CN103524753A - Ionic liquid functionalized polyamide-amine type dendritic macromolecule loaded Schiff base compound, and preparation method and application thereof - Google Patents
Ionic liquid functionalized polyamide-amine type dendritic macromolecule loaded Schiff base compound, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an ionic liquid functionalized polyamide-amine type dendritic macromolecule loaded Schiff base compound, and a preparation method and application thereof. The preparation method comprises the following steps: repeatedly performing Micheal addition reaction and ester amidation reaction on ethanediamine serving as a core and methyl acrylate to obtain a branch; grafting 1-(3-aminopropyl)imidazole at the tail end of the obtained branch through ester amidation reaction; and grafting Schiff base through N alkylation reaction of an imidazole ring to obtain the ionic liquid functionalized polyamide-amine type dendritic macromolecule loaded Schiff base compound. The prepared ionic liquid functionalized polyamide-amine type dendritic macromolecule loaded Schiff base compound has the characteristics of large adsorption capacity and strong adsorbability on heavy metal and tar of cigarette smoke; and a small amount of the ionic liquid functionalized polyamide-amine type dendritic macromolecule loaded Schiff base compound serving as an adsorbent is added into a cigarette filter stick, so that the release amount of the heavy metal and the release amount of the tar of the main stream smoke of the cigarette can be reduced effectively and simultaneously.
Description
Technical field
The present invention relates to a kind of ion liquid functionalization polyamide-amide type dendrimer load Schiff alkali cpd and its preparation method and application, belong to new cigarette heavy metal polymer adsorbing material field.
Background technology
In tobacco and tobacco product, contain the heavy metals such as lead (Pb), arsenic (As), cadmium (Cd), chromium (Cr), mercury (Hg).In cigarette smoking process, heavy metal and compound thereof can may be inhaled into as the form of flue gas aerosol or metal oxide human body and easily enrichment and produce harm [Chen, Q-H. etc. in human body, Studies of Trace Elements and Health, 2005,22,47-49].There are some researches show, smoking male sex blood cadmium concentration is obviously than non-smoker high [Xin Nan etc., Chinese Medicine biotechnology, 2009,4 (5): 390].In the processing process of cigarette filter, add proper amount of active carbon, the filter tip that adds gac is respectively 4.26,3.58 and 1.62 times of [Liu Ruoman etc. of former cellulose acetate filter tip to the adsorption effect of Cd, Ni and As, environment and health magazine, 1991,16 (4): 204], adsorption effect significantly strengthens, because the selection adsorptive power of gac is not strong, in the filter tip stick of Virginian-type cigarette, adding gac can bring certain negative impact to cigarette odor-absorbing, thereby seldom adopts.J.W. lesser calorie draws dimension to wait to have invented a kind of cigarette filter that [J.W. lesser calorie draws dimension etc., Chinese patent CN101043826A], in its strainer, contain the chitosan mutually crosslinked with glutaraldehyde and with oxalic dialdehyde mutually crosslinked chitosan make the porous resin material of high surface-area/mass ratio, alternative aldehyde, prussic acid, carbonyl compound and the heavy metal etc. of removing in cigarette smoke, but this class material affects cigarette odor-absorbing owing to can reducing 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.Zhou Guojun etc. join triacetin three esters by a kind of in Chlorophyll Cu and CHLOROPHYLLINE sodium or two kinds, spraying is 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 esters substantially, exist and add difficulty and affect the problems such as wire-beam forming, and green plain copper itself is exactly a kind of complex compound, to heavy metal, complex ability is limited again.
Yet utilize ionic liquid functional group and Schiff alkali to be incorporated into the sorbing material of simultaneously making Adsorption of Heavy Metals and tar in dendrimer simultaneously, have no so far the bibliographical information of this respect.
Summary of the invention
First object of the present invention is to be to provide a kind of compound with regular structure, height cladodification, and has the ion liquid functionalization polyamide-amide type dendrimer load Schiff alkali cpd of heavy metal and tar function in active adsorption cigarette smoke simultaneously.
Second object of the present invention is the application that is to provide the polyamide-amide type dendrimer load Schiff alkali cpd of described ion liquid functionalization, using it as sorbent material, interpolation, on a small quantity in cigarette filter rod, can reduce heavy metal and tar content in cigarette smoke effectively simultaneously.
The 3rd object of the present invention is the preparation method who is to provide a kind of described ion liquid functionalization polyamide-amide type dendrimer load Schiff alkali cpd, the method can strictly be controlled molecular structure of compounds, and preparation process is simple, can suitability for industrialized production.
The present invention also provides a kind of ion liquid functionalization polyamide-amide type dendrimer load Schiff alkali cpd, by the grafting of ion liquid functionalization polyamide-amide type dendrimer, has the compound with formula 1 structure that the Schiff alkali of formula 2 structures obtains;
Wherein,
R is
or
a kind of in substituted radical;
M is the Schiff alkali number of grafting;
R
1, R
2and R
3be selected from independently of one another in hydrogen atom, methyl or the tertiary butyl a kind of;
Described ion liquid functionalization polyamide-amide type dendrimer comprises G1, G2 or G3, and wherein, G1 is
G2 is
G3 is
Preferred ion liquid functionalization polyamide-amide type dendrimer load Schiff alkali cpd, R
1and R
2for identical substituting group.
Ion liquid functionalization polyamide-amide type dendrimer load Schiff alkali cpd more preferably, m is 4 or 8 or 16; When described ion liquid functionalization polyamide-amide type dendrimer is G1, G2 or G3, corresponding m is 4,8 or 16.
The present invention also provides a kind of application of described ion liquid functionalization polyamide-amide type dendrimer load Schiff alkali cpd, and this application is using described ion liquid functionalization polyamide-amide type dendrimer load Schiff alkali cpd as sorbent material, to be added on the burst size that is applied to simultaneously reduce heavy metal and tar in cigarette mainstream flue gas in cigarette filter rod.
The addition of described ion liquid functionalization polyamide-amide type dendrimer load Schiff alkali cpd in cigarette filter rod is that 1～10mg/ props up; Being preferably 3～8mg/ props up.
Described ion liquid functionalization polyamide-amide type dendrimer load Schiff alkali cpd is added on the close pipe tobacco section of cigarette binary compound filter candle or the interlude of Three-element composite filter core.
The present invention also provides a kind of preparation method of described ion liquid functionalization polyamide-amide type dendrimer load Schiff alkali cpd, this preparation method first be take quadrol as core, by quadrol and methyl acrylate, repeatedly carried out obtaining branch after the amidate action of Micheal addition reaction and ester, and the amidate action that passes through ester is at gained branch end grafting 1-(3-amine propyl group) imidazoles, pass through again the Schiff alkali of N alkylated reaction grafting formula 2 structures of imidazoles, obtain.
Described Schiff alkali by diamines first with there are 3 of formula 4 structures, the disubstituted salicylic aldehyde of 5-carries out the condensation reaction of amine aldehyde, then carries out the condensation reaction of amine aldehyde with 5-chloromethyl-3-substituting group salicylic aldehyde with formula 3 structures and obtain; Described diamines comprises cyclohexanediamine, quadrol or O-Phenylene Diamine;
R
1, R
2and R
3be selected from independently of one another in hydrogen atom, methyl or the tertiary butyl a kind of.
Described R
1and R
2be preferably identical substituting group.
Preferred preparation method is first reacted and obtains G0.5 with mol ratio 1:4 with methyl acrylate by quadrol, G0.5 and 1-(3-amine propyl group) imidazoles reacts with mol ratio 1:4, obtain G1, G1 and Schiff alkali, with mol ratio 1:4 reaction, obtain the first ion liquid functionalization polyamide-amide type dendrimer load Schiff alkali cpd; Or further by G1, react and obtain G1.5 with mol ratio 1:8 with methyl acrylate, G1.5 and 1-(3-amine propyl group) imidazoles reacts with mol ratio 1:8, obtain G2, G2 and Schiff alkali, with mol ratio 1:8 reaction, obtain the second ion liquid functionalization polyamide-amide type dendrimer load Schiff alkali cpd; Or further by G2, react and obtain G2.5 with mol ratio 1:16 with methyl acrylate again, G2.5 and 1-(3-amine propyl group) imidazoles reacts with mol ratio 1:16, obtain G3, G3 and Schiff alkali, with mol ratio 1:16 reaction, obtain the third ion liquid functionalization polyamide-amide type dendrimer load Schiff alkali cpd.
The preparation of ion liquid functionalization polyamide-amide type dendrimer load Schiff alkali cpd of the present invention comprises the following steps:
(1) the ion liquid functionalization polyamide-amide type dendrimer compound of synthetic different algebraically:
First by quadrol and methyl acrylate, with mol ratio 1:4, there is Micheal addition reaction and obtain G0.5, with mol ratio 1:4, there is the amidate action of ester in G0.5 and 1-(3-amine propyl group) imidazoles, obtain G1, obtain the first ion liquid functionalization polyamide-amide type dendrimer;
Or further by G1 and methyl acrylate, with mol ratio 1:8, there is Micheal addition reaction and obtain G1.5, with mol ratio 1:8, there is the amidate action of ester in G1.5 and 1-(3-amine propyl group) imidazoles, obtain G2, obtain the second ion liquid functionalization polyamide-amide type dendrimer;
Or further by G2 and methyl acrylate, with mol ratio 1:16, there is Micheal addition reaction again and obtain G2.5, with mol ratio 1:16, there is the amidate action of ester in G2.5 and 1-(3-amine propyl group) imidazoles, obtain G3, obtain the third ion liquid functionalization polyamide-amide type dendrimer;
Synthetic route is as follows:
(2) synthetic ion liquid functionalization polyamide-amide type dendrimer load Schiff alkali cpd:
A, synthetic 5-chloromethyl-3-substituted salicylic aldehydes:
First the 2-fortified phenol of being processed by Grignard reagent and paraformaldehyde back flow reaction 3h in triethylamine, preparation 3-substituted salicylic aldehydes, then the 3-substituted salicylic aldehydes of preparing of take is raw material, under Tetrabutyl amonium bromide catalysis, hydrochloric acid soln by 3-substituted salicylic aldehydes and paraformaldehyde reacts 72h at 40 ℃, 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, synthetic Schiff alkali:
Add hydrochloric acid by after the amido protecting of diamines one end, first, with 3, the disubstituted bigcatkin willow of 5-is amine aldehyde condensation reaction 4h at room temperature, then with 5-chloromethyl-3-substituting group salicylic aldehyde amine aldehyde condensation reaction 4h, prepare and contain 5-chloromethane fundamental mode Schiff alkali, synthetic route is as follows:
R
1and R
2be selected from independently of one another in hydrogen atom, methyl or the tertiary butyl a kind of;
R is
or
a kind of in substituted radical;
Described diamines comprises cyclohexanediamine, quadrol or O-Phenylene Diamine;
(3) the Schiff alkali cpd of synthetic ion liquid functionalization polyamide-amide type dendrimer load:
With mol ratio 1:4,1:8,1:16, be there is to N alkylated reaction with the Schiff alkali that step (2) makes respectively in the resulting G1 of step (1), G2 and G3, obtain respectively the compound of three kinds of ion liquid functionalization polyamide-amide type dendrimer load Schiff alkali:
Synthetic route is as follows:
Beneficial effect of the present invention: the present invention has synthesized the double-Schiff base containing chloromethyl first, Schiff alkali is introduced to polyamine-amine type dendrimer by ionic liquid functional group, obtain ion liquid functionalization polyamide-amide type dendrimer load Schiff alkali cpd, and using it as sorbent material, be added in cigarette filter rod and can adsorb heavy metal and the tar in main flume effectively simultaneously.The synthetic ion liquid functionalization polyamide-amide type dendrimer load Schiff alkali cpd of the present invention is a kind of highly branched, compound with regular structure, and the dendrimer that molecular size is controlled, particularly branch end has been introduced the Schiff base groups 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, between these supplied for electronics, play the ability of certain combination heavy metal, also further play the effect of assisting Schiff alkali chelating heavy metal, make such ion liquid functionalization polyamide-amide type dendrimer load Schiff alkali cpd large especially to the adsorptive capacity of the heavy metal in flue gas, can in the situation that consumption is little, effectively reduce the burst size of heavy metal in main flume, be specially adapted to Cd in flue gas, the absorption of Pb and As, and beyond thought is that ion liquid functionalization polyamide-amide type dendrimer load Schiff alkali cpd of the present invention is simultaneously very large to the coal-tar middle oil adsorptive capacity of flue gas, experimental results demonstrate: ion liquid functionalization polyamide-amide type dendrimer load Schiff alkali cpd of the present invention is propped up and is added in cigarette with 8mg/, and 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 polyamide-amide type dendrimer load Schiff alkali cpd is macromole solids, and good stability use safety, and preparation process is simple, is easy to suitability for industrialized production.
Accompanying drawing explanation
[Fig. 1] is G0.5, the G1 of embodiment 1 preparation and the infrared comparison diagram of G1 load Schiff alkali: a is G0.5, and b is G1.0, and c is ion liquid functionalization polyamide-amide type dendrimer grafting Shiff alkali cpd.
Embodiment
Following examples are intended to further illustrate the present invention, rather than limit the scope of the invention.
Embodiment 1
(1) first-generation polyamide-amide type dendrimer grafting imidazolium compounds G1.0's is synthetic
At 25 ℃, 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 reduced pressure at 70 ℃ rotary evaporation, when solvent is spin-dried for, is cooled to room temperature, in system, add dissolve with methanol, the rotary evaporation that reduces pressure at 70 ℃ again, the product obtaining afterwards in triplicate, 50 ℃ of vacuum-dryings, obtained 0.5 generation (G0.5) macromole, this macromole end You Sige ester group functional group.0.5G amine dendrimer (0.202g, 2mmol ester group) is dissolved in anhydrous methanol (20mL), at 0 ℃, slowly drips the methanol solution of 1-(3-amine propyl group) imidazoles (0.250g, 2mmol), reaction 1h.Then, at 40 ℃, react 72h.After having reacted, rotary evaporation is that end is the amine dendrimer G1.0 of imidazoles except desolventizing obtains yellow thick liquid.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) 5-chloromethyl-3-tertiary butyl salicylic aldehyde is synthetic
In 500mL there-necked flask, add 0.10mol (2.4g) magnesium powder and 50mL anhydrous diethyl ether, under agitation in 1h, be added dropwise to 0.10mol (9mL) monobromethane.Temperature rising reflux 1h slowly after dropwising returns to room temperature (a small amount of magnesium powder reaction) after magnesium powder fully reacts, and obtains Grignard reagent CH
3cH
2mgBr.0.10mol (15.5mL) 2-TBP is dissolved in 60mL tetrahydrofuran (THF), at room temperature in 1h, is added dropwise in the Grignard reagent of firm preparation.After there are a large amount of white precipitates, add 200mL hexanaphthene or benzene.Slowly rising temperature of reaction, steams and removes about 100mL solvent, and lower boiling solvent in system is distilled out of as best one can.Add again into 50mL hexanaphthene or benzene, 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, standing rear separatory, with after twice of appropriate normal hexane (60～90 ℃ of boiling ranges) aqueous phase extracted, merges organic phase, uses anhydrous magnesium sulfate drying.Filter distillation and remove after organic solvent, with column chromatography (normal hexane: ethyl acetate=50:1) separation, obtains 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)。
In 100mL round-bottomed flask, add by above-mentioned synthetic 3-tertiary butyl salicylic aldehyde (15.2mmol (2.7g)), 33.3mmol (1.0g) paraformaldehyde, 1.46mmol (0.47g) Tetrabutyl amonium bromide and 11mL concentrated hydrochloric acid, vigorous stirring 72h at 40 ℃, during supplement three concentrated hydrochloric acid 5mL.After reaction finishes, with the extraction of 3 * 15mL anhydrous diethyl ether, obtain organic phase, use successively sodium hydrogen carbonate solution and the saturated NaCl solution washing of 4 * 10mL of 4 * 10mL5%, anhydrous magnesium sulfate drying.After filtering, remove desolventizing and obtain 3.4g yellow solid product 5-chloromethyl-3-tertiary butyl salicylic aldehyde.
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) synthetic 5-chloromethyl-3-tertiary butyl-3 ', 5 '-di-t-butyl Schiff alkali
Cyclohexanediamine (11.2mmol) is dissolved in to chloroform (20mL), slowly adds hydrochloric acid (11.2mmol) diethyl ether solution (2mol/L) at 0 ℃, 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.The anhydrous methylene chloride mixing solutions that 20mL is mixed with to 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), obtains pale yellow powder shape solid, i.e. 5-chloromethyl-3-tertiary butyl-3 ', 5 '-di-t-butyl Schiff alkali.Calc.for?C
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) first-generation ion liquid functionalization polyamide-amide type dendrimer load 5-methylene radical-3-tertiary butyl-3 ', the preparation of 5 '-di-t-butyl Schiff alkali
By synthetic first-generation polyamide-amide type dendrimer grafting imidazolium compounds G1.0(1mmol) and the above-mentioned synthetic 5-chloromethyl-3-tertiary butyl-3 ' containing cyclohexanediamine, 5 '-di-t-butyl Schiff alkali (4mmol) is placed in 100mL flask, add 50mL tetrahydrofuran (THF) (THF), back flow reaction 48h, after reaction, rotary evaporation is removed THF, in system, add 50mL anhydrous alcohol solution, after vigorous stirring 1h, be slowly warming up to 80 ℃, continue reaction 5h.Be cooled to room temperature, filter and wash with deionized water, 40 ℃ of vacuum-dryings, obtain pale yellow powder shape solid, be 5-methylene radical-3-tertiary butyl-3 ' of first-generation ion liquid functionalization polyamide-amide type dendrimer load, 5 '-di-t-butyl Schiff alkali, first-generation polyamide-amide type dendrimer G1.0 and load 5-methylene radical-3-tertiary butyl-3 ' thereof to preparation, 5 '-di-t-butyl Schiff alkali has carried out infrared spectrum characterization, see accompanying drawing 1, accompanying drawing 1(b) 3292,1731 and 620cm in
-1wave number band is the infrared signature absorption peak of imidazoles, proves that imidazoles is successfully distributed to polyamide-amide type dendrimer surface as end-capping reagent; Accompanying drawing 1(c) 1630 and 1614cm in
-1wave number band is the infrared signature absorption peak of Schiff alkali, and has the characteristic peak of imidazoles, proves that imidazoles and Schiff alkali are all successfully grafted on polyamide-amide type 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) s-generation polyamide-amide type dendrimer grafting imidazolium compounds G2.0's is synthetic
At 25 ℃, synthetic 1.0G dendritic macromole (2.580g, the amido of 20mmol) 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, rotary evaporation that solution is reduced pressure at 70 ℃, when solvent evaporate to dryness, be cooled to room temperature, in system, add dissolve with methanol, the rotary evaporation that again reduces pressure at 70 ℃, in triplicate.Finally, the product obtaining, 50 ℃ of vacuum-dryings, is obtained to 1.5 generations (G1.5) macromole.1.5G amine dendrimer (0.304g, 2mmol ester group) is dissolved in anhydrous methanol (20mL), at 0 ℃, slowly drips the methanol solution of 1-(3-amine propyl group) imidazoles (0.250g, 2mmol), reaction 1h.Then, at 40 ℃, react 72h.After having reacted, rotary evaporation is that end is the amine dendrimer G2.0 of imidazoles except desolventizing obtains yellow thick liquid.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) 5-chloromethyl-3-tertiary butyl salicylic aldehyde is synthetic
Synthesizing with embodiment 1 of 5-chloromethyl-3-tertiary butyl salicylic aldehyde
(3) synthetic 5-chloromethyl-3-tertiary butyl-3 ', 5 '-dimethyl Schiff alkali
Cyclohexanediamine (11.2mmol) is dissolved in to chloroform (20mL), slowly adds hydrochloric acid (11.2mmol) diethyl ether solution (2mol/L) at 0 ℃, at room temperature spend the night.Then by the protected quadrol of this single amino (8mmol) and 3; 5-bis-dimethyl salicylic aldehydes (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.The anhydrous methylene chloride mixing solutions that 20mL is mixed with to 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. 5-chloromethyl-3-tertiary butyl-3 ', 5 '-dimethyl Schiff alkali.
(4) s-generation ion liquid functionalization polyamide-amide type dendrimer load 5-methylene radical-3-tertiary butyl-3 ', the preparation of 5 '-dimethyl Schiff alkali
By synthetic s-generation polyamide-amide type dendrimer grafting imidazolium compounds G2.0(1mmol) and 5-chloromethyl-3-tertiary butyl-3 ' of above-mentioned synthetic cyclohexanediamine, 5 '-dimethyl Schiff alkali (8mmol) is placed in 100mL flask, add 50mL tetrahydrofuran (THF) (THF), back flow reaction 48h, after reaction, rotary evaporation is removed THF, in system, add 50mL anhydrous alcohol solution, after vigorous stirring 1h, be slowly warming up to 80 ℃, continue reaction 5h.Be cooled to room temperature, filter and wash with deionized water, 40 ℃ of vacuum-dryings, obtain pale yellow powder shape solid, are 5-methylene radical-3-tertiary butyl-3 ' of s-generation ion liquid functionalization polyamide-amide type dendrimer load, 5 '-dimethyl Schiff alkali.To s-generation polyamide-amide type dendrimer G2.0 and load 5-methylene radical-3-tertiary butyl-3 ' thereof of preparation, 5 '-dimethyl Schiff alkali 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 alkali infrared signature absorption peak, prove that imidazoles and Schiff alkali are all successfully grafted on polyamide-amide type 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) third generation polyamide-amide type dendrimer grafting imidazolium compounds is synthetic
At 25 ℃, synthetic 2.0G dendritic macromole (2.856g, the amido of 16mmol) 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, rotary evaporation that solution is reduced pressure at 70 ℃, when solvent evaporate to dryness, be cooled to room temperature, in system, add dissolve with methanol, the rotary evaporation that reduces pressure at 70 ℃, in triplicate.Finally, the product obtaining, 50 ℃ of vacuum-dryings, is obtained to 2.5 generations (G2.5) macromole.2.5G amine dendrimer (0.351g, 2mmol ester group) is dissolved in anhydrous methanol (20mL), at 0 ℃, slowly drips the methanol solution of 1-(3-amine propyl group) imidazoles (0.250g, 2mmol), reaction 1h.Then, at 40 ℃, react 72h.After having reacted, rotary evaporation is that end is the amine dendrimer G3.0 of imidazoles except desolventizing obtains yellow thick liquid.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) 5-chloromethyl-3-tertiary butyl salicylic aldehyde is synthetic
Synthesizing with embodiment 1 of 5-chloromethyl-3-tertiary butyl salicylic aldehyde
(3) synthetic 5-chloromethyl-3-tertiary butyl Schiff alkali
Cyclohexanediamine (11.2mmol) is dissolved in to chloroform (20mL), slowly adds hydrochloric acid (11.2mmol) diethyl ether solution (2mol/L) at 0 ℃, at room temperature spend the night.Then the protected quadrol of this single amino (8mmol) and salicylic aldehyde (8mmol) are dissolved in to 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.The anhydrous methylene chloride mixing solutions that 20mL is mixed with to 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), obtains pale yellow powder shape solid, i.e. 5-chloromethyl-3-tertiary butyl Schiff alkali.
(4) third generation ion liquid functionalization polyamide-amide type dendrimer load 5-methylene radical-3-tertiary butyl-3 ', the preparation of 5 '-dimethyl Schiff alkali
By synthetic third generation polyamide-amide type dendrimer grafting imidazolium compounds G3.0(1mmol) and above-mentioned synthetic 5-chloromethyl-3-tertiary butyl Schiff alkali (16mmol) containing cyclohexanediamine be placed in 100mL flask, add 50mL tetrahydrofuran (THF) (THF), back flow reaction 48h, after reaction, rotary evaporation is removed THF, in system, add 50mL anhydrous alcohol solution, after vigorous stirring 1h, be slowly warming up to 80 ℃, continue reaction 5h.Be cooled to room temperature, filter and wash with deionized water, 40 ℃ of vacuum-dryings, obtain pale yellow powder shape solid, are 5-methylene radical-3-tertiary butyl Schiff alkali of third generation ion liquid functionalization polyamide-amide type dendrimer load.S-generation polyamide-amide type dendrimer G2.0 and load 5-methylene radical-3-tertiary butyl Schiff alkali thereof to preparation have carried out infrared spectrum characterization, have wherein all occurred 3290,1732 and 621cm
-1imidazoles wave number band charateristic avsorption band and 1635 and 1615cm
-1schiff alkali infrared signature absorption peak, prove that imidazoles and Schiff alkali are all successfully grafted on polyamide-amide type 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) s-generation polyamide-amide type dendrimer grafting imidazolium compounds is synthetic
S-generation polyamide-amide type dendrimer grafting imidazolium compounds G2.0's is synthetic with embodiment 2
(2) synthetic 5-chloromethyl-3-cresotinic acid aldehyde
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), temperature rising reflux 1h slowly after dropwising returns to room temperature after magnesium powder fully reacts, and obtains Grignard reagent CH
3cH
2mgBr.Phenol (0.10mol) is dissolved in 60mL tetrahydrofuran (THF), at room temperature in 1h, is added dropwise in the Grignard reagent of firm preparation.After there are a large amount of white precipitates, add hexanaphthene or benzene 200mL.Slowly rising temperature of reaction, steams and removes about 100mL solvent, and lower boiling solvent in system is distilled out of as best one can.Add again into 50mL hexanaphthene or benzene, 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, standing rear separatory, organic phase is with filtering after anhydrous magnesium sulfate drying, distillation is removed after organic solvent, with column chromatography (normal hexane: ethyl acetate=50:1) separation, obtains weak yellow liquid product 3-cresotinic acid aldehyde.
In 100mL round-bottomed flask, add (15.2mmol) 3-cresotinic acid aldehyde, paraformaldehyde (1.0g), Tetrabutyl amonium bromide (1.46mmol, 0.47g) and 11mL concentrated hydrochloric acid, vigorous stirring 72h at 40 ℃, during supplement three concentrated hydrochloric acid 5mL.After reaction finishes, with the extraction of 3 * 15mL anhydrous diethyl ether, obtain organic phase, use successively sodium hydrogen carbonate solution and the saturated NaCl solution washing of 4 * 10mL of 4 * 10mL5%, anhydrous magnesium sulfate drying.After filtering, remove desolventizing and obtain yellow solid product 3-methyl-5-chloro cresotinic acid aldehyde.
(3) synthetic 5-chloromethane-3-methyl-3 ', 5 '-di-t-butyl Schiff alkali
In 100mL three-necked flask, add 1; 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; in 1 hour, dripping, there are a large amount of white precipitates in solution.Room temperature continues and continues the continuous 12h of stirring under condition, filtration under diminished pressure then, 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) that adds respectively monolateral protection in 250mL three-necked flask; 25mL dehydrated alcohol and 25mL anhydrous diethyl ether; stirring at room 10 minutes; get 3,5-di-tert-butyl salicylaldehyde (5mol), with after 50mL anhydrous alcohol solution; with constant pressure funnel, drip; add a certain amount of 4A molecular sieve to slough the water producing in condensation reaction simultaneously, stir 4 hours, it is faint yellow that solution is.Drip the triethylamine of 5mmol, stirring at room 1 hour, then get 5-chloromethane-3-methyl-3 ', 5 '-di-tert-butyl salicylaldehyde is dissolved in 25mL methylene dichloride, drips 30min drip with constant pressure funnel, continue to stir 2 hours. remove after 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 alkali.
(4) s-generation ion liquid functionalization polyamide-amide type dendrimer load 5-methylene radical-3-methyl-3 ', the preparation of 5 '-di-t-butyl Schiff alkali
By synthetic s-generation polyamide-amide type dendrimer grafting imidazolium compounds G2.0(1mmol) and 5-chloromethyl-3-methyl-3 ' of above-mentioned synthetic quadrol, 5 '-di-t-butyl Schiff alkali (8mmol) is placed in 100mL flask, add 50mL tetrahydrofuran (THF) (THF), back flow reaction 48h, after reaction, rotary evaporation is removed THF, in system, add 50mL anhydrous alcohol solution, after vigorous stirring 1h, be slowly warming up to 80 ℃, continue reaction 5h.Be cooled to room temperature, filter and wash with deionized water, 40 ℃ of vacuum-dryings, obtain pale yellow powder shape solid, are 5-methylene radical-3-tertiary butyl-3 ' of s-generation ion liquid functionalization polyamide-amide type dendrimer load, 5 '-dimethyl Schiff alkali.
Embodiment 5
(1) third generation polyamide-amide type dendrimer grafting imidazolium compounds is synthetic
Third generation polyamide-amide type dendrimer grafting imidazolium compounds G3.0's is synthetic with embodiment 3
(2) synthetic 5-chloromethyl salicylaldehyde
In 100mL round-bottomed flask, add (15.2mmol) salicylic aldehyde, paraformaldehyde (1.0g), Tetrabutyl amonium bromide (1.46mmol, 0.47g) and 11mL concentrated hydrochloric acid, vigorous stirring 72h at 40 ℃, during supplement three concentrated hydrochloric acid 5mL.After reaction finishes, with the extraction of 3 * 15mL anhydrous diethyl ether, obtain organic phase, use successively sodium hydrogen carbonate solution and the saturated NaCl solution washing of 4 * 10mL of 4 * 10mL5%, anhydrous magnesium sulfate drying.After filtering, remove desolventizing and obtain yellow solid product 5-chloromethyl salicylaldehyde.
(3) synthetic 5-chloromethane fundamental mode Schiff alkali
In 100mL three-necked flask, add 1; 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; in 1 hour, dripping, there are a large amount of white precipitates in solution.Room temperature continues and continues the continuous 12h of stirring under condition, filtration under diminished pressure then, 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) that adds respectively monolateral protection in 250mL three-necked flask; 25mL dehydrated alcohol and 25mL anhydrous diethyl ether; stirring at room 10 minutes. get salicylic aldehyde (5mol); with after 50mL anhydrous alcohol solution; with constant pressure funnel, drip; add a certain amount of 4A molecular sieve to slough the water producing in condensation reaction simultaneously, stir 4 hours, it is faint yellow that solution is.Drip the triethylamine of 5mmol, stirring at room 1 hour, then get 5-chloromethyl salicylaldehyde and be dissolved in 25mL methylene dichloride, with constant pressure funnel, dripping 30min drips, continue to stir 2 hours. remove after 4A molecular sieve, with dichloromethane extraction, rotary evaporation falls methylene dichloride, obtain red-purple solid, be 5-chloromethane fundamental mode Schiff alkali.
(4) preparation of third generation ion liquid functionalization polyamide-amide type dendrimer load 5-methylene radical Schiff alkali
By synthetic third generation polyamide-amide type dendrimer grafting imidazolium compounds G3.0(1mmol) and the above-mentioned synthetic 5-chloromethane fundamental mode Schiff alkali (16mmol) containing O-Phenylene Diamine be placed in 100mL flask, add 50mL tetrahydrofuran (THF) (THF), back flow reaction 48h, after reaction, rotary evaporation is removed THF, in system, add 50mL anhydrous alcohol solution, after vigorous stirring 1h, be slowly warming up to 80 ℃, continue reaction 5h.Be cooled to room temperature, filter and wash with deionized water, 40 ℃ of vacuum-dryings, obtain pale yellow powder shape solid, are the Schiff alkali of third generation ion liquid functionalization polyamide-amide type dendrimer load.
Embodiment 6
(1) third generation polyamide-amide type dendrimer grafting imidazolium compounds is synthetic
Third generation polyamide-amide type dendrimer grafting imidazolium compounds G3.0's is synthetic with embodiment 3
(2) synthetic 5-chloromethyl-3-cresotinic acid aldehyde
Synthesizing with embodiment 4. of 5-chloromethyl-3-cresotinic acid aldehyde
(3) 5-chloromethyl-3-methyl-3 ', 5 '-dimethyl Schiff alkali synthetic
In 100mL three-necked flask, add 1; 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; in 1 hour, dripping, there are a large amount of white precipitates in solution.Room temperature continues and continues the continuous 12h of stirring under condition, filtration under diminished pressure then, 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) that adds respectively monolateral protection in 250mL three-necked flask; 25mL dehydrated alcohol and 25mL anhydrous diethyl ether; stirring at room 10 minutes. get 3; 5-dimethyl salicylic aldehyde (5mol); with after 50mL anhydrous alcohol solution, with constant pressure funnel, drip, add a certain amount of 4A molecular sieve to slough the water producing in condensation reaction simultaneously; stir 4 hours, it is faint yellow that solution is.Drip the triethylamine of 5mmol, stirring at room 1 hour, then get 3-methyl-5-chloro cresotinic acid aldehyde and be dissolved in 25mL methylene dichloride, with constant pressure funnel, drip 30min and drip, continue to stir 2 hours. remove after 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 alkali.
(4) third generation ion liquid functionalization polyamide-amide type dendrimer load 5-methylene radical-3-methyl-3 ', the preparation of 5 '-dimethyl-5-chloromethane fundamental mode Schiff alkali
By synthetic third generation polyamide-amide type dendrimer grafting imidazolium compounds G3.0(1mmol) and the above-mentioned synthetic 5-methylene radical-3-methyl-3 ' containing quadrol, 5 '-methyl-5-chloro methyl type Schiff alkali (16mmol) is placed in 100mL flask, add 50mL tetrahydrofuran (THF) (THF), back flow reaction 48h, after reaction, rotary evaporation is removed THF, in system, add 50mL anhydrous alcohol solution, after vigorous stirring 1h, be slowly warming up to 80 ℃, continue reaction 5h.Be cooled to room temperature, filter and wash with deionized water, 40 ℃ of vacuum-dryings, obtain pale yellow powder shape solid, be 5-methylene radical-3-methyl-3 ' of third generation ion liquid functionalization polyamide-amide type dendrimer load, 5 '-dimethyl-5-chloromethane fundamental mode Schiff alkali.
Embodiment 7
The Schiff alkali solid abrasive of the polyamide-amide type dendrimer load of the first-generation ion liquid functionalization that embodiment 1 is made, sieve, get 40～60 orders, think that respectively 2mg/ props up, 4mg/ props up, 6mg/ props up and 8mg/ props up in interpolation binary compound filter candle, make an addition near pipe tobacco end position.Cigarette sample is after temperature humidity balance, resistance to suction and weight screening, with R200H type disk type smoking machine, according to GB/T16450-2004, carry out cigarette smoking, in main flume grain phase composition, heavy metal adopts Electrostatic pipe to trap, in gas phase composition, heavy metal adopts the absorption bottle of the salpeter solution that is added with 20mL10% to collect, adopt YC/T379-2010 standard method of analysis, be plasma body inductance coupling-mass spectrum (ICP-MS method) analytical method, the elements such as heavy metal Cd, Pb and As of respectively two portions being collected in sample carry out analyzing and testing.Carry out the controlled trial of blank cigarette sample simultaneously.Test cigarette is relevant with the addition of the Schiff alkali sorbent material of the contrast heavy metal Cd of cigarette, the reduced rate of Pb, As and the load of polyamide-amide type dendrimer: (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
The polyamide-amide type dendrimer load Schiff alkali solid abrasive of the s-generation ion liquid functionalization that embodiment 2 is made, sieve, get 40～60 orders, think that respectively 2mg/ props up, 4mg/ props up, 6mg/ props up and 8mg/ props up in interpolation binary compound filter candle, 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 is relevant with the addition of the Schiff alkali sorbent material of the contrast heavy metal Cd of cigarette, the reduced rate of Pb, As and the load of polyamide-amide type dendrimer: (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
The Schiff alkali solid abrasive of the third generation that embodiment 3 is made (G3.0) ion liquid functionalization polyamide-amide type dendrimer load, sieve, get 40～60 orders, think that respectively 2mg/ props up, 4mg/ props up, 6mg/ props up and 8mg/ props up in interpolation binary compound filter candle, 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 is relevant with the addition of the Schiff alkali sorbent material of the contrast heavy metal Cd of cigarette, the reduced rate of Pb, As and the load of polyamide-amide type dendrimer: (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
The Schiff alkali solid abrasive of the s-generation that embodiment 4 is made (G2.0) ion liquid functionalization polyamide-amide type dendrimer load, sieve, get 40～60 orders, think that respectively 2mg/ props up, 4mg/ props up, 6mg/ props up and 8mg/ props up in interpolation binary compound filter candle, 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 is relevant with the addition of the Schiff alkali sorbent material of the contrast heavy metal Cd of cigarette, the reduced rate of Pb, As and the load of polyamide-amide type dendrimer: (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
The Schiff alkali solid abrasive of the third generation ion liquid functionalization polyamide-amide type dendrimer load that embodiment 5 is made, sieve, get 40～60 orders, think that respectively 2mg/ props up, 4mg/ props up, 6mg/ props up and 8mg/ props up in interpolation binary compound filter candle, 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 is relevant with the addition of the Schiff alkali sorbent material of the contrast heavy metal Cd of cigarette, the reduced rate of Pb, As and the load of polyamide-amide type dendrimer: (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
The Schiff alkali solid abrasive of the third generation ion liquid functionalization polyamide-amide type dendrimer load that embodiment 6 is made, sieve, get 40～60 orders, think that respectively 2mg/ props up, 4mg/ props up, 6mg/ props up and 8mg/ props up in interpolation binary compound filter candle, 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 is relevant with the addition of the Schiff alkali sorbent material of the contrast heavy metal Cd of cigarette, the reduced rate of Pb, As and the load of polyamide-amide type dendrimer: (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 (10)
1. an ion liquid functionalization polyamide-amide type dendrimer load Schiff alkali cpd, it is characterized in that thering is by the grafting of ion liquid functionalization polyamide-amide type dendrimer the compound with formula 1 structure that the Schiff alkali of formula 2 structures obtains;
Wherein,
R is
or
a kind of in substituted radical;
M is the Schiff alkali number of grafting;
R
1, R
2and R
3be selected from independently of one another in hydrogen atom, methyl or the tertiary butyl a kind of;
Described ion liquid functionalization polyamide-amide type dendrimer comprises G1, G2 or G3, wherein,
G1 is
G2 is
G3 is
2. ion liquid functionalization polyamide-amide type dendrimer load Schiff alkali cpd as claimed in claim 1, is characterized in that, described R1 and R2 are identical substituting group.
3. ion liquid functionalization polyamide-amide type dendrimer load Schiff alkali cpd as claimed in claim 1, is characterized in that, m is 4 or 8 or 16.
4. the application of the ion liquid functionalization polyamide-amide type dendrimer load Schiff alkali cpd as described in right 1～3 any one, it is characterized in that, using described ion liquid functionalization polyamide-amide type dendrimer load Schiff alkali cpd as sorbent material, be added on the burst size that is applied to simultaneously reduce heavy metal and tar in cigarette mainstream flue gas in cigarette filter rod.
5. application as claimed in claim 4, is characterized in that, the addition of described ion liquid functionalization polyamide-amide type dendrimer load Schiff alkali cpd in cigarette filter rod is that 1～10mg/ props up.
6. application as claimed in claim 5, is characterized in that, the addition of described ion liquid functionalization polyamide-amide type dendrimer load Schiff alkali cpd in cigarette filter rod is that 3～8mg/ props up.
7. application as claimed in claim 4, is characterized in that, described ion liquid functionalization polyamide-amide type dendrimer load Schiff alkali cpd 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 polyamide-amide type dendrimer load Schiff alkali cpd as described in right 1～3 any one, it is characterized in that, first take quadrol as core, by quadrol and methyl acrylate, repeatedly carried out obtaining branch after the amidate action of Micheal addition reaction and ester, and the amidate action that passes through ester is at gained branch end grafting 1-(3-amine propyl group) imidazoles, pass through again the Schiff alkali of N alkylated reaction grafting formula 2 structures of imidazole ring, obtain.
9. preparation method as claimed in claim 8, it is characterized in that, described Schiff alkali by diamines first with there are 3 of formula 4 structures, the disubstituted salicylic aldehyde of 5-carries out the condensation reaction of amine aldehyde, then carries out the condensation reaction of amine aldehyde with 5-chloromethyl-3-substituting group salicylic aldehyde with formula 3 structures and obtain; Described diamines comprises cyclohexanediamine, quadrol or O-Phenylene Diamine;
R
1, R
2and R
3be selected from independently of one another in hydrogen atom, methyl or the tertiary butyl a kind of.
10. preparation method as claimed in claim 9, is characterized in that, described R
1and R
2for identical substituting group.11, preparation method as claimed in claim 8, it is characterized in that, first by quadrol, react and obtain G0.5 with mol ratio 1:4 with methyl acrylate, G0.5 and 1-(3-amine propyl group) imidazoles reacts with mol ratio 1:4, obtain G1, G1 and Schiff alkali, with mol ratio 1:4 reaction, obtain the first ion liquid functionalization polyamide-amide type dendrimer load Schiff alkali cpd; Or further by G1, react and obtain G1.5 with mol ratio 1:8 with methyl acrylate, G1.5 and 1-(3-amine propyl group) imidazoles reacts with mol ratio 1:8, obtain G2, G2 and Schiff alkali, with mol ratio 1:8 reaction, obtain the second ion liquid functionalization polyamide-amide type dendrimer load Schiff alkali cpd; Or further by G2, react and obtain G2.5 with mol ratio 1:16 with methyl acrylate again, G2.5 and 1-(3-amine propyl group) imidazoles reacts with mol ratio 1:16, obtain G3, G3 and Schiff alkali, with mol ratio 1:16 reaction, obtain the third ion liquid functionalization polyamide-amide type dendrimer load Schiff alkali cpd.
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| WO2002033412A1 (en) * | 2000-10-14 | 2002-04-25 | Macrogen Inc. | Bio-support and preparing method of the same |
| WO2010033137A1 (en) * | 2008-09-19 | 2010-03-25 | Trustees Of Boston University | Polymeric biolubricants for medical use |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107519845A (en) * | 2017-10-18 | 2017-12-29 | 福州大学 | A kind of ion liquid modified cross-linked porous chitosan absorbent and its preparation and application |
| CN107519845B (en) * | 2017-10-18 | 2019-09-13 | 福州大学 | A kind of ion liquid modified cross-linked porous chitosan absorbent and its preparation and application |
| CN108047384A (en) * | 2017-12-15 | 2018-05-18 | 合众（佛山）化工有限公司 | A kind of lasting anti-corrosive properties water-based acrylic resin and preparation method thereof |
| CN108047384B (en) * | 2017-12-15 | 2020-04-21 | 合众（佛山）化工有限公司 | Durable anti-corrosion water-based acrylic resin and preparation method thereof |
| CN113075146A (en) * | 2020-01-03 | 2021-07-06 | 国家烟草质量监督检验中心 | Organic color developing agent, organic complex probe based on organic color developing agent, and preparation method and application of organic color developing agent |
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