reactions and carry out pre-polymerization in 1 ~ 60 minute, plastic film mulch on horizontal glass plate further, first dry 0.5 ~ 6 hour for 60 ~ 120 DEG C, dry 2 ~ 6 hours for 160 ~ 200 DEG C again, obtain tawny film object product.
2. preparation method according to claim 1, is characterized in that, the structure of described aromatic diamines, fragrant triamine is as follows:
3. preparation method according to claim 2, is characterized in that, described formaldehyde strictly follows the principle of measuring than 1:1 with the primary amino mol ratio in aromatic amine and amination Graphene; In the mixed solvent of end reaction system, the volume content of water is 0.5% ~ 60%, and the volume adding mixed solvent in every gram of reactant is 3 ~ 20ml.
4. preparation method according to claim 3, is characterized in that, the preparation of described amination graphene aqueous solution:
In graphene oxide water solution, add aprotic solvent, aromatic amine and catalyzer, chemically modified is carried out to graphene oxide, further by centrifugal, washing, obtained amination graphene aqueous solution.
5. preparation method according to claim 4, is characterized in that, described catalyzer is methyldiethanolamine, trolamine, diethyl amino propylamine, m-xylylene two (dimethylamine), N, N '-dimethyl piperazine, N-crassitude, N-methylhydroxy piperidines, N, N, N ', N '-tetramethyl-diaminoethanes, N, N, N ', N ', N '-five methyl diethylentriamine, triethylamine, Tributylamine, Trimethylamine, triethylenediamine, N-methylmorpholine, N-methyl piperidine or pyridine, Isosorbide-5-Nitrae-diazabicyclo [2.2.2]-octane, 1,8-diazo bicyclic [5,4,0] 11 carbon-7-alkene, 1,8-diazabicyclo [2,2,2] octane, 4-dimethylaminopyridine, 4-(N-pyrrolidino) pyridine, benzyl dimethyl amine, benzyldiethylamine, dimethylaminomethyl phenol, 2,6-bis-(dimethylaminomethyl) phenol, 2,4,6-tri-(dimethylaminomethyl) phenol, N-N xylidine, N-N dimethyl benzylamine, one or more in triphenylphosphine, every gram of graphene oxide correspondence 0.01 ~ 1g aromatic amine, 0.01 ~ 0.1g catalyzer, 20 ~ 200ml aprotic solvent.
6. the preparation method according to claim 1 or 2 or 3 or 4 or 5, is characterized in that, described paraformaldehyde be the polymerization degree lower than 100 lower molecular weight formaldehyde white crystalline powder.
7. preparation method according to claim 6, it is characterized in that, described aprotic solvent is one or more in N-Methyl pyrrolidone, dimethyl formamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), 2,5-dimethyl furans, hexamethylphosphoramide.
8. the thermosetting polymer laminated film prepared of any one of claim 1 ~ 7 method.
9. the recoverying and utilizing method of film described in claim 8, it is characterized in that, every gram of film is after the strong acid that 5 ~ 20ml concentration is 0.1 ~ 1mol/L soaks 1 ~ 24 hour at 50 ~ 95 DEG C, cool to room temperature, washed by centrifugal, washing, alkaline solution, wash the rear recyclable amination Graphene of process, by centrifugate further across after alkaline solution neutralization, precipitation, filtration, washing, drying and processing, obtain aromatic amine.
10. a thermosetting polymer composite, is characterized in that, this mixture has following structure:
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