CN103524753B - A kind of ion liquid functionalization polyamidoamine dendrimer load Schiff compound and its preparation method and application - Google Patents
A kind of ion liquid functionalization polyamidoamine dendrimer load Schiff compound and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of ion liquid functionalization polyamidoamine branch macromolecule loading Schiff compound and its preparation method and application, preparation method is first is core with quadrol, branch is obtained after repeatedly carrying out the amidate action of Micheal addition reaction and ester by quadrol and methyl acrylate, and by the amidate action of ester at gained branch terminal graft 1-(3-amine propyl group) imidazoles, again by the N alkylated reaction grafting Schiff of imidazole ring, to obtain final product; This preparation method's process is simple, can suitability for industrialized production; It is large that obtained ion liquid functionalization polyamidoamine branch macromolecule loading Schiff compound has loading capacity to the heavy metal in cigarette smoke and tar, the feature of high adsorption capacity, it can be used as sorbent material to add the burst size that effectively simultaneously can reduce heavy metal and tar in cigarette mainstream flue gas on a small quantity in cigarette filter rod.
Description
Technical field
The present invention relates to a kind of ion liquid functionalization polyamidoamine dendrimer load Schiff compound and its preparation method and application, belong to new cigarette heavy metal polymer adsorbing material field.
Background technology
The heavy metal such as plumbous (Pb), arsenic (As), cadmium (Cd), chromium (Cr), mercury (Hg) is contained in tobacco and tobacco product.In cigarette smoking process, heavy metal and compound thereof can be inhaled into human body as the form of flue gas aerosol or metal oxide and easily enrichment and produce harm [Chen, Q-H. etc. in human body, StudiesofTraceElementsandHealth, 2005,22,47-49].There are some researches show, tobacco-using male blood cadmium concentration is higher than non-smoker [Xin Nan etc., Chinese Medicine biotechnology, 2009,4 (5): 390] obviously.Proper amount of active carbon is added in the processing process of cigarette filter, the adsorption effect of filter tip to Cd, Ni and As adding gac is respectively 4.26,3.58 and 1.62 times of [Liu Ruoman etc. of former cellulose acetate filter tip, environment and health magazine, 1991,16 (4): 204], adsorption effect significantly strengthens, because the adsorption selection of gac is indifferent, in the filter tip stick of Virginian-type cigarette, add gac can bring certain negative impact to cigarette odor-absorbing, thus seldom adopt.J.W. little OK a karaoke club dimension etc. have invented a kind of cigarette filter [little OK a karaoke club dimension of J.W. etc., Chinese patent CN101043826A], contain the chitosan be cross-linked mutually with glutaraldehyde in its strainer and make the porous resin material of high surface-area/mass ratio with the chitosan that oxalic dialdehyde is cross-linked mutually, alternative aldehyde, prussic acid, carbonyl compound and the heavy metal etc. removed in cigarette smoke, but this kind of material affects cigarette odor-absorbing owing to can reduce the carbonyl compound with fragrance effect.Chen Yuru etc. adopt phthalocyanine-like compound as cigarette harm-reducing agent [Chen Yuru etc., Chinese patent CN1709171A], phthalocyanine-like compound has obvious reducing effect to objectionable impuritiess such as the CO in flue gas, oxynitride, aldehydes, amines, can also heavy-metal ion removal, cancellation free radical.One in Chlorophyll Cu and CHLOROPHYLLINE sodium or two kinds are joined triacetin three ester by Zhou Guojun etc., spray in tow, or being prepared into 40 ~ 80 order particles adds in mouth rod, can effectively catching heavy metal [Zhou Guojun etc., Chinese patent CN101238913A], but green plain copper and CHLOROPHYLLINE sodium are insoluble to triacetin three ester substantially, exist and add difficulty and affect the problems such as wire-beam forming, and green plain copper inherently a kind of complex compound, heavy metal again complex ability is limited.
But utilize ionic liquid functional group and Schiff to be incorporated into the sorbing material simultaneously making Adsorption of Heavy Metals and tar in dendrimer simultaneously, have no the bibliographical information of this respect so far.
Summary of the invention
First object of the present invention is to provide a kind of compound with regular structure, height cladodification, and the ion liquid functionalization polyamidoamine dendrimer load Schiff compound of heavy metal and tar function during there is active adsorption cigarette smoke simultaneously.
Second object of the present invention is the application of the polyamidoamine dendrimer load Schiff compound being to provide described ion liquid functionalization, it can be used as sorbent material to add a small amount of in cigarette filter rod, the heavy metal in cigarette smoke and tar content can be reduced effectively simultaneously.
3rd object of the present invention is the preparation method being to provide a kind of described ion liquid functionalization polyamidoamine dendrimer load Schiff compound, the method strictly can control molecular structure of compounds, and preparation process is simple, can suitability for industrialized production.
Present invention also offers a kind of ion liquid functionalization polyamidoamine dendrimer load Schiff compound, the compound with formula 1 structure that the Schiff having formula 2 structure by the grafting of ion liquid functionalization polyamidoamine dendrimer obtains;
Wherein,
R is
or
a kind of in substituted radical;
M is the Schiff number of grafting;
R
1, R
2and R
3be selected from hydrogen atom, methyl or the tertiary butyl a kind of independently of one another;
Described ion liquid functionalization polyamidoamine dendrimer comprises G1, G2 or G3, and wherein, G1 is
G2 is
G3 is
Preferred ion liquid functionalization polyamidoamine dendrimer load Schiff compound, R
1and R
2for identical substituting group.
More preferably ion liquid functionalization polyamidoamine dendrimer load Schiff compound, m is 4 or 8 or 16; Namely, when described ion liquid functionalization polyamidoamine dendrimer is G1, G2 or G3, corresponding m is 4,8 or 16.
Present invention also offers a kind of application of described ion liquid functionalization polyamidoamine dendrimer load Schiff compound, this application is that described ion liquid functionalization polyamidoamine dendrimer load Schiff compound is added in cigarette filter rod as sorbent material the burst size being applied to and reducing heavy metal and tar in cigarette mainstream flue gas simultaneously.
The described addition of ion liquid functionalization polyamidoamine dendrimer load Schiff compound in cigarette filter rod is that 1 ~ 10mg/ props up; Be preferably 3 ~ 8mg/ to prop up.
Described ion liquid functionalization polyamidoamine dendrimer load 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 ion liquid functionalization polyamidoamine dendrimer load Schiff compound, this preparation method is first is core with quadrol, branch is obtained after repeatedly carrying out the amidate action of Micheal addition reaction and ester by quadrol and methyl acrylate, and by the amidate action of ester at gained branch terminal graft 1-(3-amine propyl group) imidazoles, again by the Schiff of N alkylated reaction grafting formula 2 structure of imidazoles, to obtain final product.
Described Schiff first carries out the condensation reaction of amine aldehyde with 3, the 5-disubstituted salicylic aldehydes with formula 4 structure by diamines, then carries out the condensation reaction of amine aldehyde with the 5-chloromethyl-3-substituting group salicylic aldehyde with formula 3 structure and obtain; Described diamines comprises cyclohexanediamine, quadrol or O-Phenylene Diamine;
R
1, R
2and R
3be selected from hydrogen atom, methyl or the tertiary butyl a kind of independently of one another.
Described R
1and R
2be preferably identical substituting group.
Preferred preparation method is first obtained by reacting G0.5 by quadrol and methyl acrylate with mol ratio 1:4, G0.5 and 1-(3-amine propyl group) imidazoles reacts with mol ratio 1:4, obtain G1, G1 and Schiff, with mol ratio 1:4 reaction, obtain the first ion liquid functionalization polyamidoamine dendrimer load Schiff compound; Or be obtained by reacting G1.5 by G1 and methyl acrylate with mol ratio 1:8 further, G1.5 and 1-(3-amine propyl group) imidazoles reacts with mol ratio 1:8, obtain G2, G2 and Schiff, with mol ratio 1:8 reaction, obtain the second ion liquid functionalization polyamidoamine dendrimer load Schiff compound; Or be obtained by reacting G2.5 by G2 and methyl acrylate with mol ratio 1:16 further again, G2.5 and 1-(3-amine propyl group) imidazoles reacts with mol ratio 1:16, obtain G3, G3 and Schiff, with mol ratio 1:16 reaction, obtain the third ion liquid functionalization polyamidoamine dendrimer load Schiff compound.
The preparation of ion liquid functionalization polyamidoamine dendrimer load Schiff compound of the present invention comprises the following steps:
(1) the ion liquid functionalization polyamidoamine dendrimer compound of different algebraically is synthesized:
First with mol ratio 1:4, Micheal addition reaction occurring by quadrol and methyl acrylate obtains G0.5, the amidate action of ester is there is in G0.5 and 1-(3-amine propyl group) imidazoles with mol ratio 1:4, obtain G1, obtain the first ion liquid functionalization polyamidoamine dendrimer;
Or there is Micheal addition reaction by G1 and methyl acrylate with mol ratio 1:8 further and obtain G1.5, the amidate action of ester is there is in G1.5 and 1-(3-amine propyl group) imidazoles with mol ratio 1:8, obtain G2, obtain the second ion liquid functionalization polyamidoamine dendrimer;
Or there is Micheal addition reaction by G2 and methyl acrylate with mol ratio 1:16 further again and obtain G2.5, the amidate action of ester is there is in G2.5 and 1-(3-amine propyl group) imidazoles with mol ratio 1:16, obtain G3, obtain the third ion liquid functionalization polyamidoamine dendrimer;
Synthetic route is as follows:
(2) ion liquid functionalization polyamidoamine dendrimer load Schiff compound is synthesized:
A, synthesis 5-chloromethyl-3-substituted salicylic aldehydes:
First by 2-fortified phenol and paraformaldehyde back flow reaction 3h in triethylamine of Grignard reagent process, preparation 3-substituted salicylic aldehydes, then with preparation 3-substituted salicylic aldehydes for raw material, under Tetrabutyl amonium bromide catalysis, 72h are reacted at 40 DEG C by the hydrochloric acid soln of 3-substituted salicylic aldehydes and paraformaldehyde, preparation 5-chloromethyl-3-substituting group salicylic aldehyde, synthetic route is as follows:
R
3be selected from hydrogen atom, methyl or the tertiary butyl 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 salicylic aldehyde 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 tertiary butyl a kind of independently of one another;
R is
or
a kind of in substituted radical;
Described diamines comprises cyclohexanediamine, quadrol or O-Phenylene Diamine;
(3) the Schiff compound of ion liquid functionalization polyamidoamine dendrimer load is synthesized:
There is N alkylated reaction with mol ratio 1:4,1:8,1:16 in the Schiff that G1, G2 and G3 of step (1) being obtained obtain with step (2) respectively, obtains the compound of three kinds of ion liquid functionalization polyamidoamine dendrimer load Schiff respectively:
Synthetic route is as follows:
Beneficial effect of the present invention: the present invention has synthesized the double-Schiff base containing chloromethyl first, Schiff is introduced polyamine-amine type dendrimer by ionic liquid functional group, obtain ion liquid functionalization polyamidoamine dendrimer load Schiff compound, and it can be used as sorbent material to be added in cigarette filter rod to adsorb the heavy metal in main flume and tar effectively simultaneously.The ion liquid functionalization polyamidoamine dendrimer load Schiff compound of the present invention's synthesis is a kind of highly branched, compound with regular structure, and the dendrimer that molecular size is controlled, particularly branch end introduces the Schiff group of imidazole ring and bisphenol type simultaneously, these groups have very strong Coordination Adsorption effect to the heavy metal in flue gas, on macromolecular compound branch, also there is the electron donors such as a large amount of amide groups and nitrogen-atoms simultaneously, certain ability in conjunction with heavy metal is played between these supplied for electronics, also the effect of assisting Schiff chelate heavy metals is played further, make such ion liquid functionalization polyamidoamine dendrimer load Schiff compound large especially to the adsorptive capacity of the heavy metal in flue gas, the burst size of heavy metal in main flume effectively can be reduced when consumption is little, be specially adapted to Cd in flue gas, the absorption of Pb and As, and surprisingly ion liquid functionalization polyamidoamine dendrimer load Schiff compound of the present invention is simultaneously very large to the adsorptive capacity that flue gas is coal-tar middle oil, experimental results demonstrate: propped up with 8mg/ by ion liquid functionalization polyamidoamine dendrimer load Schiff compound of the present invention and be added in cigarette, the coal-tar middle oil content reduced rate of cigarette smoke can reach 30.8%, the reduced rate of Cd can reach 35.7% simultaneously, the reduced rate of Pb can reach 26.3%, the reduced rate of As can reach 29.1%, in addition, this ion liquid functionalization polyamidoamine dendrimer load Schiff compound is macromolecular solid thing, good stability, use safety, and preparation process is simple, is easy to suitability for industrialized production.
Accompanying drawing explanation
[Fig. 1] is the infrared comparison diagram of G0.5, G1 and G1 load Schiff prepared by embodiment 1: a is G0.5, b be G1.0, c is ion liquid functionalization polyamidoamine dendrimer grafting Shiff alkali cpd.
Embodiment
Following examples are intended to further illustrate the present invention, instead of limit the scope of the invention.
Embodiment 1
(1) synthesis of first-generation polyamidoamine dendrimer grafting imidazolium compounds G1.0
At 25 DEG C, by quadrol (EDA) (1.202g, 20mmol) as macromolecular core, with methyl acrylate (MA) 6.887g, 80mmol) in 50mL methanol solution, react the 72h(the first step), after reaction, solution is carried out decompression rotary evaporation at 70 DEG C, when solvent is spin-dried for, is cooled to room temperature, dissolve with methanol is added in system, decompression rotary evaporation is carried out again, the product obtained afterwards in triplicate, 50 DEG C of vacuum-dryings at 70 DEG C, obtain 0.5 generation (G0.5) macromole, this macromole end has four ester functional groups.0.5G amine dendrimer (0.202g, 2mmol ester group) is dissolved in anhydrous methanol (20mL), at 0 DEG C, slowly drips the methanol solution of 1-(3-amine propyl group) imidazoles (0.250g, 2mmol), reaction 1h.Then, at 40 DEG C, 72h is reacted.After having reacted, except desolventizing, to obtain yellow viscous liquid be end to rotary evaporation is the amine dendrimer G1.0 of imidazoles.FT-IR(KBr):γ
max/cm
-1:3292,3106,3054,2944,2871,2833,1731,1656,1554,1542,1508,1456,1436,1359,1280,1230,1108,1079,1029,910,815,738,663,620。
(2) synthesis of 5-chloromethyl-3-tertiary butyl salicylic aldehyde
In 500mL there-necked flask, add 0.10mol (2.4g) magnesium powder and 50mL anhydrous diethyl ether, in 1h, be under agitation added dropwise to 0.10mol (9mL) monobromethane.Slowly temperature rising reflux 1h after dropwising, returns to room temperature (a small amount of magnesium powder reaction), obtains Grignard reagent CH after magnesium powder fully reacts
3cH
2mgBr.0.10mol (15.5mL) 2-TBP is dissolved in 60mL tetrahydrofuran (THF), is at room temperature added dropwise in 1h in the Grignard reagent of just preparation.When after a large amount of white precipitate of appearance, add 200mL hexanaphthene or benzene.Slow rising temperature of reaction, steams and removes about 100mL solvent, lower boiling solvent in system is distilled out of as best one can.Add into 50mL hexanaphthene or benzene again, then in reaction solution, add 0.15mol (21mL) triethylamine and 0.75mol (22.5g) paraformaldehyde immediately.After reflux 3h, TLC follows the tracks of reaction process, then is cooled to room temperature.By in reaction solution impouring 500mL10% hydrochloric acid soln, after fully stirring, separatory after leaving standstill, after appropriate normal hexane (boiling range 60 ~ 90 DEG C) aqueous phase extracted twice, merges organic phase, uses anhydrous magnesium sulfate drying.After filtering distillation removing organic solvent, be separated with column chromatography (normal hexane: ethyl acetate=50:1), obtain weak yellow liquid product 3-tertiary butyl salicylic aldehyde (15.5g).
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)。
Add by the 3-tertiary butyl salicylic aldehyde of above-mentioned synthesis (15.2mmol (2.7g)) in 100mL round-bottomed flask, 33.3mmol (1.0g) paraformaldehyde, 1.46mmol (0.47g) Tetrabutyl amonium bromide 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 anhydrous diethyl ether, use the sodium hydrogen carbonate solution of 4 × 10mL5% and the saturated NaCl solution washing of 4 × 10mL successively, anhydrous magnesium sulfate drying.Except desolventizing obtains 3.4g yellow solid product 5-chloromethyl-3-tertiary butyl salicylic aldehyde after filtering.
1HNMR(CDCl
3,500MHz):δ
H,ppm:1.43(s,9H,Me),4.59(s,2H,CH
2),7.44(d,1H,Ar),7.53(d,1H,Ar),9.87(s,1H,CHO),11.87(s,1H,OH)。
(3) the 5-chloromethyl-3-tertiary butyl-3 is synthesized ', 5 '-di-t-butyl Schiff
Cyclohexanediamine (11.2mmol) is dissolved in chloroform (20mL), slowly adds hydrochloric acid (11.2mmol) diethyl ether solution (2mol/L) at 0 DEG C, at room temperature spend the night.Then by the protected quadrol of this single amino (8mmol) and 3; 5-di-tert-butyl salicylaldehyde (8mmol) is dissolved in anhydrous methanol and the dehydrated alcohol (1/1 that 60mL is added with active 4A molecular sieve (1g); V/V) in mixed solvent; at room temperature react 4h, obtain faint yellow solid.Anhydrous methylene chloride mixing solutions 20mL being mixed with the 3-tertiary butyl-5-chloromethyl salicylaldehyde (8mmol) and triethylamine (16mmol) is slowly added dropwise in above-mentioned solution, at room temperature react 4h, reacted rear filtration, in dehydrated alcohol, recrystallization obtains thick product.Through column chromatography purification (SiO
2, ethyl acetate/normal hexane=1/5, V/V), obtain pale yellow powder shape solid, i.e. the 5-chloromethyl-3-tertiary butyl-3 ', 5 '-di-t-butyl 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。
(4) the first-generation ion liquid functionalization polyamidoamine dendrimer load 5-methylene radical-3-tertiary butyl-3 ', the preparation of 5 '-di-t-butyl Schiff
First-generation polyamidoamine dendrimer grafting imidazolium compounds G1.0(1mmol by synthesis) and above-mentioned synthesis contain the 5-chloromethyl-3-tertiary butyl-3 of cyclohexanediamine ', 5 '-di-t-butyl Schiff (4mmol) is placed in 100mL flask, add 50mL tetrahydrofuran (THF) (THF), back flow reaction 48h, rotary evaporation removing THF after reaction, in system, add 50mL anhydrous alcohol solution, after vigorous stirring 1h, be slowly warming up to 80 DEG C, continue reaction 5h.Be cooled to room temperature, filter and wash with deionized water, 40 DEG C of vacuum-dryings, obtain pale yellow powder shape solid, be the 5-methylene radical-3-tertiary butyl-3 of first-generation ion liquid functionalization polyamidoamine dendrimer load ', 5 '-di-t-butyl Schiff, first-generation polyamidoamine dendrimer G1.0 and the load 5-methylene radical-3-tertiary butyl-3 thereof to preparation ', 5 '-di-t-butyl Schiff has carried out infrared spectrum characterization, see accompanying drawing 1, accompanying drawing 1(b) in 3292,1731 and 620cm
-1wave number band is the infrared signature absorption peak of imidazoles, proves that imidazoles is successfully distributed to polyamidoamine dendrimer surface as end-capping reagent; Accompanying drawing 1(c) in 1630 and 1614cm
-1wave number band is the infrared signature absorption peak of Schiff, and has the characteristic peak of imidazoles, proves that imidazoles and Schiff are all successfully grafted on polyamidoamine dendrimer carrier.FT-IR(KBr):γ
max/cm
-1:3290,1737,1731,1650,1630,1614,1538,1533,1506,1461,1376,1361,1338,1309,1268,1251,1230,1199,1172,1108,1083,1027,927,889,885,875,836,813,781,748,723,698,663,620cm
-1。
Embodiment 2
(1) synthesis of s-generation polyamidoamine dendrimer grafting imidazolium compounds G2.0
At 25 DEG C, the 1.0G dendritic macromole (amido of 2.580g, 20mmol) of synthesis is dissolved in the middle of anhydrous methanol, then, then by methyl acrylate MA (3.440g, 40mmol) dropwise join in the middle of system, mixture at room temperature reacts 72h, after reaction, solution is carried out decompression rotary evaporation at 70 DEG C, when solvent evaporate to dryness, be cooled to room temperature, in system, add dissolve with methanol, at 70 DEG C, again carry out decompression rotary evaporation, in triplicate.Finally, by the product that obtains 50 DEG C of vacuum-dryings, 1.5 generations (G1.5) macromole is obtained.1.5G amine dendrimer (0.304g, 2mmol ester group) is dissolved in anhydrous methanol (20mL), at 0 DEG C, slowly drips the methanol solution of 1-(3-amine propyl group) imidazoles (0.250g, 2mmol), reaction 1h.Then, at 40 DEG C, 72h is reacted.After having reacted, except desolventizing, to obtain yellow viscous liquid be end to rotary evaporation is the amine dendrimer G2.0 of imidazoles.FT-IR(KBr):γ
max/cm
-1:3290,3104,3053,2942,2877,2833,1730,1658,1552,1546,1510,1458,1432,1354,1281,1233,1109,1079,1027,912,816,739,667,621。
(2) synthesis of 5-chloromethyl-3-tertiary butyl salicylic aldehyde
The synthesis of 5-chloromethyl-3-tertiary butyl salicylic aldehyde is with embodiment 1
(3) the 5-chloromethyl-3-tertiary butyl-3 is synthesized ', 5 '-dimethyl Schiff
Cyclohexanediamine (11.2mmol) is dissolved in chloroform (20mL), slowly adds hydrochloric acid (11.2mmol) diethyl ether solution (2mol/L) at 0 DEG C, at room temperature spend the night.Then by the protected quadrol of this single amino (8mmol) and 3; 5-bis-dimethyl salicylic aldehyde (8mmol) is dissolved in anhydrous methanol and the dehydrated alcohol (1/1 that 60mL is added with active 4A molecular sieve (1g); V/V) in mixed solvent; at room temperature react 4h, obtain faint yellow solid.Anhydrous methylene chloride mixing solutions 20mL being mixed with the 3-tertiary butyl-5-chloromethyl salicylaldehyde (8mmol) and triethylamine (16mmol) is slowly added dropwise in above-mentioned solution, at room temperature react 4h, reacted rear filtration, in dehydrated alcohol, recrystallization obtains thick product.Through column chromatography purification (SiO2, ethyl acetate/normal hexane=1/5, V/V), obtain pale yellow powder shape solid, i.e. the 5-chloromethyl-3-tertiary butyl-3 ', 5 '-dimethyl Schiff.
(4) the s-generation ion liquid functionalization polyamidoamine dendrimer load 5-methylene radical-3-tertiary butyl-3 ', the preparation of 5 '-dimethyl Schiff
S-generation polyamidoamine dendrimer grafting imidazolium compounds G2.0(1mmol by synthesis) and the 5-chloromethyl-3-tertiary butyl-3 of cyclohexanediamine of above-mentioned synthesis ', 5 '-dimethyl Schiff (8mmol) is placed in 100mL flask, add 50mL tetrahydrofuran (THF) (THF), back flow reaction 48h, rotary evaporation removing THF after reaction, in system, add 50mL anhydrous alcohol solution, after vigorous stirring 1h, be slowly warming up to 80 DEG C, continue reaction 5h.Be cooled to room temperature, filter and wash with deionized water, 40 DEG C of vacuum-dryings, obtaining pale yellow powder shape solid, be the 5-methylene radical-3-tertiary butyl-3 of s-generation ion liquid functionalization polyamidoamine dendrimer load ', 5 '-dimethyl Schiff.S-generation polyamidoamine dendrimer G2.0 and the load 5-methylene radical-3-tertiary butyl-3 thereof to preparation ', 5 '-dimethyl Schiff has carried out infrared spectrum characterization, has wherein all occurred 3292,1732 and 620cm
-1imidazoles wave number band charateristic avsorption band and 1632 and 1615cm
-1schiff infrared signature absorption peak, prove that imidazoles and Schiff are all successfully grafted on polyamidoamine dendrimer carrier.FT-IR(KBr):γ
max/cm
-1:3292,1736,1732,1651,1632,1615,1554,1535,1532,1506,1464,1376,1362,1338,1310,1251,1230,1199,1172,1108,1089,1027,925,889,885,875,833,816,780,750,725,698,667,620cm
-1。
Embodiment 3
(1) synthesis of third generation polyamidoamine dendrimer grafting imidazolium compounds
At 25 DEG C, the 2.0G dendritic macromole (amido of 2.856g, 16mmol) of synthesis is dissolved in the middle of anhydrous methanol, then, then by methyl acrylate (MA) (2.752g, 32mmol) dropwise join in the middle of system, mixture at room temperature reacts 72h, after reaction, solution is carried out decompression rotary evaporation at 70 DEG C, when solvent evaporate to dryness, be cooled to room temperature, in system, add dissolve with methanol, at 70 DEG C, carry out decompression rotary evaporation, in triplicate.Finally, by the product that obtains 50 DEG C of vacuum-dryings, 2.5 generations (G2.5) macromole is obtained.2.5G amine dendrimer (0.351g, 2mmol ester group) is dissolved in anhydrous methanol (20mL), at 0 DEG C, slowly drips the methanol solution of 1-(3-amine propyl group) imidazoles (0.250g, 2mmol), reaction 1h.Then, at 40 DEG C, 72h is reacted.After having reacted, except desolventizing, to obtain yellow viscous liquid be end to rotary evaporation is the amine dendrimer G3.0 of imidazoles.FT-IR(KBr):γ
max/cm
-1:3292,3106,3055,2946,2874,2833,1733,1658,1553,1541,1509,1455,1437,1358,1283,1230,1107,1080,1030,911,815,737,663,620。
(2) synthesis of 5-chloromethyl-3-tertiary butyl salicylic aldehyde
The synthesis of 5-chloromethyl-3-tertiary butyl salicylic aldehyde is with embodiment 1
(3) 5-chloromethyl-3-tertiary butyl Schiff is synthesized
Cyclohexanediamine (11.2mmol) is dissolved in chloroform (20mL), slowly adds hydrochloric acid (11.2mmol) diethyl ether solution (2mol/L) at 0 DEG C, at room temperature spend the night.Then the protected quadrol of this single amino (8mmol) and salicylic aldehyde (8mmol) are dissolved in anhydrous methanol and the dehydrated alcohol (1/1 that 60mL is added with active 4A molecular sieve (1g); V/V) in mixed solvent; at room temperature react 4h, obtain faint yellow solid.Anhydrous methylene chloride mixing solutions 20mL being mixed with the 3-tertiary butyl-5-chloromethyl salicylaldehyde (8mmol) and triethylamine (16mmol) is slowly added dropwise in above-mentioned solution, at room temperature react 4h, reacted rear filtration, in dehydrated alcohol, recrystallization obtains thick product.Through column chromatography purification (SiO
2, ethyl acetate/normal hexane=1/5, V/V), obtain pale yellow powder shape solid, i.e. 5-chloromethyl-3-tertiary butyl Schiff.
(4) the third generation ion liquid functionalization polyamidoamine dendrimer load 5-methylene radical-3-tertiary butyl-3 ', the preparation of 5 '-dimethyl Schiff
Third generation polyamidoamine dendrimer grafting imidazolium compounds G3.0(1mmol by synthesis) and 5-chloromethyl-3-tertiary butyl Schiff (16mmol) of cyclohexanediamine of containing of above-mentioned synthesis be placed in 100mL flask, add 50mL tetrahydrofuran (THF) (THF), back flow reaction 48h, rotary evaporation removing THF after reaction, 50mL anhydrous alcohol solution is added in system, slowly be warming up to 80 DEG C after vigorous stirring 1h, continue reaction 5h.Be cooled to room temperature, filter and wash with deionized water, 40 DEG C of vacuum-dryings, obtaining pale yellow powder shape solid, be the 5-methylene radical-3-tertiary butyl Schiff of third generation ion liquid functionalization polyamidoamine dendrimer load.Infrared spectrum characterization is carried out to the s-generation polyamidoamine dendrimer G2.0 prepared and load 5-methylene radical-3-tertiary butyl Schiff thereof, has wherein all occurred 3290,1732 and 621cm
-1imidazoles wave number band charateristic avsorption band and 1635 and 1615cm
-1schiff infrared signature absorption peak, prove that imidazoles and Schiff are all successfully grafted on polyamidoamine dendrimer carrier.FT-IR(KBr):γ
max/cm
-1:3290,1732,1653,1635,1615,1552,1534,1531,1507,1464,1375,1363,1337,1311,1248,1230,1197,1172,1108,1090,1027,925,887,885,876,832,814,783,750,725,697,667,621cm
-1。
Embodiment 4
(1) synthesis of s-generation polyamidoamine dendrimer grafting imidazolium compounds
The synthesis of s-generation polyamidoamine dendrimer grafting imidazolium compounds G2.0 is with embodiment 2
(2) 5-chloromethyl-3-cresotinic acid aldehyde is synthesized
In 500mL there-necked flask, add magnesium powder (2.4g, 0.10mol) and 50mL anhydrous diethyl ether, under agitation in 1h, drip monobromethane (0.10mol, 9mL), slowly temperature rising reflux 1h after dropwising, returns to room temperature, obtains Grignard reagent CH after magnesium powder fully reacts
3cH
2mgBr.Phenol (0.10mol) is dissolved in 60mL tetrahydrofuran (THF), is at room temperature added dropwise in 1h in the Grignard reagent of just preparation.When after a large amount of white precipitate of appearance, add hexanaphthene or benzene 200mL.Slow rising temperature of reaction, steams and removes about 100mL solvent, lower boiling solvent in system is distilled out of as best one can.Add into 50mL hexanaphthene or benzene again, then in reaction solution, add triethylamine (0.15mol) and paraformaldehyde (22.5g) immediately.After reflux 3h, TLC follows the tracks of reaction process, then is cooled to room temperature.By in reaction solution impouring 500mL10% hydrochloric acid soln, 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 (normal 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), Tetrabutyl amonium bromide (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 anhydrous diethyl ether, use the sodium hydrogen carbonate 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.
(3) 5-chloromethane-3-methyl-3 is synthesized ', 5 '-di-t-butyl Schiff
1 is added in 100mL three-necked flask; 2-quadrol (10mmol); add 30mL dehydrated 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 anhydrous diethyl 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-necked flask; 25mL dehydrated alcohol and 25mL anhydrous diethyl 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 5-chloromethane-3-methyl-3 is got ', 5 '-di-tert-butyl salicylaldehyde is dissolved in 25mL methylene dichloride, drips 30min drip with constant pressure funnel, continue stirring 2 hours. after removing 4A molecular sieve, with dichloromethane extraction, rotary evaporation falls methylene dichloride, obtains red-purple solid, be 3-methyl-3 ', 5 '-di-t-butyl-5-chloromethane fundamental mode Schiff.
(4) s-generation ion liquid functionalization polyamidoamine dendrimer load 5-methylene radical-3-methyl-3 ', the preparation of 5 '-di-t-butyl Schiff
S-generation polyamidoamine dendrimer grafting imidazolium compounds G2.0(1mmol by synthesis) and the 5-chloromethyl-3-methyl-3 of quadrol of above-mentioned synthesis ', 5 '-di-t-butyl Schiff (8mmol) is placed in 100mL flask, add 50mL tetrahydrofuran (THF) (THF), back flow reaction 48h, rotary evaporation removing THF after reaction, in system, add 50mL anhydrous alcohol solution, after vigorous stirring 1h, be slowly warming up to 80 DEG C, continue reaction 5h.Be cooled to room temperature, filter and wash with deionized water, 40 DEG C of vacuum-dryings, obtaining pale yellow powder shape solid, be the 5-methylene radical-3-tertiary butyl-3 of s-generation ion liquid functionalization polyamidoamine dendrimer load ', 5 '-dimethyl Schiff.
Embodiment 5
(1) synthesis of third generation polyamidoamine dendrimer grafting imidazolium compounds
The synthesis of third generation polyamidoamine dendrimer grafting imidazolium compounds G3.0 is with embodiment 3
(2) 5-chloromethyl salicylaldehyde is synthesized
(15.2mmol) salicylic aldehyde is added in 100mL round-bottomed flask, paraformaldehyde (1.0g), Tetrabutyl amonium bromide (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 anhydrous diethyl ether, use the sodium hydrogen carbonate solution of 4 × 10mL5% and the saturated NaCl solution washing of 4 × 10mL successively, anhydrous magnesium sulfate drying.Except desolventizing obtains yellow solid product 5-chloromethyl salicylaldehyde after filtering.
(3) 5-chloromethane fundamental mode Schiff is synthesized
1 is added in 100mL three-necked flask; 2-O-Phenylene Diamine (10mmol); add 30mL dehydrated 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 anhydrous diethyl ether washing (5 × 20mL), vacuum-drying, obtains, without the white pressed powder of colour cast, obtaining the cyclohexanediamine hydrochloride of monolateral protection.
The o-phenylendiamine dihydrochloride (5mmol) of monolateral protection is added respectively in 250mL three-necked flask; 25mL dehydrated alcohol and 25mL anhydrous diethyl ether; stirring at room temperature 10 minutes. get salicylic aldehyde (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 5-chloromethyl salicylaldehyde and be dissolved in 25mL methylene dichloride, drip 30min with constant pressure funnel to drip, continuing stirring 2 hours. after removing 4A molecular sieve, with dichloromethane extraction, rotary evaporation falls methylene dichloride, obtain red-purple solid, be 5-chloromethane fundamental mode Schiff.
(4) preparation of third generation ion liquid functionalization polyamidoamine dendrimer load 5-methylene radical Schiff
Third generation polyamidoamine dendrimer grafting imidazolium compounds G3.0(1mmol by synthesis) and 5-chloromethane fundamental mode Schiff (16mmol) of O-Phenylene Diamine of containing of above-mentioned synthesis be placed in 100mL flask, add 50mL tetrahydrofuran (THF) (THF), back flow reaction 48h, rotary evaporation removing THF after reaction, 50mL anhydrous alcohol solution is added in system, slowly be warming up to 80 DEG C after vigorous stirring 1h, continue reaction 5h.Be cooled to room temperature, filter and wash with deionized water, 40 DEG C of vacuum-dryings, obtaining pale yellow powder shape solid, be the Schiff of third generation ion liquid functionalization polyamidoamine dendrimer load.
Embodiment 6
(1) synthesis of third generation polyamidoamine dendrimer grafting imidazolium compounds
The synthesis of third generation polyamidoamine dendrimer grafting imidazolium compounds G3.0 is with embodiment 3
(2) 5-chloromethyl-3-cresotinic acid aldehyde is synthesized
The synthesis of 5-chloromethyl-3-cresotinic acid aldehyde is with embodiment 4.
(3) 5-chloromethyl-3-methyl-3 ', the synthesis of 5 '-dimethyl Schiff
1 is added in 100mL three-necked flask; 2-quadrol (10mmol); add 30mL dehydrated 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 anhydrous diethyl 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-necked flask; 25mL dehydrated alcohol and 25mL anhydrous diethyl ether; stirring at room temperature 10 minutes. get 3; 5-dimethyl salicylic aldehyde (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 methylene dichloride, drip 30min with constant pressure funnel to drip, continue stirring 2 hours. after removing 4A molecular sieve, with dichloromethane extraction, rotary evaporation falls methylene dichloride, obtain red-purple solid, be 3-methyl-3 ', 5 '-dimethyl-5-chloromethane fundamental mode Schiff.
(4) third generation ion liquid functionalization polyamidoamine dendrimer load 5-methylene radical-3-methyl-3 ', the preparation of 5 '-dimethyl-5-chloromethane fundamental mode Schiff
Third generation polyamidoamine dendrimer grafting imidazolium compounds G3.0(1mmol by synthesis) and above-mentioned synthesis contain the 5-methylene radical-3-methyl-3 of quadrol ', 5 '-methyl-5-chloro methyl type Schiff (16mmol) is placed in 100mL flask, add 50mL tetrahydrofuran (THF) (THF), back flow reaction 48h, rotary evaporation removing THF after reaction, in system, add 50mL anhydrous alcohol solution, after vigorous stirring 1h, be slowly warming up to 80 DEG C, continue reaction 5h.Be cooled to room temperature, filter and wash with deionized water, 40 DEG C of vacuum-dryings, obtaining pale yellow powder shape solid, be the 5-methylene radical-3-methyl-3 of third generation ion liquid functionalization polyamidoamine dendrimer load ', 5 '-dimethyl-5-chloromethane fundamental mode Schiff.
Embodiment 7
By the Schiff solid abrasive of the polyamidoamine dendrimer load of first-generation ion liquid functionalization obtained for embodiment 1, sieve, get 40 ~ 60 orders, think that 2mg/ props up, 4mg/ props up, 6mg/ props up and 8mg/ props up in interpolation binary compound filter candle respectively, make an addition near pipe tobacco end position.Cigarette sample is after temperature humidity balance, resistance to suction and weight screening, cigarette smoking is carried out according to GB/T16450-2004 with R200H type disk type smoking machine, in main flume grain phase composition, 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 body inductance coupling-mass spectrum (ICP-MS method) analytical method, carries out analyzing and testing to the element such as heavy metal Cd, Pb and As that two portions are collected in sample respectively.Carry out the controlled trial of blank cigarette sample simultaneously.Test cigarette with contrast the heavy metal Cd of cigarette, the reduced rate of Pb, As and the load of polyamidoamine dendrimer the addition of Schiff sorbent material relevant: (1) is when addition props up with 2mg/ respectively, coke tar in cigarette declines 5.2%, and the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 16.5%, 9.2% and 10.3%; (2) when sorbent material props up with 4mg/ respectively, coke tar in cigarette declines 12.3%, and the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 25.3%, 16.7% and 20.1%; (3) when sorbent material props up with 6mg/ respectively, coke tar in cigarette declines 20.5%, and the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 35.5%, 23.1% and 24.3%; (4) when sorbent material props up with 8mg/ respectively, coke tar in cigarette declines 25.6%, and the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 40.8%, 27.6% and 30.5%.
Embodiment 8
By the polyamidoamine dendrimer load Schiff solid abrasive of s-generation ion liquid functionalization obtained for embodiment 2, sieve, get 40 ~ 60 orders, think that 2mg/ props up, 4mg/ props up, 6mg/ props up and 8mg/ props up in interpolation binary compound filter candle respectively, make an addition near pipe tobacco end position.Cigarette sample, after temperature humidity balance, resistance to suction and weight screening, carries out cigarette smoking with R200H type disk type smoking machine according to GB/T16450-2004, and in main flume grain phase composition, the Collection and analysis of heavy metal adopts the method for embodiment 14.Carry out the controlled trial of blank cigarette sample simultaneously.Test cigarette with contrast the heavy metal Cd of cigarette, the reduced rate of Pb, As and the load of polyamidoamine dendrimer the addition of Schiff sorbent material relevant: (1) is when addition props up with 2mg/ respectively, coke tar in cigarette declines 4.5%, and the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 12.4%, 6.4% and 9.6%; (2) when sorbent material props up with 4mg/ respectively, coke tar in cigarette declines 10.6%, and the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 20.8%, 13.7% and 15.2%; (3) when sorbent material props up with 6mg/ respectively, coke tar in cigarette declines 22.6%, and the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 30.4%, 22.5% and 23.8%; (4) when sorbent material props up with 8mg/ respectively, coke tar in cigarette declines 28.7%, and the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 36.1%, 25.1% and 27.2%.
Embodiment 9
By the Schiff solid abrasive of the third generation (G3.0) ion liquid functionalization polyamidoamine dendrimer load obtained for embodiment 3, sieve, get 40 ~ 60 orders, think that 2mg/ props up, 4mg/ props up, 6mg/ props up and 8mg/ props up in interpolation binary compound filter candle respectively, make an addition near pipe tobacco end position.Cigarette sample, after temperature humidity balance, resistance to suction and weight screening, carries out cigarette smoking with R200H type disk type smoking machine according to GB/T16450-2004, and in main flume grain phase composition, the Collection and analysis of heavy metal adopts the method for embodiment 14.Carry out the controlled trial of blank cigarette sample simultaneously.Test cigarette with contrast the heavy metal Cd of cigarette, the reduced rate of Pb, As and the load of polyamidoamine dendrimer the addition of Schiff sorbent material relevant: (1) is when addition props up with 2mg/ respectively, coke tar in cigarette declines 4.9%, and the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 9.2%, 4.6% and 8.9%; (2) when sorbent material props up with 4mg/ respectively, coke tar in cigarette declines 11.3%, and the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 18.5%, 12.1% and 13.4%; (3) when sorbent material props up with 6mg/ respectively, coke tar in cigarette declines 18.9%, and the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 23.2%, 16.8% and 17.3%; (4) when sorbent material props up with 8mg/ respectively, coke tar in cigarette declines 21.6%, and the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 25.8%, 19.5% and 20.1%.
Embodiment 10
By the Schiff solid abrasive of the s-generation (G2.0) ion liquid functionalization polyamidoamine dendrimer load obtained for embodiment 4, sieve, get 40 ~ 60 orders, think that 2mg/ props up, 4mg/ props up, 6mg/ props up and 8mg/ props up in interpolation binary compound filter candle respectively, make an addition near pipe tobacco end position.Cigarette sample, after temperature humidity balance, resistance to suction and weight screening, carries out cigarette smoking with R200H type disk type smoking machine according to GB/T16450-2004, and in main flume grain phase composition, the Collection and analysis of heavy metal adopts the method for embodiment 14.Carry out the controlled trial of blank cigarette sample simultaneously.Test cigarette with contrast the heavy metal Cd of cigarette, the reduced rate of Pb, As and the load of polyamidoamine dendrimer the addition of Schiff sorbent material relevant: (1) is when addition props up with 2mg/ respectively, coke tar in cigarette declines 5.7%, and the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 11.5%, 7.2% and 9.3%; (2) when sorbent material props up with 4mg/ respectively, coke tar in cigarette declines 12.3%, and the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 21.7%, 14.2% and 15.6%; (3) when sorbent material props up with 6mg/ respectively, coke tar in cigarette declines 23.1%, and the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 32.6%, 22.1% and 20.9%; (4) when sorbent material props up with 8mg/ respectively, coke tar in cigarette declines 30.8%, and the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 35.7%, 26.3% and 29.1%.
Embodiment 11
By the Schiff solid abrasive of third generation ion liquid functionalization polyamidoamine dendrimer load obtained for embodiment 5, sieve, get 40 ~ 60 orders, think that 2mg/ props up, 4mg/ props up, 6mg/ props up and 8mg/ props up in interpolation binary compound filter candle respectively, make an addition near pipe tobacco end position.Cigarette sample, after temperature humidity balance, resistance to suction and weight screening, carries out cigarette smoking with R200H type disk type smoking machine according to GB/T16450-2004, and in main flume grain phase composition, the Collection and analysis of heavy metal adopts the method for embodiment 14.Carry out the controlled trial of blank cigarette sample simultaneously.Test cigarette with contrast the heavy metal Cd of cigarette, the reduced rate of Pb, As and the load of polyamidoamine dendrimer the addition of Schiff sorbent material relevant: (1) is when addition props up with 2mg/ respectively, coke tar in cigarette declines 5.7%, and the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 12.3%, 6.9% and 10.6%; (2) when sorbent material props up with 4mg/ respectively, coke tar in cigarette declines 15.1%, and the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 23.5%, 12.6% and 18.1%; (3) when sorbent material props up with 6mg/ respectively, coke tar in cigarette declines 20.5%, and the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 28.1%, 18.8% and 23.1%; (4) when sorbent material props up with 8mg/ respectively, coke tar in cigarette declines 29.5%, and the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 33.6%, 24.7% and 25.1%.
Embodiment 12
By the Schiff solid abrasive of third generation ion liquid functionalization polyamidoamine dendrimer load obtained for embodiment 6, sieve, get 40 ~ 60 orders, think that 2mg/ props up, 4mg/ props up, 6mg/ props up and 8mg/ props up in interpolation binary compound filter candle respectively, make an addition near pipe tobacco end position.Cigarette sample, after temperature humidity balance, resistance to suction and weight screening, carries out cigarette smoking with R200H type disk type smoking machine according to GB/T16450-2004, and in main flume grain phase composition, the Collection and analysis of heavy metal adopts the method for embodiment 14.Carry out the controlled trial of blank cigarette sample simultaneously.Test cigarette with contrast the heavy metal Cd of cigarette, the reduced rate of Pb, As and the load of polyamidoamine dendrimer the addition of Schiff sorbent material relevant: (1) is when addition props up with 2mg/ respectively, coke tar in cigarette declines 5.3%, and the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 10.7%, 6.2% and 10.9%; (2) when sorbent material props up with 4mg/ respectively, coke tar in cigarette declines 13.9%, and the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 22.1%, 15.2% and 17.9%; (3) when sorbent material props up with 6mg/ respectively, coke tar in cigarette declines 21.6%, and the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 28.1%, 19.2% and 20.5%; (4) when sorbent material props up with 8mg/ respectively, coke tar in cigarette declines 26.3%, and the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 29.7%, 20.6% and 25.8%.
Claims (11)
1. an ion liquid functionalization polyamidoamine dendrimer load Schiff compound, it is characterized in that, the compound with formula 1 structure obtained by the Schiff that the N alkylated reaction grafting of imidazole ring has formula 2 structure by ion liquid functionalization polyamidoamine dendrimer;
Wherein,
R is
a kind of in substituted radical;
M is the Schiff number of grafting;
R
1, R
2and R
3be selected from hydrogen atom, methyl or the tertiary butyl a kind of independently of one another;
Described ion liquid functionalization polyamidoamine dendrimer comprises G1, G2 or G3, wherein,
G1 is
G2 is
G3 is
2. ion liquid functionalization polyamidoamine dendrimer load Schiff compound as claimed in claim 1, is characterized in that, described R
1and R
2for identical substituting group.
3. ion liquid functionalization polyamidoamine dendrimer load Schiff compound as claimed in claim 1, it is characterized in that, m is 4 or 8 or 16.
4. the application of the ion liquid functionalization polyamidoamine dendrimer load Schiff compound as described in any one of right 1 ~ 3, it is characterized in that, described ion liquid functionalization polyamidoamine dendrimer load Schiff compound is added in cigarette filter rod as sorbent material the burst size being applied to and reducing heavy metal and tar in cigarette mainstream flue gas simultaneously.
5. apply as claimed in claim 4, it is characterized in that, the described addition of ion liquid functionalization polyamidoamine dendrimer load Schiff compound in cigarette filter rod is that 1 ~ 10mg/ props up.
6. apply as claimed in claim 5, it is characterized in that, the described addition of ion liquid functionalization polyamidoamine dendrimer load Schiff compound in cigarette filter rod is that 3 ~ 8mg/ props up.
7. apply as claimed in claim 4, it is characterized in that, described ion liquid functionalization polyamidoamine dendrimer load 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.
8. the preparation method of the ion liquid functionalization polyamidoamine dendrimer load Schiff compound as described in any one of right 1 ~ 3, it is characterized in that, first is core with quadrol, branch is obtained after repeatedly carrying out the amidate action of Michael addition reaction and ester by quadrol and methyl acrylate, and by the amidate action of ester at gained branch terminal graft 1-(3-amine propyl group) imidazoles, again by the Schiff of N alkylated reaction grafting formula 2 structure of imidazole ring, to obtain final product.
9. preparation method as claimed in claim 8, it is characterized in that, described Schiff first carries out the condensation reaction of amine aldehyde with 3, the 5-disubstituted salicylic aldehydes with formula 4 structure by diamines, then carries out the condensation reaction of amine aldehyde with the 5-chloromethyl-3-substituting group salicylic aldehyde with formula 3 structure and obtain; Described diamines comprises cyclohexanediamine, quadrol or O-Phenylene Diamine;
R
1, R
2and R
3be selected from hydrogen atom, methyl or the tertiary butyl a kind of independently of one another.
10. preparation method as claimed in claim 9, is characterized in that, described R
1and R
2for identical substituting group.
11. preparation methods as claimed in claim 8, it is characterized in that, first be obtained by reacting G0.5 by quadrol and methyl acrylate with mol ratio 1:4, G0.5 and 1-(3-amine propyl group) imidazoles reacts with mol ratio 1:4, obtain G1, G1 and Schiff, with mol ratio 1:4 reaction, obtain the first ion liquid functionalization polyamidoamine dendrimer load Schiff compound; Or be obtained by reacting G1.5 by G1 and methyl acrylate with mol ratio 1:8 further, G1.5 and 1-(3-amine propyl group) imidazoles reacts with mol ratio 1:8, obtain G2, G2 and Schiff, with mol ratio 1:8 reaction, obtain the second ion liquid functionalization polyamidoamine dendrimer load Schiff compound; Or be obtained by reacting G2.5 by G2 and methyl acrylate with mol ratio 1:16 further again, G2.5 and 1-(3-amine propyl group) imidazoles reacts with mol ratio 1:16, obtain G3, G3 and Schiff, with mol ratio 1:16 reaction, obtain the third ion liquid functionalization polyamidoamine dendrimer load Schiff compound.
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