CN103333367B - 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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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, the preparation method that particularly the organic covalent chemical of trimeric cyanamide is modified the nano-hybrid material of graphene oxide, belongs to field of material preparation.
Background technology
Graphene (Graphene) is by individual layer sp
2the cellular hexaplanar crystal of hydridization carbon atom arrangement composition, 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 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.But Graphene surface is unreactiveness, interlayer has again van der Waals interaction, 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 being got through liquid phase deep oxidation by graphite, a large amount of oxy radicals (according to Lerf-Klinowski model) such as carboxyl, hydroxyl, epoxy group(ing) are contained on layer surface, have good wetting ability.GO is easy to modification, and has good consistency with many polymeric matrixs; Also can make graphite oxide surface become lipophilicity, surperficial can reduction from wetting ability by modification, the increase of interlamellar spacing reduces interlayer Van der Waals force, processes and very easily realizes dispersion at the aqueous solution or in organic solvent through suitable ultrasonic oscillation.Therefore, it can further pass through covalency and non-covalent synthetic technology preparation in macroscopic quantity functionalization graphene.The preparation technology of graphite oxide is relatively ripe, and more traditional chemical process mainly contains Brodie method, Staudenmaier method, Hummers method.Features such as wherein, Hummer method is simple because having reaction, and the reaction times is short, and security is higher, the less pollution to environment and become one of method generally using at present.Now, increasing researchist, using GO as a kind of important presoma, has developed many methods of preparing 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 weightless temperature interval is narrow, can only be scattered in intensive polar solvent.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 built different types of functionalization graphene hybrid nano-material.Practical function functionalized graphene has a series of problem in science such as polymolecularity and high thermal stability concurrently, also becomes one of work that at present most important and tool is challenged.（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, it is different from the method that the present invention adopts that material is prepared adopted method.Usually, the reaction based on GO surface oxy radical of reporting in document mostly is covalent functionalization or non-covalent functionalization, and pays close attention to the upper a certain functionalization containing oxygen functional group of GO more.Wherein, covalent functionalization method adopts hypertoxicity material more, and such as tolylene diisocyanate (TDI) etc., easily meet water decomposition, pollute high, be difficult to large-scale industrialization produce.But not covalent functionalization research is relatively less, and in building-up process, the polymer macromolecules that adopt carry out the coated of GO more, the less covalent modification of following, and performance of control is poor.
Summary of the invention
The present invention is directed to the deficiencies such as complex operation, coupling reagent toxicity is huge that prior art exists.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 strong natural graphite powder degree of depth oxide treatment is obtained to oxidation graphite solid, then warp exists
n,
nultrasonic dispersion in-dimethyl formamide (DMF), obtain graphene oxide DMF dispersion liquid, after activated carboxylic, the trimeric cyanamide (MA) that adds dimethyl sulfoxide (DMSO) (DMSO) to dissolve, heated and stirred, filtration and dry after, obtain MA functionalization graphene nano-hybrid material.
Its concrete technique comprises the following steps:
Step 1, prepare oxidation graphite solid with natural flake graphite powder;
Step 2, ultrasonic under, prepare graphene oxide DMF suspension, the ratio of graphite oxide and DMF solvent is 7.5 ~ 15 mg/mL;
Step 3, prepare the graphene oxide (GOCl) of 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, GOCl that step 3 is obtained mix with the melamine solution of preparation in step 4, and heated and stirred is reacted, and wherein, the mass ratio of graphene oxide and trimeric cyanamide is (10:1) ~ (1:10);
Step 6, filtration under diminished pressure, washing, obtain functionalization graphene nano-hybrid material (GO-MA) after dry.
Oxidation graphite solid described in step 1 adopts the Hummers method preparation after improving.
Ultrasonic time described in step 2 is 3 ~ 10h.
GOCl described in step 3 by adding excessive thionyl chloride to react at 70-90 ℃ after at least one day in 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 with the ratio of thionyl chloride.
Further, for fast reaction speed, in step 5, in the mixing solutions of GOCl and trimeric cyanamide, add pyridine, wherein said graphene oxide and the amount ratio of pyridine are 40:(1 ~ 3) mg/mL.
Temperature of reaction described in 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 two kinds of classical covalent modification technology in Synthetic Organic Chemistry, fire retardant MA is anchored on to surface and the edge of GO by one pot of nucleophilic addition(Adn) and acidylate linked reaction simultaneously.This process mainly makes the ether-oxygen bond open loop on GO surface and carboxyl carry out amidation.And then by simple heated and stirred, the routine operations such as filtration are prepared from.MA functionalization graphene nano-hybrid material prepared by the present invention simultaneously can be easily by regulating temperature of reaction, 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 it more be conducive to improve the thermal stability of polymer composites as Nano filling and build 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, and is conducive to industrialized mass.
Below in conjunction with accompanying drawing, embodiments of the invention are described in further detail.
Accompanying drawing explanation
Fig. 1 is the preparation process schematic diagram of the MA functionalization graphene nano-hybrid material prepared of the present invention.
Fig. 2 is MA functionalization graphene nano-hybrid material synthetic in the embodiment of the present invention 3 dispersing property photo in solvent.
Fig. 3 is the infrared spectrogram of MA functionalization graphene nano-hybrid material synthetic in embodiment of the present invention 1-4.
Fig. 4 is the thermally-stabilised analytic curve of MA functionalization graphene nano-hybrid material synthetic in the embodiment of the present invention 2,4.
Embodiment
Below in conjunction with accompanying drawing, embodiments of the invention are described in further detail; the present embodiment is implemented under with 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, the method comprises the following steps:
Step 1, adopt the Hummers method preparation preparation oxidation graphite solid after improving with natural flake graphite powder;
Step 2, ultrasonic lower 3-10h, prepare graphene oxide DMF suspension, and the ratio of graphite oxide and DMF solvent is 7.5 ~ 15 mg/mL;
Step 3, by graphene oxide DMF suspension, add excessive thionyl chloride at 70-90 ℃, react at least one day after, 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 step 4, for fast reaction speed adds pyridine in mixing solutions, stirring reaction 1-3 days at heating 100 ~ 160 ℃, wherein, the mass ratio of graphene oxide and trimeric cyanamide is that (10:1) ~ (1:10), the amount ratio of graphene oxide and pyridine is 40:(1 ~ 3) mg/mL;
Step 6, filtration under diminished pressure, washing, obtain functionalization graphene nano-hybrid material (GO-MA) after dry;
Embodiment 1
The first step, the preparation of oxidation graphite solid;
At 80 ℃, by after 20 g natural graphites (400 order) preoxidation, be washed to pH=7 with the 30 mL vitriol oils, 10 g Potassium Persulphates and 10 g Vanadium Pentoxide in FLAKESs, Air drying spends the night stand-by;
The 460 mL vitriol oils are cooled to 0 ℃ of left and right, then the graphite of 20 g preoxidation is joined wherein, slowly add 60 g potassium permanganate, make system temperature be no more than 20 ℃, after interpolation, be warmed up to 35 ℃, after stirring 2 h, and slowly add 920 mL deionized waters in batches, make system temperature be no more than 98 ℃, then after stirring 15 minutes, add 2.8 L deionized waters and 50 mL 30 % hydrogen peroxide.By the glassy yellow suspension decompress filter obtaining, washing.Until there is no sulfate ion in filtrate, and while being neutrality, product is dried in 60 ℃ of vacuum, oxidation graphite solid obtained;
Second step, packs 200 mg graphite oxide powder into round-bottomed flask, then adds 21 mL DMF (DMF) solvents, after ultrasonic 3 h, obtains the suspension of graphene oxide;
The 3rd step adds 40 mL thionyl chloride (SOCl in the suspension in second step
2), at 70 ℃, to react after 24 h, underpressure distillation is to remove unnecessary SOCl
2obtain the product (GOCl) of activated carboxylic.
The 4th step, takes 500 mg MA and joins in 35 mL DMSO, to be stirred to completely and dissolve, preparation MA solution;
The 5th step, in the GOCl that the 3rd step is obtained and the solution of the 4th step, adds 7 mL pyridines, regulates temperature to 100 ℃, constant temperature stirring reaction 24 h;
The 6th step, the crude product that the 5th step is obtained is through suction filtration, and washing, after being dried, obtains product GO-MA
100.
Infrared spectra as shown in Figure 3 c, proves that this nano-hybrid material is successfully synthetic.
Embodiment 2
First to fourth step, with step 1 to four in embodiment 1.
The 5th step, in the GOCl that the 3rd step is obtained and the solution of the 4th step, adds 7 mL pyridines, regulates temperature to 110 ℃, constant temperature stirring reaction 24 h;
The 6th step, the crude product that the 5th step is obtained is through suction filtration, and washing, after being dried, obtains product GO-MA
110.
Infrared spectra as shown in Figure 3 d, proves that this nano-hybrid material is successfully synthetic.
As shown in Figure 4, in figure, the thermal stability of functionalization graphene nano-hybrid material is higher than the graphene oxide of unmodified for its thermostability.
Embodiment 3
First to fourth step, with step 1 to four in embodiment 1.
The 5th step, in the GOCl that the 3rd step is obtained and the solution of the 4th step, adds 7 mL pyridines, regulates temperature to 120 ℃, constant temperature stirring reaction 24 h;
The 6th step, the crude product that the 5th step is obtained is through suction filtration, and washing, after being dried, obtains product GO-MA
120.
As shown in Figure 2, research shows the dispersing property of functionalization graphene nano-hybrid material in solvent: this nano-hybrid material can better disperse in solvent.
Infrared spectra as shown in Figure 3 e, proves that this nano-hybrid material is successfully synthetic.
As shown in Figure 4, in figure, the thermal stability of functionalization graphene nano-hybrid material is higher than the graphene oxide of unmodified for its thermostability.
Embodiment 4
First to fourth step, with step 1 to four in embodiment 1.
The 5th step, in the GOCl that the 3rd step is obtained and the solution of the 4th step, adds 7 mL pyridines, regulates temperature to 130 ℃, constant temperature stirring reaction 24 h;
The 6th step, the crude product that the 5th step is obtained is through suction filtration, and washing, after being dried, obtains product GO-MA
130.
Infrared spectra, as shown in Fig. 3 f, proves that this nano-hybrid material is successfully synthetic.
Embodiment 5
First to fourth step, with step 1 to four in embodiment 1.
The 5th step, in the GOCl that the 3rd step is obtained and the solution of the 4th step, adds 7 mL pyridines, regulates temperature to 140 ℃, constant temperature stirring reaction 24 h;
The 6th step, the crude product that the 5th step is obtained is through suction filtration, and washing, after being dried, obtains product GO-MA
140.
Embodiment 6
First to fourth step, with step 1 to four in embodiment 1.
The 5th step, in the GOCl that the 3rd step is obtained and the solution of the 4th step, adds 7 mL pyridines, regulates temperature to 150 ℃, constant temperature stirring reaction 24 h;
The 6th step, the crude product that the 5th step is obtained is through suction filtration, and washing, after being dried, obtains product GO-MA
150.
Embodiment 7
First to fourth step, with step 1 to four in embodiment 1.
The 5th step, in the GOCl that the 3rd step is obtained and the solution of the 4th step, adds 7 mL pyridines, regulates temperature to 160 ℃, constant temperature stirring reaction 24 h;
The 6th step, the crude product that the 5th step is obtained is through suction filtration, and washing, after being dried, obtains product GO-MA
160.
Embodiment 8
First to fourth step, with step 1 to four in embodiment 1.
The 5th step, in the GOCl that the 3rd step is obtained and the solution of the 4th step, adds 7 mL pyridines, regulates temperature to 110 ℃, constant temperature stirring reaction 3 days;
The 6th step, with step 6 in embodiment 2.
Embodiment 9
First to fourth step, with step 1 to four in embodiment 1.
The 5th step, in the GOCl that the 3rd step is obtained and the solution of the 4th step, adds 7 mL pyridines, regulates temperature to 100 ℃, constant temperature stirring reaction 3 days;
The 6th step, with step 6 in embodiment 2.
Embodiment 10
The first step, with step 1 in embodiment 1.
Second step, packs 200 mg graphite oxide powder into round-bottomed flask, then adds 26.7 mL DMF (DMF) solvents, after ultrasonic 5 h, obtains the suspension of graphene oxide;
The the 3rd to the 6th step, with step 3 to six in embodiment 1.
Embodiment 11
The first step, with step 1 in embodiment 1.
Second step, packs 200 mg graphite oxide powder into round-bottomed flask, then adds 13.3 mL DMF (DMF) solvents, after ultrasonic 10 h, obtains the suspension of graphene oxide;
The the 3rd to the 6th step, with step 3 to six in embodiment 1.
Embodiment 12
The first step, with step 1 in embodiment 1.
Second step, packs 200 mg graphite oxide powder into round-bottomed flask, then adds 20 mL DMF (DMF) solvents, after ultrasonic 8 h, obtains the suspension of graphene oxide;
The 3rd step, with step 3 in embodiment 1.
The 4th step, takes 500 mg MA and joins in 10 mL DMSO and be stirred to dissolving, preparation MA solution;
The the 5th to the 6th step, with step 5 to six in embodiment 1.
Embodiment 13
The first step, with step 1 in embodiment 1.
Second step, packs 200 mg graphite oxide powder into round-bottomed flask, then adds 15 mL DMF (DMF) solvents, after ultrasonic 6 h, obtains the suspension of graphene oxide;
The 3rd step adds 20 mL thionyl chloride (SOCl in the suspension in second step
2), at 80 ℃, to react after 24 h, underpressure distillation is to remove unnecessary SOCl
2obtain the product (GOCl) of activated carboxylic.
The 4th step, takes 500 mg MA and joins in 100 mL DMSO and be stirred to dissolving, preparation MA solution;
The 5th step, under room temperature, joins the suspension of second step in the solution of the 4th step; Add 15 mL pyridines, regulate temperature to 130 ℃, constant temperature stirring reaction 24 h;
The 6th step, with step 6 in embodiment 1.
Embodiment 13
The first step to the three steps, with step 1 to three in embodiment 1.
The 4th step, takes 20 mg MA and joins in 4 mL DMSO and be stirred to dissolving, preparation MA solution;
The the 5th to the 6th step, with step 5 to six in embodiment 1.
Embodiment 14
The first step to the three steps, with step 1 to three in embodiment 1.
The 4th step, takes 2 g MA and joins in 40 mL DMSO and be stirred to dissolving, preparation MA solution;
The the 5th to the 6th step, with step 5 to six in embodiment 1.
Embodiment 15
The first step, with step 1 in embodiment 1.
Second step, packs 200 mg graphite oxide powder into round-bottomed flask, then adds 16 mL DMF (DMF) solvents, after ultrasonic 7 h, obtains the suspension of graphene oxide;
The 3rd step, with step 3 in embodiment 1.
The 4th step, takes 1.5 g MA and joins in 200 mL DMSO and be stirred to dissolving, preparation MA solution;
The 5th step, under room temperature, joins the suspension of second step in the solution of the 4th step; Regulate temperature to 110 ℃, add 5 mL pyridines, constant temperature stirring reaction 2 days;
The 6th step, with step 6 in embodiment 1.
Embodiment 16
The first step to the four steps, with step 1 to four in embodiment 15.
The 5th step, under room temperature, joins the suspension of second step in the solution of the 4th step; Add 15 mL pyridines, regulate temperature to 100 ℃, constant temperature stirring reaction 3 days.
The 6th step, with step 6 in embodiment 1.
From above-described embodiment; the preparation method of MA functionalization graphene nano-hybrid material provided by the invention dexterously integrated use two kinds of classical covalent modification technology in Synthetic Organic Chemistry, fire retardant MA is anchored on to surface and the edge of GO by one pot of nucleophilic addition(Adn) and acidylate linked reaction simultaneously.This process mainly makes the ether-oxygen bond open loop on GO surface and carboxyl carry out amidation.At a certain temperature, fire retardant trimeric cyanamide is passed through to the efficient complex functionality nano hybridization of one kettle way grapheme material.Successfully realize the nano-hybrid material of a kind of trimeric cyanamide chemically modified graphene oxide that has dispersiveness and thermostability raising concurrently.
Claims (7)
1. a preparation method for the trimeric cyanamide covalent functionalization graphene base nano-hybrid material that thermostability strengthens, is characterized in that said method comprising the steps of:
Step 1, prepare oxidation graphite solid with natural flake graphite powder;
Step 2, ultrasonic under, prepare graphene oxide DMF suspension, the ratio of graphite oxide and DMF solvent is 7.5 ~ 15 mg/mL;
Step 3, prepare the graphene oxide GOCl of 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, GOCl that step 3 is obtained mix with the melamine solution of preparation in step 4, and heated and stirred is reacted, and wherein, the mass ratio of graphene oxide and trimeric cyanamide is (10:1) ~ (1:10);
Step 6, filtration under diminished pressure, washing, obtain functionalization graphene nano-hybrid material after dry.
2. the preparation method of the trimeric cyanamide covalent functionalization graphene base nano-hybrid material that thermostability according to claim 1 strengthens, is characterized in that the oxidation graphite solid described in step 1 adopts the Hummers method preparation after improving.
3. the preparation method of the trimeric cyanamide covalent functionalization graphene base nano-hybrid material that thermostability according to claim 1 strengthens, is characterized in that the ultrasonic time described in step 2 is 3 ~ 10h.
4. the preparation method of the trimeric cyanamide covalent functionalization graphene base nano-hybrid material that thermostability according to claim 1 strengthens, it is characterized in that the GOCl described in step 3 is that unnecessary SOCl is removed in underpressure distillation by adding excessive thionyl chloride to react after at least 1 day at 70 ~ 90 ℃ in graphene oxide DMF suspension
2after obtain.
5. the preparation method of the trimeric cyanamide covalent functionalization graphene base nano-hybrid material that thermostability according to claim 4 strengthens, is characterized in that described graphite oxide is not more than 10 mg/mL with the ratio of thionyl chloride.
6. the preparation method of the trimeric cyanamide covalent functionalization graphene base nano-hybrid material that thermostability according to claim 1 strengthens, it is characterized in that in the mixing solutions of described GOCl and trimeric cyanamide, adding pyridine in step 5, described graphene oxide and the amount ratio of pyridine are 40:(1 ~ 3) mg/mL.
7. the preparation method of the trimeric cyanamide covalent functionalization graphene base nano-hybrid material that thermostability according to claim 1 strengthens, is characterized in that described temperature of reaction is 100 ~ 160 ℃; The described stirring reaction time is 1 ~ 3 day.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101935030A (en) * | 2010-08-31 | 2011-01-05 | 南京理工大学 | Functional graphene oxide for adjusting and controlling dispersibility of solvent by using organic chain segment as well as preparation method thereof |
| CN102167310A (en) * | 2011-01-30 | 2011-08-31 | 黑龙江大学 | Method for preparing nitrogen-doped graphene material with hydrothermal process |
-
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101935030A (en) * | 2010-08-31 | 2011-01-05 | 南京理工大学 | Functional graphene oxide for adjusting and controlling dispersibility of solvent by using organic chain segment as well as preparation method thereof |
| CN102167310A (en) * | 2011-01-30 | 2011-08-31 | 黑龙江大学 | Method for preparing nitrogen-doped graphene material with hydrothermal process |
Non-Patent Citations (2)
| Title |
|---|
| "Enhanced thermal stability in graphene oxide covalently functionalized with 2-amino-4,6-didodecylamino-1,3,5-triazine";Xiu-Zhi Tang;《Carbon》;20110430;第49卷(第4期);第1258-1265页 * |
| Xiu-Zhi Tang."Enhanced thermal stability in graphene oxide covalently functionalized with 2-amino-4,6-didodecylamino-1,3,5-triazine".《Carbon》.2011,第49卷(第4期),第1258-1265页. |
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