CN103537263B - A kind of graphite oxide surface grafting Schiff compound and its preparation method and application - Google Patents
A kind of graphite oxide surface grafting Schiff compound and its preparation method and application Download PDFInfo
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- CN103537263B CN103537263B CN201310444860.XA CN201310444860A CN103537263B CN 103537263 B CN103537263 B CN 103537263B CN 201310444860 A CN201310444860 A CN 201310444860A CN 103537263 B CN103537263 B CN 103537263B
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Abstract
The present invention discloses a kind of graphite oxide surface grafting Schiff compound and its preparation method and application, and preparation method is after crystalline flake graphite being adopted the oxidation of improvement Hummers method, and aliphatic hydrocarbon diamines carries out amidation process, then grafting Schiff, to obtain final product; This preparation method's process is simple, easy to operate, can suitability for industrialized production; It is large that obtained graphite oxide surface grafting Schiff compound has adsorption capacity to the heavy metal in flue gas, the feature of high adsorption capacity, adds in cigarette filter rod, just can reach the effect that effective selectivity reduces heavy metal release amount in cigarette mainstream flue gas on a small quantity.
Description
Technical field
The present invention relates to a kind of graphite oxide surface grafting Schiff macromolecular compound and its preparation method and application, belong to new cigarette and fall burnt and fall heavy-metal adsorption material field.
Background technology
Heavy metal in cigarette smoke is mainly derived from tobacco itself, and the heavy metal element in tobacco is mainly derived from soil, water and air etc. containing heavy metal pollution in tobacco planting environment.The heavy metal elements such as the lead in tobacco, arsenic, cadmium, chromium, mercury can enter human body with the form of aerosol or metal oxide by flue gas, after formation accumulation, may damage to human body.In the flue gas of a research discovery cigarette, the most absorbable heavy metal is cadmium.For the control of content of beary metal in tobacco, main employing two kinds of thinkings are at present the effective control to tobacco leaf home environment heavy metal on the one hand, and the emphasis of research concentrates on tobacco variety screening and biotechnology aspect.Produce the absorptivity that the content of heavy metal in smoke hallway and existing forms directly affect tobacco leaf heavy metal, in general soil, the content of soluble heavy metal is higher, the absorptivity of tobacco leaf heavy metal is also higher, and its absorptivity is subject to the impact of the factors such as soil pH, clay, organic matter and cation exchange capacity.Be in production of cigarettes process, adopt some technology to reduce content of beary metal in main flume on the other hand, the emphasis of research concentrates on filter tip absorption and retains technology.It is generally acknowledged the heavy metal particles thing in the adsorbable flue gas of filter tip, reduce its harm to human body.Active carbon filter and the good NEW TYPE OF COMPOSITE filter tip of some other effect are developed now, to poisonous and hazardous trace element (cadmium, nickel, arsenic) and organic compound etc., there is suction-operated, the adsorption capacity of active carbon filter to Cd, Ni and As is respectively 4.25,3.58 and 1.61 times of acetate fiber filter tip to have result of study to show, adsorption effect obviously strengthens.Composite filter tip prepared by acetate fiber and yellow Siberian cocklebur, effectively can reduce cadmium in cigarette main flume and plumbous paramorphogen, and for reducing, smoker sucks heavy metal lead, the Cumulative exposure dose of cadmium has positive effect with depositing in lung.In addition, the Active carbon composite filter of chitosan-containing has stronger Selective absorber ability to the heavy metal in flue gas and other harmful substances.The result of study of Zhou Guojun etc. shows, the one in copper chlorophyll and chlorophyllin sodium or two kinds is joined triacetin three ester, is sprayed onto in tow, or is prepared into 40-80 order particle and adds in mouth rod, can effectively catching heavy metal.The research of Wang Ying etc. shows, CNT has stronger selective absorption effect to heavy metals such as Cd, Pb.But the addition of these heavy metal absorbents of the prior art is large, and adsorption effect is not obvious.
Summary of the invention
The present invention is directed to heavy metal absorbent of the prior art to there is addition large, and the unconspicuous defect of adsorption effect, object is that providing a kind of has to heavy metal in cigarette smoke the graphite oxide surface grafting Schiff compound that adsorption capacity is large, suction-operated is strong.
Second object of the present invention is the application being to provide a kind of described graphite oxide surface grafting Schiff compound, small amounts graphite surface grafting Schiff compound is added in cigarette filter rod, just can reaches the effect that effective selectivity reduces the heavy metal release amount in cigarette smoke.
3rd object of the present invention is the method being the graphite oxide surface grafting Schiff compound provided described in simple, the easy to operate preparation of a kind of process, and the method is conducive to suitability for industrialized production.
The invention provides a kind of graphite oxide surface grafting Schiff compound, this compound is that the group having formula 1 structure by graphite oxide surface grafting is formed;
Wherein, n is 2 ~ 4;
R is
or
a kind of in substituted radical;
R
1, R
2and R
3be selected from hydrogen atom, methyl or the tert-butyl group a kind of independently of one another.
Preferred graphite oxide surface grafting Schiff compound, R
1and R
2for identical substituted radical.
Described graphite oxide is oxidized crystalline flake graphite by improvement Hummers method to obtain.
Described improvement Hummers method oxidation crystalline flake graphite is dispersed in sulfuric acid solution by crystalline flake graphite, first uses the KMNO of crystalline flake graphite quality 3 ~ 4 times
4be oxidized after 1 ~ 2h being not more than under the condition of 5 DEG C, be warmed up to 30 ~ 40 DEG C and continue oxidation 1.5 ~ 2.5h, then with hydrogen peroxide solution 90 ~ 100 DEG C of oxidations further, until reactant liquor becomes golden yellow.
Present invention also offers a kind of application of described graphite oxide surface grafting Schiff compound, this application is that described graphite oxide surface grafting Schiff compound is added in cigarette filter rod as adsorbent the burst size being applied to heavy metal in selectivity reducing cigarette main flume.
The described addition of graphite oxide surface grafting Schiff compound in cigarette filter rod is that 1 ~ 10mg/ props up; Be preferably 2 ~ 6mg/ to prop up.
Described graphite oxide surface grafting Schiff compound is added on the close pipe tobacco section of cigarette binary compound filter candle, or the interlude of Three-element composite filter core.
Present invention also offers a kind of preparation method of described graphite oxide surface grafting Schiff compound, this preparation method is, improvement hummers method is adopted by crystalline flake graphite to be oxidized to surperficial carboxylic graphite oxide, again carboxylic graphite oxide and aliphatic hydrocarbon diamines are carried out amidation process, obtain graphite oxide surface grafting amino-compound; Gained graphite oxide surface grafting amino-compound and the Schiff generation substitution reaction with formula 2 structure, to obtain final product; Described aliphatic hydrocarbon diamines comprises ethylenediamine, 1,3-propane diamine or Putriscine;
R is
or
a kind of in substituted radical;
R
1, R
2and R
3be selected from hydrogen atom, methyl or the tert-butyl group a kind of independently of one another.
Described Schiff first carries out the condensation reaction of amine aldehyde with 3, the 5-disubstituted salicylides with formula 4 structure by ethylenediamine, cyclohexanediamine or o-phenylenediamine, then carry out the condensation reaction of amine aldehyde with the 5-chloromethyl-3-substituting group salicylide with formula 3 structure and obtain;
R
1, R
2and R
3be selected from hydrogen atom, methyl or the tert-butyl group a kind of independently of one another.
Described preparation method, preferred 3,5-disubstituted salicylides, R
1and R
2for identical substituting group.
Described preparation method, improves the graphite oxide that hummers method oxidation crystalline flake graphite is made, the carboxyl that the distribution of its surface uniform is abundant.
The preparation method of graphite oxide surface grafting Schiff compound of the present invention comprises the following steps:
(1) the hummers legal system improved is for graphite oxide:
Natural flake graphite is placed in the concentrated sulfuric acid, first uses potassium permanganate (be 3 ~ 4:1 with graphite quality ratio) being not more than under the condition of 5 DEG C, stir oxidation reaction 60 ~ 120min, then be warmed up to 30 ~ 40 DEG C of oxidation 1.5 ~ 2.5h, until solution becomes purple green; Add hydrogen peroxide solution again and carry out further oxidation reaction at 90 ~ 100 DEG C, until reactant liquor becomes golden yellow, use salt acid elution, then be washed to neutrality, dry, obtain the sheet graphite oxide of surface containing a large amount of carboxyl;
The addition of hydrogen peroxide solution take mass percent concentration as the addition of the relative graphite of hydrogen peroxide of 30% is 3 ~ 5mL/1g metering;
Synthetic route is as follows:
M is the carboxyl number on graphite oxide surface;
(2) graphite oxide surface grafting amino-compound is prepared in amidatioon:
By step (1) gained containing carboxylic-oxidized graphite and aliphatic hydrocarbon diamines at 60 DEG C, after stirring and refluxing reacts 6 hours, dilution, filters, and with absolute ethanol washing, drying, obtains graphite oxide surface grafting amino-compound:
Synthetic route is as follows:
N is 2 ~ 4;
(3) Schiff is synthesized:
A, synthesis 5-chloromethyl-3-substituted salicylic aldehydes:
By 2-fortified phenol and paraformaldehyde back flow reaction 3h in triethylamine of RMgBr process, preparation 3-substituted salicylic aldehydes, then with preparation 3-substituted salicylic aldehydes for raw material, under TBAB catalysis, 72h are reacted at 40 DEG C by the hydrochloric acid solution of 3-substituted salicylic aldehydes and paraformaldehyde, preparation 5-chloromethyl-3-substituting group salicylide, synthetic route is as follows:
R
3be selected from hydrogen atom, methyl or the tert-butyl group a kind of;
B, synthesis Schiff:
Add hydrochloric acid by after the amido protecting of diamines one end, first with 3,5-disubstituted bigcatkin willows at room temperature amine aldehyde condensation reaction 4h, then with 5-chloromethyl-3-substituting group salicylide amine aldehyde condensation reaction 4h, prepare containing 5-chloromethane fundamental mode Schiff, synthetic route is as follows:
R
1and R
2be selected from hydrogen atom, methyl or the tert-butyl group a kind of independently of one another;
R is
or
a kind of in substituted radical;
(4) graphite oxide surface grafting Schiff macromolecular compound is prepared in substitution reaction:
By the Schiff that the graphite oxide surface grafting amino-compound of step (2) gained and step (3) synthesize, under nitrogen protection, in reflux in toluene after 24 hours, filter, wash with absolute ether, then 24h is carried with carrene rope, dry, obtain graphite oxide surface grafting Schiff compound;
Beneficial effect of the present invention: the present invention has synthesized a kind of double-Schiff base with chloromethyl first, and be grafted to graphite oxide surface by aliphatic diamine, synthesized a kind of graphite oxide surface grafting Schiff compound, this compound is added in cigarette filter rod the heavy metal release amount that can effectively reduce in cigarette mainstream flue gas.The present invention, first by improving hummers legal system for graphite oxide, makes the surface uniform of graphite oxide distribute more carboxyl; Schiff is introduced again by aliphatic diamine, the Schiff heavy metal introduced has chelation well, and the nitrogen-atoms on aliphatic diamine and the amide group of generation itself are also electron donors, heavy metal has certain coordination, simultaneously also can and Schiff between produce the effect of collaborative Coordination Adsorption heavy metal, further increase the ability of graphite oxide surface grafting Schiff compounds adsorb heavy metal.Therefore graphite oxide surface grafting Schiff compound of the present invention has adsorbing metal ability by force, the feature that adsorbance is large, only needs to add in cigarette filter rod just to play the good effect reducing heavy metal in cigarette mainstream flue gas on a small quantity; Be specially adapted to the absorption to Cd, Pb and Cr; Experimental results demonstrate: propped up with 5mg/ by graphite oxide surface grafting Schiff compound of the present invention and be added in cigarette, the reduced rate that the reduced rate of Cd can reach 25.2%, Pb can reach 15.3%; The reduced rate of Cr can reach 23.1%.In addition, this polyamidoamine dendrimer load Schiff compound is polymeric solid thing, use safety, and preparation process is simple, is easy to suitability for industrialized production.
Accompanying drawing explanation
The infrared spectrogram comparison diagram that [Fig. 1] is the obtained graphite oxide of the embodiment of the present invention 1 and graphite oxide surface grafting ethylene diamine compound and graphite oxide surface grafting Schiff compound: a is graphite oxide, and b is graphite oxide surface grafting ethylene diamine compound; C is graphite oxide surface grafting Schiff.
Detailed description of the invention
Following examples are intended to further illustrate the present invention, instead of limiting the scope of the present invention.
Embodiment 1
(1) preparation of graphite oxide
The preparation of graphite oxide adopts and improves hummers method, is reacted prepare graphite oxide by natural flake graphite.In ice-water bath, put into 1000mL there-necked flask, add the dense H of 110mL
2sO
4, open magnetic stirrer, cool the temperature to about 0 DEG C.Add 100 order flaky graphite 5g, then add 2.5gNaNO
3, then slowly add 15gKMnO
4, keep system temperature lower than 5 DEG C in whole process, continue stirring reaction 90min, reaction system slowly become the green pasty state of dense thick purple.Then, change ice-water bath into tepidarium, temperature controlled at 35 DEG C under stirring, allow it react 120min, solution is in purple green.Slowly add 220mL deionized water, heating keeps temperature about 95 DEG C 30min, slowly adds 20mL (30%) hydrogen peroxide, and now reactant liquor becomes golden yellow.Filter, the hydrochloric acid cyclic washing with 10% is until BaCl
2detect and generate without white precipitate, illustrate there is no SO
4 2-existence, by deionized water, repeatedly centrifuge washing is close to neutral, and gained sample is dried at 40 ~ 50 DEG C of temperature, namely obtains graphite oxide.And carried out IR Characterization (see accompanying drawing 1(a)), FT-IR (KBr): 3390,1735,1616,1380,1224,1050,830,580cm
-1.In accompanying drawing 1a, result shows, at 1735cm
-1there is the characteristic absorption peak of the carbonyl belonged in graphite oxide surface carboxyl groups-COOH in place, at 3390cm
-1in place's appearance-COOH, the larger broad peak of hydroxyl, confirms that graphite oxide surface exists a large amount of carboxyl.
(2) preparation of amino functional graphite oxide
Graphite oxide (0.5g) is added, DMF (DMF) solvent 150mL in 500mL flask; Ultrasonic disperse 30 minutes, at room temperature stirs 1 hour by mixed liquor, then adds ethylenediamine 300mL, continue ultrasonic 15 minutes, stirred at ambient temperature 1h, be warming up to 60 DEG C, stop reaction after stirring and refluxing 6h, filter with after absolute ethyl alcohol (500mL) dilution, and with the unreacted diamines of absolute ethyl alcohol cyclic washing, 50 DEG C of vacuum drying, obtain the amino functional graphite oxide of black, and have carried out IR Characterization (see accompanying drawing 1(b)), FT-IR (KBr): 3420,3190,2920,2820,1657,1560,1224,1150,968,868,571, cm
-1.In accompanying drawing 1b, result shows, compared with graphite oxide (accompanying drawing 1a), and 1735cm in spectrogram
-1and 3390cm
-1the characteristic peak that place belongs to-COOH disappears, and at 1657cm
-1place defines the amide groups characteristic peak of new CO-NH, prove graphite oxide surface carboxyl groups with the amino (-NH of ethylenediamine
2) reaction define acid amides, at 3420, cm
-1left and right creates-NH
2characteristic peak, therefore, accompanying drawing 1b illustrates graphite oxide surface successful grafting ethylenediamine.
(3) 5-chloromethyl-3-tert-butyl group salicylide is synthesized
In 500mL there-necked flask, add magnesium powder (2.4g, 0.10mol) and 50mL absolute ether, under agitation in 1h, drip bromoethane (0.10mol, 9mL), slowly temperature rising reflux 1h after dropwising, returns to room temperature, obtains RMgBr CH after magnesium powder fully reacts
3cH
2mgBr.2-TBP (0.10mol) is dissolved in 60mL oxolane, is at room temperature added dropwise in 1h in the RMgBr of just preparation.When after a large amount of white precipitate of appearance, add cyclohexane or benzene 200mL.Slow rising reaction temperature, steams and removes about 100mL solvent, lower boiling solvent in system is distilled out of as best one can.Add into 50mL cyclohexane or benzene again, then in reactant liquor, add triethylamine (0.15mol) and paraformaldehyde (22.5g) immediately.After adding hot reflux 3h, TLC follows the tracks of reaction process, then is cooled to room temperature.By in reactant liquor impouring 500mL10% hydrochloric acid solution, after fully stirring, separatory after leaving standstill, filter after organic phase anhydrous magnesium sulfate drying, after distillation removing organic solvent, be separated with column chromatography (n-hexane: ethyl acetate=50:1), obtain weak yellow liquid product 3-tert-butyl group salicylide.
1HNMR(CDCl
3,500MHz):δ
H,ppm:1.42(s,9H,Me),6.93-6.98(t,1H,Ar),7.39-7.43(d,1H,Ar),7.52-7.55(d,1H,Ar),9.88(s,1H,CHO),11.79(s,1H,OH)。
(2.7g, 15.2mmol) 3-tert-butyl group salicylide is added, paraformaldehyde (1.0g) in 100mL round-bottomed flask, TBAB (1.46mmol, 0.47g) with 11mL concentrated hydrochloric acid, vigorous stirring 72h at 40 DEG C, period supplements three concentrated hydrochloric acid 5mL.After reaction terminates, obtain organic phase with the extraction of 3 × 15mL absolute ether, use the sodium bicarbonate solution of 4 × 10mL5% and the saturated NaCl solution washing of 4 × 10mL successively, anhydrous magnesium sulfate drying.Except desolventizing obtains the yellow solid product 3-tert-butyl group-5-chloromethyl salicylaldehyde after filtering.
1HNMR(CDCl
3,500MHz):δH,ppm:1.43(s,9H,Me),4.59(s,2H,CH2),7.44(d,1H,Ar),7.53(d,1H,Ar),9.87(s,1H,CHO),11.87(s,1H,OH)。
(4) 3,3 ', 5 '-tri-tert-5-chloromethane fundamental mode Schiff are synthesized
1 is added in 100mL three-neck flask; 2-cyclohexanediamine (10mmol); add 30mL absolute ethyl alcohol; logical argon shield; be placed in ice-water bath cooling, magnetic agitation, slowly drips the HCl/ diethyl ether solution (10mmol) of 2mmol/L with constant pressure funnel; dripping in 1 hour, there is a large amount of white precipitate in solution.Room temperature continues and to continue under condition continuously to stir 12h, then filtration under diminished pressure, and absolute ether washing (5 × 20mL), vacuum drying, obtains, without the white pressed powder of colour cast, obtaining the cyclohexanediamine hydrochloride of monolateral protection.
The cyclohexanediamine hydrochloride (5mmol) of monolateral protection is added respectively in 250mL three-neck flask; 25mL absolute ethyl alcohol and 25mL absolute ether; stirring at room temperature 10 minutes. get 3; 5-di-tert-butyl salicylaldehyde (5mol); after 50mL anhydrous alcohol solution, drip with constant pressure funnel, add a certain amount of 4A molecular sieve simultaneously and slough the water produced in condensation reaction; stir 4 hours, solution is faint yellow.Drip the triethylamine of 5mmol, stirring at room temperature 1 hour, then get 3-chloromethyl-5-tert-butyl group salicylide (5mmol) and be dissolved in 25mL carrene, drip 30min with constant pressure funnel and drip, continue stirring 2 hours. after removing 4A molecular sieve, with dichloromethane extraction, rotary evaporation falls carrene, obtains aubergine solid, is 3,3 ', 5 '-tri-tert-5-chloromethane fundamental mode Schiff.Calc.forC
33H
47ClN
2O
2:C,73.51;H,8.79;N,5.20.Found:C,73.46;H,8.91;N,5.12%.
1H-NMR(CDCl
3,400MHz):δppm14.29(s,1H),13.67(s,1H),8.44(s,1H),8.31(s,1H),7.30(d,1H),7.26(d,1H),6.99(d,1H),6.89(d,1H),4.43(s,2H),3.55-3.32(m,2H),1.97-1.46(m,8H),1.40(s,9H),1.23(s,18H).FT-IR(KBr):3446,2954,2862,1629,1591,1479,1469,1439,1391,1361,1271,1252,1241,1201,1174,1144,1086,1040,981,934,879,828,803,772,731,711,644cm
-1。
(5) preparation of graphite oxide surface grafting Schiff
The graphite oxide (1.0g) of amino functional is added in 250mL flask, 100mL toluene, 3, 3 ', 5 '-tri-tert-5-chloromethane fundamental mode Schiff (0.5g), mixture is refluxed under nitrogen protection 24 hours, filter, wash with absolute ether, then 24h is carried with carrene rope, 40 DEG C of vacuum drying, obtain the graphite oxide surface grafting 3 of black, 3 ', 5 '-tri-tert-5-methylene fundamental mode Schiff, and IR Characterization (see accompanying drawing 1(c) has been carried out to the sample of preparation), FT-IR (KBr): 3670, 2950, 2860, 3250, 1620, 1535, 1450, 1380, 1340, 1310, 1260, 1180, 1110, 1020, 935, 843, 748, 643, 568cm
-1.In accompanying drawing 1c, result shows, compared with (Fig. 1 b), in spectrogram, wave number is 1657cm
-1the characteristic peak belonging to amide groups (CO-NH) moves to 1648cm
-1, 3420, cm
-1-NH
2characteristic peak disappear, in addition, be 1620cm in wave number
-1there is the characteristic absorption peak of C=N in Schiff ligand structure in place; Therefore, accompanying drawing 1c illustrates the successful grafting in graphite oxide surface 3,3 ', 5 '-tri-tert-5-methylene fundamental mode schiff alkali cpds.
Embodiment 2
(1) preparation of graphite oxide
With embodiment 1.
(2) preparation of amino functional graphite oxide
Graphite oxide (0.5g) is added, DMF (DMF) solvent 150mL in 500mL flask; Ultrasonic disperse 30 minutes, mixed liquor is at room temperature stirred 1 hour, then add propane diamine 300mL, continue ultrasonic 15 minutes, stirred at ambient temperature 1h, be warming up to 60 DEG C, stop reaction after stirring and refluxing 6h, filter with after absolute ethyl alcohol (500mL) dilution, and with the unreacted diamines of absolute ethyl alcohol cyclic washing, 50 DEG C of vacuum drying, obtain the amino functional graphite oxide of black.
(3) 5-chloromethyl-3-cresotinic acid aldehyde is synthesized
In 500mL there-necked flask, add magnesium powder (2.4g, 0.10mol) and 50mL absolute ether, under agitation in 1h, drip bromoethane (0.10mol, 9mL), slowly temperature rising reflux 1h after dropwising, returns to room temperature, obtains RMgBr CH after magnesium powder fully reacts
3cH
2mgBr.2-methylphenol (0.10mol) is dissolved in 60mL oxolane, is at room temperature added dropwise in 1h in the RMgBr of just preparation.When after a large amount of white precipitate of appearance, add cyclohexane or benzene 200mL.Slow rising reaction temperature, steams and removes about 100mL solvent, lower boiling solvent in system is distilled out of as best one can.Add into 50mL cyclohexane or benzene again, then in reactant liquor, add triethylamine (0.15mol) and paraformaldehyde (22.5g) immediately.After adding hot reflux 3h, TLC follows the tracks of reaction process, then is cooled to room temperature.By in reactant liquor impouring 500mL10% hydrochloric acid solution, after fully stirring, separatory after leaving standstill, filter after organic phase anhydrous magnesium sulfate drying, after distillation removing organic solvent, be separated with column chromatography (n-hexane: ethyl acetate=50:1), obtain weak yellow liquid product 3-cresotinic acid aldehyde.
(15.2mmol) 3-cresotinic acid aldehyde is added in 100mL round-bottomed flask, paraformaldehyde (1.0g), TBAB (1.46mmol, 0.47g) and 11mL concentrated hydrochloric acid, vigorous stirring 72h at 40 DEG C, period supplements three concentrated hydrochloric acid 5mL.After reaction terminates, obtain organic phase with the extraction of 3 × 15mL absolute ether, use the sodium bicarbonate solution of 4 × 10mL5% and the saturated NaCl solution washing of 4 × 10mL successively, anhydrous magnesium sulfate drying.Except desolventizing obtains yellow solid product 3-methyl-5-chloro cresotinic acid aldehyde after filtering.
(4) 3-methyl-3 is synthesized ', 5 '-di-t-butyl-5-chloromethane fundamental mode Schiff
1 is added in 100mL three-neck flask; 2-cyclohexanediamine (10mmol); add 30mL absolute ethyl alcohol; logical argon shield; be placed in ice-water bath cooling, magnetic agitation, slowly drips the HCl/ diethyl ether solution (10mmol) of 2mmol/L with constant pressure funnel; dripping in 1 hour, there is a large amount of white precipitate in solution.Room temperature continues and to continue under condition continuously to stir 12h, then filtration under diminished pressure, and absolute ether washing (5 × 20mL), vacuum drying, obtains, without the white pressed powder of colour cast, obtaining the cyclohexanediamine hydrochloride of monolateral protection.
The cyclohexanediamine hydrochloride (5mmol) of monolateral protection is added respectively in 250mL three-neck flask; 25mL absolute ethyl alcohol and 25mL absolute ether; stirring at room temperature 10 minutes. get 3; 5-di-tert-butyl salicylaldehyde (5mol); after 50mL anhydrous alcohol solution, drip with constant pressure funnel, add a certain amount of 4A molecular sieve simultaneously and slough the water produced in condensation reaction; stir 4 hours, solution is faint yellow.Drip the triethylamine of 5mmol, stirring at room temperature 1 hour, then get 3-methyl-5-chloro cresotinic acid aldehyde and be dissolved in 25mL carrene, drip 30min with constant pressure funnel to drip, continue stirring 2 hours. after removing 4A molecular sieve, with dichloromethane extraction, rotary evaporation falls carrene, obtain aubergine solid, be 3-methyl-3 ', 5 '-di-t-butyl-5-chloromethane fundamental mode Schiff.
(5) preparation of graphite oxide surface grafting Schiff
The preparation (1.0g) of amino functional graphite oxide is added in 250mL flask; 100mL toluene; 3-methyl-3 ', 5 '-di-t-butyl-5-chloromethane fundamental mode Schiff (1.0g), refluxes under nitrogen protection by mixture 24 hours; filter; with absolute ether washing, then carry 24h with carrene rope, 40 DEG C of vacuum drying; obtain the 3-methyl-3 of the graphite oxide surface grafting of black ', 5 '-di-t-butyl-5-methylene fundamental mode Schiff.
Embodiment 3
(1) preparation of graphite oxide
With embodiment 1.
(2) preparation of amino functional graphite oxide
Graphite oxide (0.5g) is added, DMF (DMF) solvent 150mL in 500mL flask; Ultrasonic disperse 30 minutes, mixed liquor is at room temperature stirred 1 hour, then add butanediamine 300mL, continue ultrasonic 15 minutes, stirred at ambient temperature 1h, be warming up to 60 DEG C, stop reaction after stirring and refluxing 6h, filter with after absolute ethyl alcohol (500mL) dilution, and with the unreacted diamines of absolute ethyl alcohol cyclic washing, 50 DEG C of vacuum drying, obtain the amino functional graphite oxide of black.
(3) 5-chloromethyl-3-tert-butyl group salicylide is synthesized
With embodiment 1.
(4) the 3-tert-butyl group-5-chloromethane fundamental mode Schiff is synthesized
1 is added in 100mL three-neck flask; 2-cyclohexanediamine (10mmol); add 30mL absolute ethyl alcohol; logical argon shield; be placed in ice-water bath cooling, magnetic agitation, slowly drips the HCl/ diethyl ether solution (10mmol) of 2mmol/L with constant pressure funnel; dripping in 1 hour, there is a large amount of white precipitate in solution.Room temperature continues and to continue under condition continuously to stir 12h, then filtration under diminished pressure, and absolute ether washing (5 × 20mL), vacuum drying, obtains, without the white pressed powder of colour cast, obtaining the cyclohexanediamine hydrochloride of monolateral protection.
The cyclohexanediamine hydrochloride (5mmol) of monolateral protection is added respectively in 250mL three-neck flask; 25mL absolute ethyl alcohol and 25mL absolute ether; stirring at room temperature 10 minutes. get salicylide (5mol); after 50mL anhydrous alcohol solution; drip with constant pressure funnel; add a certain amount of 4A molecular sieve simultaneously and slough the water produced in condensation reaction, stir 4 hours, solution is faint yellow.Drip the triethylamine of 5mmol, stirring at room temperature 1 hour, then get 3-methyl-5-chloro cresotinic acid aldehyde and be dissolved in 25mL carrene, drip 30min with constant pressure funnel to drip, continuing stirring 2 hours. after removing 4A molecular sieve, with dichloromethane extraction, rotary evaporation falls carrene, obtain aubergine solid, be the 3-tert-butyl group-5-chloromethane fundamental mode Schiff.
(5) preparation of graphite oxide surface grafting Schiff
Amino functional graphite oxide (1.0g) is added in 250mL flask; 100mL toluene; the 3-tert-butyl group-5-chloromethane fundamental mode Schiff (1.0g); mixture is refluxed under nitrogen protection 24 hours; filter, with absolute ether washing, then carry 24h with carrene rope; 40 DEG C of vacuum drying, obtain the 3-tert-butyl group-5-methylene fundamental mode Schiff of the graphite oxide surface grafting of black.
Embodiment 4
(1) preparation of graphite oxide
With embodiment 1.
(2) preparation of amino functional graphite oxide
With embodiment 1.
(3) 5-chloromethyl-3-tert-butyl group salicylide is synthesized
With embodiment 1.
(4) 3,3 ', 5 '-tri-tert-5-chloromethane fundamental mode Schiff are synthesized
Ethylenediamine (10mmol) is added in 100mL three-neck flask; add 30mL absolute ethyl alcohol; logical argon shield; be placed in ice-water bath cooling; magnetic agitation; slowly drip the HCl/ diethyl ether solution (10mmol) of 2mmol/L with constant pressure funnel, dripping in 1 hour, there is a large amount of white precipitate in solution.Room temperature continues and to continue under condition continuously to stir 12h, then filtration under diminished pressure, and absolute ether washing (5 × 20mL), vacuum drying, obtains, without the white pressed powder of colour cast, obtaining the ethylenediamine-hydrochloride of monolateral protection.
The ethylenediamine-hydrochloride (5mmol) of monolateral protection is added respectively in 250mL three-neck flask; 25mL absolute ethyl alcohol and 25mL absolute ether; stirring at room temperature 10 minutes. get 3; 5-di-tert-butyl salicylaldehyde (5mol); after 50mL anhydrous alcohol solution, drip with constant pressure funnel, add a certain amount of 4A molecular sieve simultaneously and slough the water produced in condensation reaction; stir 4 hours, solution is faint yellow.Drip the triethylamine of 5mmol, stirring at room temperature 1 hour, then get 3-chloromethyl-5-tert-butyl group salicylide (5mmol) and be dissolved in 25mL carrene, drip 30min with constant pressure funnel and drip, continue stirring 2 hours. after removing 4A molecular sieve, with dichloromethane extraction, rotary evaporation falls carrene, obtains aubergine solid, is 3,3 ', 5 '-tri-tert-5-chloromethane fundamental mode Schiff.
(5) preparation of graphite oxide surface grafting Schiff
Amino functional graphite oxide (1.0g) is added in 250mL flask; 100mL toluene; the 3-tert-butyl group-5-chloromethane fundamental mode Schiff (1.0g), refluxes under nitrogen protection by mixture 24 hours, filters; wash with absolute ether; then carry 24h with carrene rope, 40 DEG C of vacuum drying, obtain 3 of the graphite oxide surface grafting of black; 3 ', 5 '-tri-tert-5-methylene fundamental mode Schiff.
Embodiment 5
(1) preparation of graphite oxide
With embodiment 1.
(2) preparation of amino functional graphite oxide
With embodiment 2.
(3) 5-chloromethyl-3-tert-butyl group salicylide is synthesized
With embodiment 1.
(4) the 3-tert-butyl group-5-chloromethane fundamental mode Schiff is synthesized
1 is added in 100mL three-neck flask; 2-o-phenylenediamine (10mmol); add 30mL absolute ethyl alcohol; logical argon shield; be placed in ice-water bath cooling, magnetic agitation, slowly drips the HCl/ diethyl ether solution (10mmol) of 2mmol/L with constant pressure funnel; dripping in 1 hour, there is a large amount of white precipitate in solution.Room temperature continues and to continue under condition continuously to stir 12h, then filtration under diminished pressure, and absolute ether washing (5 × 20mL), vacuum drying, obtains, without the white pressed powder of colour cast, obtaining the o-phenylendiamine dihydrochloride of monolateral protection.
The o-phenylendiamine dihydrochloride (5mmol) of monolateral protection is added respectively in 250mL three-neck flask; 25mL absolute ethyl alcohol and 25mL absolute ether; stirring at room temperature 10 minutes. get salicylide (5mol); after 50mL anhydrous alcohol solution; drip with constant pressure funnel; add a certain amount of 4A molecular sieve simultaneously and slough the water produced in condensation reaction, stir 4 hours, solution is faint yellow.Drip the triethylamine of 5mmol, stirring at room temperature 1 hour, then get 3-methyl-5-chloro cresotinic acid aldehyde and be dissolved in 25mL carrene, drip 30min with constant pressure funnel to drip, continuing stirring 2 hours. after removing 4A molecular sieve, with dichloromethane extraction, rotary evaporation falls carrene, obtain aubergine solid, be the 3-tert-butyl group-5-chloromethane fundamental mode Schiff.
(5) preparation of graphite oxide surface grafting Schiff
Amino functional graphite oxide (1.0g) is added in 250mL flask; 100mL toluene; the 3-tert-butyl group-5-chloromethane fundamental mode Schiff (1.0g); mixture is refluxed under nitrogen protection 24 hours; filter, with absolute ether washing, then carry 24h with carrene rope; 40 DEG C of vacuum drying, obtain the 3-tert-butyl group-5-methylene fundamental mode Schiff of the graphite oxide surface grafting of black.
Embodiment 6
Graphite oxide surface grafting 3 prepared by embodiment 1, 3 ', 5 '-tri-tert-5-methylene fundamental mode Schiff adsorbent props up with 2mg/ and adds cigarette binary combined filter tip to, roll into cigarette, cigarette sample balances through temperature humidity, after resistance to suction and weight are screened, cigarette smoking is carried out according to GB/T16450-2004 with R200H type disk type smoking machine, in main flume grain phase constituent, heavy metal adopts Electrostatic pipe to trap, in gas phase composition, heavy metal adopts the absorption bottle being added with the salpeter solution of 20mL10% to collect, adopt YC/T379-2010 standard method of analysis, i.e. plasma inductance coupling-mass spectrum (ICP-MS method) analytic approach, respectively the heavy metal Cd in sample is collected to two parts, the elements such as Pb and Cr carry out analysis inspection.Carry out the check experiment of blank cigarette sample simultaneously.Test cigarette and contrast the heavy metal Cd of cigarette, the reduced rate of Pb and Cr is respectively 10.7%, 5.3% and 12.1%.
Embodiment 7
Graphite oxide surface grafting 3 prepared by embodiment 1, 3 ', 5 '-tri-tert-5-methylene fundamental mode Schiff adsorbent props up with 5mg/ and adds cigarette binary combined filter tip to, roll into cigarette, cigarette sample balances through temperature humidity, after resistance to suction and weight are screened, cigarette smoking is carried out according to GB/T16450-2004 with R200H type disk type smoking machine, in main flume grain phase constituent, heavy metal adopts Electrostatic pipe to trap, in gas phase composition, heavy metal adopts the absorption bottle being added with the salpeter solution of 20mL10% to collect, adopt YC/T379-2010 standard method of analysis, i.e. plasma inductance coupling-mass spectrum (ICP-MS method) analytic approach, respectively the heavy metal Cd in sample is collected to two parts, the elements such as Pb and Cr carry out analysis inspection.Carry out the check experiment of blank cigarette sample simultaneously.Test cigarette and contrast the heavy metal Cd of cigarette, the reduced rate of Pb and Cr is respectively 25.2%, 15.3% and 23.1%.
Embodiment 8
Graphite oxide surface grafting 3 prepared by embodiment 1, 3 ', 5 '-tri-tert-5-methylene fundamental mode Schiff adsorbent props up with 10mg/ and adds cigarette binary combined filter tip to, roll into cigarette, cigarette sample balances through temperature humidity, after resistance to suction and weight are screened, cigarette smoking is carried out according to GB/T16450-2004 with R200H type disk type smoking machine, in main flume grain phase constituent, heavy metal adopts Electrostatic pipe to trap, in gas phase composition, heavy metal adopts the absorption bottle being added with the salpeter solution of 20mL10% to collect, adopt YC/T379-2010 standard method of analysis, i.e. plasma inductance coupling-mass spectrum (ICP-MS method) analytic approach, respectively the heavy metal Cd in sample is collected to two parts, the elements such as Pb and Cr carry out analysis inspection.Carry out the check experiment of blank cigarette sample simultaneously.Test cigarette and contrast the heavy metal Cd of cigarette, the reduced rate of Pb and Cr is respectively 26.5%, 19.6% and 23.7%.
Embodiment 9
The 3-methyl-3 of graphite oxide surface grafting prepared by embodiment 2 ', 5 '-di-t-butyl-5-methylene fundamental mode Schiff adsorbent props up with 6mg/ and adds cigarette binary combined filter tip to, roll into cigarette, cigarette sample balances through temperature humidity, after resistance to suction and weight are screened, cigarette smoking is carried out according to GB/T16450-2004 with R200H type disk type smoking machine, in main flume grain phase constituent, heavy metal adopts Electrostatic pipe to trap, in gas phase composition, heavy metal adopts the absorption bottle being added with the salpeter solution of 20mL10% to collect, adopt YC/T379-2010 standard method of analysis, i.e. plasma inductance coupling-mass spectrum (ICP-MS method) analytic approach, respectively the heavy metal Cd in sample is collected to two parts, the elements such as Pb and Cr carry out analysis inspection.Carry out the check experiment of blank cigarette sample simultaneously.Test cigarette and contrast the heavy metal Cd of cigarette, the reduced rate of Pb and Cr is respectively 24.5%, 20.3% and 21.7%.
Embodiment 10
The 3-tert-butyl group-5-methylene fundamental mode Schiff the adsorbent of graphite oxide surface grafting embodiment 3 prepared props up with 4mg/ and adds cigarette binary combined filter tip to, roll into cigarette, cigarette sample balances through temperature humidity, after resistance to suction and weight are screened, cigarette smoking is carried out according to GB/T16450-2004 with R200H type disk type smoking machine, in main flume grain phase constituent, heavy metal adopts Electrostatic pipe to trap, in gas phase composition, heavy metal adopts the absorption bottle being added with the salpeter solution of 20mL10% to collect, adopt YC/T379-2010 standard method of analysis, i.e. plasma inductance coupling-mass spectrum (ICP-MS method) analytic approach, respectively the heavy metal Cd in sample is collected to two parts, the elements such as Pb and Cr carry out analysis inspection.Carry out the check experiment of blank cigarette sample simultaneously.Test cigarette and contrast the heavy metal Cd of cigarette, the reduced rate of Pb and Cr is respectively 17.3%, 16.2% and 21.1%.
Embodiment 11
3 of graphite oxide surface grafting prepared by embodiment 4, 3 ', 5 '-tri-tert-5-methylene fundamental mode Schiff adsorbent props up with 5mg/ and adds cigarette binary combined filter tip to, roll into cigarette, cigarette sample balances through temperature humidity, after resistance to suction and weight are screened, cigarette smoking is carried out according to GB/T16450-2004 with R200H type disk type smoking machine, in main flume grain phase constituent, heavy metal adopts Electrostatic pipe to trap, in gas phase composition, heavy metal adopts the absorption bottle being added with the salpeter solution of 20mL10% to collect, adopt YC/T379-2010 standard method of analysis, i.e. plasma inductance coupling-mass spectrum (ICP-MS method) analytic approach, respectively the heavy metal Cd in sample is collected to two parts, the elements such as Pb and Cr carry out analysis inspection.Carry out the check experiment of blank cigarette sample simultaneously.Test cigarette and contrast the heavy metal Cd of cigarette, the reduced rate of Pb and Cr is respectively 23.7%, 18.5% and 21.3%.
Embodiment 12
The 3-tert-butyl group-5-methylene fundamental mode Schiff the adsorbent of graphite oxide surface grafting embodiment 5 prepared props up with 4mg/ and adds cigarette binary combined filter tip to, roll into cigarette, cigarette sample balances through temperature humidity, after resistance to suction and weight are screened, cigarette smoking is carried out according to GB/T16450-2004 with R200H type disk type smoking machine, in main flume grain phase constituent, heavy metal adopts Electrostatic pipe to trap, in gas phase composition, heavy metal adopts the absorption bottle being added with the salpeter solution of 20mL10% to collect, adopt YC/T379-2010 standard method of analysis, i.e. plasma inductance coupling-mass spectrum (ICP-MS method) analytic approach, respectively the heavy metal Cd in sample is collected to two parts, the elements such as Pb and Cr carry out analysis inspection.Carry out the check experiment of blank cigarette sample simultaneously.Test cigarette and contrast the heavy metal Cd of cigarette, the reduced rate of Pb and Cr is respectively 20.1%, 16.6% and 19.7%.
Claims (11)
1. a graphite oxide surface grafting Schiff compound, is characterized in that, the group by graphite oxide surface grafting with formula 1 structure is formed;
Wherein, n is 2 ~ 4;
R is
a kind of in substituted radical;
R
1, R
2and R
3be selected from hydrogen atom, methyl or the tert-butyl group a kind of independently of one another.
2. graphite oxide surface grafting Schiff compound as claimed in claim 1, is characterized in that, R
1and R
2for identical substituted radical.
3. graphite oxide surface grafting Schiff compound as claimed in claim 1, is characterized in that, described graphite oxide is oxidized crystalline flake graphite by improvement Hummers method to obtain.
4. graphite oxide surface grafting Schiff compound as claimed in claim 3, is characterized in that, described improvement Hummers method oxidation crystalline flake graphite is dispersed in sulfuric acid solution by crystalline flake graphite, first uses the KMnO of crystalline flake graphite quality 3 ~ 4 times
4be oxidized after 1 ~ 2h being not more than under the condition of 5 DEG C, be warmed up to 30 ~ 40 DEG C and continue oxidation 1.5 ~ 2.5h, then with hydrogen peroxide solution 90 ~ 100 DEG C of oxidations further, until reactant liquor becomes golden yellow.
5. the application of the graphite oxide surface grafting Schiff compound as described in any one of Claims 1 to 4, it is characterized in that, described graphite oxide surface grafting Schiff compound is added in cigarette filter rod as adsorbent the burst size being applied to heavy metal Cd, Pb and Cr in selectivity reducing cigarette main flume.
6. apply as claimed in claim 5, it is characterized in that, the described addition of graphite oxide surface grafting Schiff compound in cigarette filter rod is that 1 ~ 10mg/ props up.
7. apply as claimed in claim 6, it is characterized in that, the described addition of graphite oxide surface grafting Schiff compound in cigarette filter rod is that 2 ~ 6mg/ props up.
8. apply as claimed in claim 5, it is characterized in that, described graphite oxide surface grafting Schiff compound is added on the close pipe tobacco section of cigarette binary compound filter candle or the interlude of Three-element composite filter core.
9. the preparation method of the graphite oxide surface grafting Schiff compound as described in any one of Claims 1 to 4, it is characterized in that, improvement hummers method is adopted by crystalline flake graphite to be oxidized to surperficial carboxylic graphite oxide, again carboxylic graphite oxide and aliphatic hydrocarbon diamines are carried out amidation process, obtain graphite oxide surface grafting amino-compound; Gained graphite oxide surface grafting amino-compound and the Schiff generation substitution reaction with formula 2 structure, to obtain final product; Described aliphatic hydrocarbon diamines comprises ethylenediamine, 1,3-propane diamine or Putriscine;
R is
a kind of in substituted radical;
R
1, R
2and R
3be selected from hydrogen atom, methyl or the tert-butyl group a kind of independently of one another.
10. preparation method as claimed in claim 9, it is characterized in that, described Schiff is by ethylenediamine, 1,2-cyclohexanediamine or o-phenylenediamine first with there is 3 of formula 4 structure, the disubstituted salicylide of 5-carries out the condensation reaction of amine aldehyde, then carries out the condensation reaction of amine aldehyde with the 5-chloromethyl-3-substituting group salicylide with formula 3 structure and obtain;
R
1, R
2and R
3be selected from hydrogen atom, methyl or the tert-butyl group a kind of independently of one another.
11. preparation methods as claimed in claim 10, is characterized in that, described R
1and R
2for identical substituting group.
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| WO2009105881A1 (en) * | 2008-02-28 | 2009-09-03 | Saint Mary's University | Ionic liquids comprising ligands containing positively charged heterocyclic ring useful as catalyst and for metal extractions |
| CN103209606A (en) * | 2010-10-06 | 2013-07-17 | 塞拉尼斯醋酸纤维有限公司 | Smoke filters for smoking devices with porous masses having a carbon particle loading and an encapsulated pressure drop |
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| CN1709171A (en) * | 2005-07-06 | 2005-12-21 | 南京师范大学 | Use of phthalocyanin compound as cigarette harm-reducing agent |
| WO2009105881A1 (en) * | 2008-02-28 | 2009-09-03 | Saint Mary's University | Ionic liquids comprising ligands containing positively charged heterocyclic ring useful as catalyst and for metal extractions |
| CN103209606A (en) * | 2010-10-06 | 2013-07-17 | 塞拉尼斯醋酸纤维有限公司 | Smoke filters for smoking devices with porous masses having a carbon particle loading and an encapsulated pressure drop |
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