CN103333367A - Preparation method of thermostability enhanced melamine covalent functionalized graphene based nanohybrid material - Google Patents
Preparation method of thermostability enhanced melamine covalent functionalized graphene based nanohybrid material Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 49
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- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 title claims abstract description 7
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- 229910002804 graphite Inorganic materials 0.000 claims abstract description 19
- 239000010439 graphite Substances 0.000 claims abstract description 19
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- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 31
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Abstract
The invention discloses a preparation method of a thermostability enhanced melamine covalent functionalized graphene based nanohybrid material. The preparation process mainly includes preparation of graphite oxide and preparation of the functionalized graphene nanohybrid material. The invention perfectly combines two covalent modification technologies. The thermostability of the hybrid nano material synthesized by one step is significantly superior to that of unmodified graphene oxide, and the loading amount of modifying melamine on the graphene oxide can be adjusted, thus further realizing effective control of the functionalized hybrid material solvent's dispersing performance. The synthesis steps are simple and efficient, and the post-treatment is concise, so that the method is convenient for mass preparation. Due to the introduction of the flame retardant melamine, the nano material is particularly suitable to serve as a nano filler for preparation of the high heat resistant and flame retardant polymer nanocomposite material. Therefore, the nano material has good application prospects and economic benefits.
Description
Technical field
The present invention relates to a kind of preparation method of trimeric cyanamide covalent functionalization graphene base nano-hybrid material of thermostability enhancing, particularly the preparation method of the nano-hybrid material of the organic covalent chemical modification of a kind of trimeric cyanamide graphene oxide belongs to field of material preparation.
Background technology
Graphene (Graphene) is by individual layer sp
2The cellular hexaplanar crystal that the hydridization carbon atom arrangement is formed, its discoverer Geim etc. has obtained Nobel Prize in physics.Come from its outstanding physical and chemical performance, now become a kind of very popular new nano material in the charcoal family.Graphene is with a wide range of applications in hydrogen storage material, support of the catalyst, electron device, electrode materials, fire retardant material, prepare composite.In numerous application prospects of Graphene, utilize Graphene to prepare functional composite material and most possibly make a breakthrough in actual applications.Yet the Graphene surface is unreactiveness, and interlayer has the Van der Waals force effect again, and it is very easily reunited, and has seriously hindered its dispersion in any solvent, has limited the application in polymer nanocomposites.
Graphene oxide (Graphene oxide, GO) be typical accurate two-dimensional layer material, it is a kind of stratified material that is got through the liquid phase deep oxidation by graphite, laminar surface contains a large amount of oxy radicals (according to the Lerf-Klinowski model) such as carboxyl, hydroxyl, epoxy group(ing), has good hydrophilicity.GO is easy to modification, and with many polymeric matrixs consistency is preferably arranged; Also can make the graphite oxide surface become lipophilicity, surface energy reduction by wetting ability by modification, the increase of interlamellar spacing makes the interlayer Van der Waals force reduce, and handles through suitable ultrasonic oscillation and very easily realizes dispersion at the aqueous solution or in organic solvent.Therefore, it can further prepare functionalization graphene by covalency and non-covalent synthetic technology magnanimity.The preparation technology of graphite oxide is ripe relatively, and more traditional chemical process mainly contains Brodie method, Staudenmaier method, Hummers method.Wherein, the Hummer method is simple because having reaction, and the reaction times is short, and security is higher, and characteristics such as the pollution of environment is less are become one of method of generally using at present.Now, increasing researchist GO as a kind of important presoma, developed many methods that prepare hybrid inorganic-organic materials.
But the existence of GO surface oxy radical makes its thermostability very low, the very easily degraded of being heated, and the weightless temperature interval is narrow, can only be scattered in the intensive polar solvent.The various countries investigator is by a series of organic covalency and non-covalent technology, and for example, isocyanic ester method, esterification, amidation, silanization, nucleophilic substitution and phase transfer of technology etc. have made up different types of functionalization graphene hybrid nano-material.Realize that functionalization graphene has a series of problem in science such as polymolecularity and high thermal stability concurrently, also become one of work that most important and tool at present challenges.（1.?Sasha?Stankovich,?Richard?D.?Piner,?SonBinh?T.?Nguyen,?et?al.?
Carbon.?2006,?44:?3342-3347.?2.?Tang?X?Z,?Li?W?J,?Yu?Z?Z,?et?al.?
Carbon,?2011,?49(4):?1258-1265.）
But in aforesaid method, the method that material preparation is adopted is different with the method that the present invention adopts.Usually, the reaction of reporting in the document based on GO surface oxy radical mostly is covalent functionalization or non-covalent functionalization, and pays close attention to GO more and go up a certain functionalization that contains the oxygen functional group.Wherein, the covalent functionalization method adopts the hypertoxicity material more, and for example tolylene diisocyanate (TDI) etc. is met water decomposition easily, pollutes highly, is difficult to large-scale industrialization production.But not covalent functionalization research is less relatively, and the polymer macromolecules that adopt carry out the coating of GO more in the building-up process, the less covalent modification of following, regulation and control poor-performing.
Summary of the invention
The present invention is directed to deficiencies such as complex operation, coupling reagent toxicity that prior art exists is huge.Trimeric cyanamide covalent functionalization graphene base nano-hybrid material of a kind of thermostability enhancing and preparation method thereof is provided.
The technical solution that realizes the object of the invention is: the trimeric cyanamide covalent functionalization graphene base nano-hybrid material that a kind of thermostability strengthens, and its general structure is:
The nano-hybrid material of the organic covalent chemical functionalization of above-mentioned trimeric cyanamide graphene oxide is by obtaining oxidation graphite solid with the strong oxide treatment of the natural graphite powder degree of depth, and warp exists again
N,
NUltra-sonic dispersion in the-dimethyl formamide (DMF), obtain graphene oxide DMF dispersion liquid, behind the activated carboxylic, add the trimeric cyanamide (MA) of dimethyl sulfoxide (DMSO) (DMSO) dissolving, after heated and stirred, filtration and the drying, obtain MA functionalization graphene nano-hybrid material.
Its concrete technology may further comprise the steps:
Step 2, ultrasonic following, preparation graphene oxide DMF suspension, the ratio of graphite oxide and DMF solvent is 7.5 ~ 15 mg/mL;
The graphene oxide (GOCl) of step 3, preparation activated carboxylic;
The DMSO solution of step 4, preparation trimeric cyanamide (MA), the ratio of trimeric cyanamide and DMSO is (50:1) ~ (5:1) mg/mL;
Step 5, the GOCl that step 3 is obtained mix with the melamine solution of preparation in the step 4, the heated and stirred reaction, and wherein, the mass ratio of graphene oxide and trimeric cyanamide is (10:1) ~ (1:10);
Namely obtain functionalization graphene nano-hybrid material (GO-MA) after step 6, filtration under diminished pressure, washing, the drying.
Oxidation graphite solid described in the step 1 adopts the Hummers method preparation after improving.
Ultrasonic time described in the step 2 is 3 ~ 10h.
Reaction is after at least one day down at 70-90 ℃ by add excessive thionyl chloride in graphene oxide DMF suspension for GOCl described in the step 3, and underpressure distillation is to remove unnecessary SOCl
2After obtain, wherein said graphite oxide is not more than 10 mg/mL with the ratio of thionyl chloride.
Further for fast reaction speed, add pyridine in the mixing solutions of GOCl and trimeric cyanamide in step 5, the amount ratio of wherein said graphene oxide and pyridine is 40:(1 ~ 3) mg/mL.
Temperature of reaction described in the step 5 is 100 ~ 160 ℃; The described reaction times is 1 ~ 3 day.
Compared with prior art; the preparation method of MA functionalization graphene nano-hybrid material provided by the invention dexterously integrated use the covalent modification technology of two kinds of classics in the Synthetic Organic Chemistry, by nucleophilic addition(Adn) and one pot of surface and edge that simultaneously fire retardant MA is anchored on GO of acidylate linked reaction.This process mainly makes the ether-oxygen bond open loop on GO surface and carboxyl carry out amidation.And then, stirring by simple heating, routine operations such as filtration are prepared from.The MA functionalization graphene nano-hybrid material of the preparation of the present invention simultaneously can pass through the conditioned reaction temperature easily, the charge capacity of the ratio control MA of reaction mass on GO, and then regulate dispersiveness and the thermal stability of hybrid material in solvent.The introducing of MA has improved the thermal stability of GO effectively, improved simultaneously and polymeric matrix between interface compatibility, make its thermal stability that is conducive to improve as Nano filling polymer composites more make up novel flame retardant resistance nano composite material.Preparation method of the present invention presses close to the requirement of Green Chemistry, and simple to operate, is easy to control, is conducive to industrialized mass.
Below in conjunction with accompanying drawing embodiments of the invention are described in further detail.
Description of drawings
Fig. 1 is the preparation process synoptic diagram of the MA functionalization graphene nano-hybrid material for preparing of the present invention.
Fig. 2 is the dispersing property photo of MA functionalization graphene nano-hybrid material in solvent synthetic in the embodiment of the invention 3.
Fig. 3 is the infrared spectrogram of MA functionalization graphene nano-hybrid material synthetic among the embodiment of the invention 1-4.
Fig. 4 is the thermally-stabilised analytic curve of MA functionalization graphene nano-hybrid material synthetic in the embodiment of the invention 2,4.
Embodiment
Below in conjunction with accompanying drawing embodiments of the invention are described in further detail; present embodiment is implemented under with the technical solution of the present invention prerequisite; provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
As shown in Figure 1, trimeric cyanamide covalent functionalization graphene base nano-hybrid material that a kind of thermostability strengthens and preparation method thereof, this method may further comprise the steps:
Step 2, ultrasonic 3-10h down, preparation graphene oxide DMF suspension, the ratio of graphite oxide and DMF solvent is 7.5 ~ 15 mg/mL;
Step 3, reaction is after at least one day down at 70-90 ℃ by adding excessive thionyl chloride in the graphene oxide DMF suspension, and underpressure distillation is to remove unnecessary SOCl
2After obtain, wherein said graphite oxide is not more than 10 mg/mL(GOCl with the ratio of thionyl chloride);
The DMSO solution of step 4, preparation trimeric cyanamide (MA); The ratio of trimeric cyanamide and DMSO is (50:1) ~ (5:1) mg/mL;
Step 5, the GOCl that step 3 is obtained mix with the melamine solution of preparation in the step 4, for fast reaction speed adds pyridine in mixing solutions, heated 100 ~ 160 ℃ of following stirring reaction 1-3 days, wherein, the mass ratio of graphene oxide and trimeric cyanamide is (10:1) ~ (1:10), and the amount ratio of graphene oxide and pyridine is 40:(1 ~ 3) mg/mL;
Namely obtain functionalization graphene nano-hybrid material (GO-MA) after step 6, filtration under diminished pressure, washing, the drying;
The first step, the preparation of oxidation graphite solid;
At 80 ℃, with the 30 mL vitriol oils, 10 g Potassium Persulphates and 10 g Vanadium Pentoxide in FLAKESs with 20 g natural graphites (400 order) preoxidation after, be washed to pH=7, Air drying spends the night stand-by;
The 460 mL vitriol oils are cooled to about 0 ℃, graphite with 20 g preoxidation joins wherein then, slowly add 60 g potassium permanganate, make system temperature be no more than 20 ℃, be warmed up to 35 ℃ after interpolation finishes, stir after 2 h, and slowly add 920 mL deionized waters in batches, make system temperature be no more than 98 ℃, restir added 2.8 L deionized waters and 50 mL, 30 % hydrogen peroxide after 15 minutes.With the glassy yellow suspension decompress filter that obtains, washing.Until do not have sulfate ion in the filtrate, and when being neutrality, product is dried in 60 ℃ of vacuum, oxidation graphite solid obtained;
Second step with the 200 mg graphite oxide powder round-bottomed flask of packing into, added 21 mL N again, and dinethylformamide (DMF) solvent behind ultrasonic 3 h, obtains the suspension of graphene oxide;
The 3rd goes on foot, and adds 40 mL thionyl chloride (SOCl in the suspension in going on foot to second
2), behind reaction 24 h under 70 ℃, underpressure distillation is to remove unnecessary SOCl
2Obtain the product (GOCl) of activated carboxylic.
In the 4th step, take by weighing 500 mg MA and join and be stirred to fully dissolving among the 35 mL DMSO, preparation MA solution;
The 5th step in the solution with the 3rd GOCl that obtain of step and the 4th step, added 7 mL pyridines, adjusting temperature to 100 ℃, constant temperature stirring reaction 24 h;
In the 6th step, through suction filtration, washing after the drying, namely gets product GO-MA with the 5th crude product that obtain of step
100
Infrared spectra proves that this nano-hybrid material is successfully synthetic shown in Fig. 3 c.
Embodiment 2
First to fourth step is with step 1 to four among the embodiment 1.
The 5th step in the solution with the 3rd GOCl that obtain of step and the 4th step, added 7 mL pyridines, adjusting temperature to 110 ℃, constant temperature stirring reaction 24 h;
In the 6th step, through suction filtration, washing after the drying, namely gets product GO-MA with the 5th crude product that obtain of step
110
Infrared spectra proves that this nano-hybrid material is successfully synthetic shown in Fig. 3 d.
Its thermostability as shown in Figure 4, among the figure, the thermal stability of functionalization graphene nano-hybrid material is higher than the graphene oxide of unmodified.
Embodiment 3
First to fourth step is with step 1 to four among the embodiment 1.
The 5th step in the solution with the 3rd GOCl that obtain of step and the 4th step, added 7 mL pyridines, adjusting temperature to 120 ℃, constant temperature stirring reaction 24 h;
In the 6th step, through suction filtration, washing after the drying, namely gets product GO-MA with the 5th crude product that obtain of step
120
The dispersing property of functionalization graphene nano-hybrid material in solvent studies show that as shown in Figure 2: this nano-hybrid material can better disperse in solvent.
Infrared spectra proves that this nano-hybrid material is successfully synthetic shown in Fig. 3 e.
Its thermostability as shown in Figure 4, among the figure, the thermal stability of functionalization graphene nano-hybrid material is higher than the graphene oxide of unmodified.
Embodiment 4
First to fourth step is with step 1 to four among the embodiment 1.
The 5th step in the solution with the 3rd GOCl that obtain of step and the 4th step, added 7 mL pyridines, adjusting temperature to 130 ℃, constant temperature stirring reaction 24 h;
In the 6th step, through suction filtration, washing after the drying, namely gets product GO-MA with the 5th crude product that obtain of step
130
Infrared spectra proves that this nano-hybrid material is successfully synthetic shown in Fig. 3 f.
Embodiment 5
First to fourth step is with step 1 to four among the embodiment 1.
The 5th step in the solution with the 3rd GOCl that obtain of step and the 4th step, added 7 mL pyridines, adjusting temperature to 140 ℃, constant temperature stirring reaction 24 h;
In the 6th step, through suction filtration, washing after the drying, namely gets product GO-MA with the 5th crude product that obtain of step
140
Embodiment 6
First to fourth step is with step 1 to four among the embodiment 1.
The 5th step in the solution with the 3rd GOCl that obtain of step and the 4th step, added 7 mL pyridines, adjusting temperature to 150 ℃, constant temperature stirring reaction 24 h;
In the 6th step, through suction filtration, washing after the drying, namely gets product GO-MA with the 5th crude product that obtain of step
150
Embodiment 7
First to fourth step is with step 1 to four among the embodiment 1.
The 5th step in the solution with the 3rd GOCl that obtain of step and the 4th step, added 7 mL pyridines, adjusting temperature to 160 ℃, constant temperature stirring reaction 24 h;
In the 6th step, through suction filtration, washing after the drying, namely gets product GO-MA with the 5th crude product that obtain of step
160
Embodiment 8
First to fourth step is with step 1 to four among the embodiment 1.
The 5th step in the solution with the 3rd GOCl that obtain of step and the 4th step, added 7 mL pyridines, adjusting temperature to 110 ℃, constant temperature stirring reaction 3 days;
The 6th step is with step 6 among the embodiment 2.
Embodiment 9
First to fourth step is with step 1 to four among the embodiment 1.
The 5th step in the solution with the 3rd GOCl that obtain of step and the 4th step, added 7 mL pyridines, adjusting temperature to 100 ℃, constant temperature stirring reaction 3 days;
The 6th step is with step 6 among the embodiment 2.
The first step is with step 1 among the embodiment 1.
Second step with the 200 mg graphite oxide powder round-bottomed flask of packing into, added 26.7 mL N again, and dinethylformamide (DMF) solvent behind ultrasonic 5 h, obtains the suspension of graphene oxide;
The the 3rd to the 6th step is with step 3 to six among the embodiment 1.
Embodiment 11
The first step is with step 1 among the embodiment 1.
Second step with the 200 mg graphite oxide powder round-bottomed flask of packing into, added 13.3 mL N again, and dinethylformamide (DMF) solvent behind ultrasonic 10 h, obtains the suspension of graphene oxide;
The the 3rd to the 6th step is with step 3 to six among the embodiment 1.
Embodiment 12
The first step is with step 1 among the embodiment 1.
Second step with the 200 mg graphite oxide powder round-bottomed flask of packing into, added 20 mL N again, and dinethylformamide (DMF) solvent behind ultrasonic 8 h, obtains the suspension of graphene oxide;
The 3rd step is with step 3 among the embodiment 1.
The 4th step took by weighing 500 mg MA and joins among the 10 mL DMSO and be stirred to dissolving, preparation MA solution;
The the 5th to the 6th step is with step 5 to six among the embodiment 1.
Embodiment 13
The first step is with step 1 among the embodiment 1.
Second step with the 200 mg graphite oxide powder round-bottomed flask of packing into, added 15 mL N again, and dinethylformamide (DMF) solvent behind ultrasonic 6 h, obtains the suspension of graphene oxide;
The 3rd goes on foot, and adds 20 mL thionyl chloride (SOCl in the suspension in going on foot to second
2), behind reaction 24 h under 80 ℃, underpressure distillation is to remove unnecessary SOCl
2Obtain the product (GOCl) of activated carboxylic.
The 4th step took by weighing 500 mg MA and joins among the 100 mL DMSO and be stirred to dissolving, preparation MA solution;
In the 5th step, under the room temperature, second suspension that goes on foot is joined in the solution in the 4th step; Add 15 mL pyridines, regulate temperature to 130 ℃, constant temperature stirring reaction 24 h;
The 6th step is with step 6 among the embodiment 1.
Embodiment 13
Three steps of the first step to the are with step 1 to three among the embodiment 1.
The 4th step took by weighing 20 mg MA and joins among the 4 mL DMSO and be stirred to dissolving, preparation MA solution;
The the 5th to the 6th step is with step 5 to six among the embodiment 1.
Embodiment 14
Three steps of the first step to the are with step 1 to three among the embodiment 1.
The 4th step took by weighing 2 g MA and joins among the 40 mL DMSO and be stirred to dissolving, preparation MA solution;
The the 5th to the 6th step is with step 5 to six among the embodiment 1.
Embodiment 15
The first step is with step 1 among the embodiment 1.
Second step with the 200 mg graphite oxide powder round-bottomed flask of packing into, added 16 mL N again, and dinethylformamide (DMF) solvent behind ultrasonic 7 h, obtains the suspension of graphene oxide;
The 3rd step is with step 3 among the embodiment 1.
The 4th step took by weighing 1.5 g MA and joins among the 200 mL DMSO and be stirred to dissolving, preparation MA solution;
In the 5th step, under the room temperature, second suspension that goes on foot is joined in the solution in the 4th step; Regulate temperature to 110 ℃, add 5 mL pyridines, constant temperature stirring reaction 2 days;
The 6th step is with step 6 among the embodiment 1.
Embodiment 16
Four steps of the first step to the are with step 1 to four among the embodiment 15.
In the 5th step, under the room temperature, second suspension that goes on foot is joined in the solution in the 4th step; Add 15 mL pyridines, regulate temperature to 100 ℃, constant temperature stirring reaction 3 days.
The 6th step is with step 6 among the embodiment 1.
From above-described embodiment as can be known; the preparation method of MA functionalization graphene nano-hybrid material provided by the invention dexterously integrated use the covalent modification technology of two kinds of classics in the Synthetic Organic Chemistry, by nucleophilic addition(Adn) and one pot of surface and edge that simultaneously fire retardant MA is anchored on GO of acidylate linked reaction.This process mainly makes the ether-oxygen bond open loop on GO surface and carboxyl carry out amidation.At a certain temperature, the fire retardant trimeric cyanamide is passed through the efficient complex functionality nano hybridization of one kettle way grapheme material.Successfully realized having concurrently the nano-hybrid material of a kind of trimeric cyanamide chemically modified graphene oxide that dispersiveness and thermostability improve.
Claims (7)
1. the preparation method of the trimeric cyanamide covalent functionalization graphene base nano-hybrid material that strengthens of a thermostability is characterized in that said method comprising the steps of:
Step 1, prepare oxidation graphite solid with the natural flake graphite powder;
Step 2, ultrasonic following, preparation graphene oxide DMF suspension, the ratio of graphite oxide and DMF solvent is 7.5 ~ 15 mg/mL;
The graphene oxide GOCl of step 3, preparation activated carboxylic;
The DMSO solution of step 4, preparation trimeric cyanamide, the ratio of trimeric cyanamide and DMSO is (50:1) ~ (5:1) mg/mL;
Step 5, the GOCl that step 3 is obtained mix with the melamine solution of preparation in the step 4, the heated and stirred reaction, and wherein, the mass ratio of graphene oxide and trimeric cyanamide is (10:1) ~ (1:10);
Namely obtain the functionalization graphene nano-hybrid material after step 6, filtration under diminished pressure, washing, the drying.
2. the preparation method of the trimeric cyanamide covalent functionalization graphene base nano-hybrid material of thermostability enhancing according to claim 1 is characterized in that the oxidation graphite solid described in the step 1 adopts the Hummers method preparation after improving.
3. the preparation method of the trimeric cyanamide covalent functionalization graphene base nano-hybrid material of thermostability enhancing according to claim 1 is characterized in that the ultrasonic time described in the step 2 is 3 ~ 10h.
4. the preparation method of the trimeric cyanamide covalent functionalization graphene base nano-hybrid material that strengthens of thermostability according to claim 1, it is characterized in that the GOCl described in the step 3 is that reaction is after at least 1 day down at 70 ~ 90 ℃ by add excessive thionyl chloride in graphene oxide DMF suspension, unnecessary SOCl is removed in underpressure distillation
2After obtain.
5. the preparation method of the trimeric cyanamide covalent functionalization graphene base nano-hybrid material of thermostability enhancing according to claim 4 is characterized in that described graphite oxide and the ratio of thionyl chloride are not more than 10 mg/mL.
6. the preparation method of the trimeric cyanamide covalent functionalization graphene base nano-hybrid material that strengthens of thermostability according to claim 1, it is characterized in that adding pyridine in the step 5 in the mixing solutions of described GOCl and trimeric cyanamide, the amount ratio of described graphene oxide and pyridine is 40:(1 ~ 3) mg/mL.
7. the preparation method of the trimeric cyanamide covalent functionalization graphene base nano-hybrid material of thermostability enhancing according to claim 1 is characterized in that described temperature of reaction is 100 ~ 160 ℃; The described stirring reaction time is 1 ~ 3 day.
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| CN111087816A (en) * | 2019-12-06 | 2020-05-01 | 沈阳化工大学 | Preparation method of 2-amino-3-fluoro-5-trifluoromethylpyridine modified GO flame-retardant silicone rubber |
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| CN107488889A (en) * | 2017-09-19 | 2017-12-19 | 旷达纤维科技有限公司 | A kind of hollow coloured polyester fiber of high fire-retardance fine denier profiled and preparation method thereof |
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| CN111073289A (en) * | 2019-12-04 | 2020-04-28 | 沈阳化工大学 | Mimosa pudica element modified graphene oxide flame-retardant silicone rubber |
| CN111087816A (en) * | 2019-12-06 | 2020-05-01 | 沈阳化工大学 | Preparation method of 2-amino-3-fluoro-5-trifluoromethylpyridine modified GO flame-retardant silicone rubber |
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