CN103524754B - A kind of polyamidoamine dendrimer load Schiff compound and its preparation method and application - Google Patents
A kind of polyamidoamine dendrimer load Schiff compound and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of polyamidoamine dendrimer load Schiff compound and its preparation method and application; Preparation method take quadrol as core, obtains branch after repeatedly carrying out the amidate action of Micheal addition reaction and ester by quadrol and methyl acrylate, at gained branch terminal graft Schiff compound, to obtain final product; Obtained polyamidoamine dendrimer load Schiff compound has to the heavy metal in flue gas that adsorptive capacity is large, the feature of high adsorption capacity, the effect that just can reach on a small quantity and effectively reduce heavy metal release amount in cigarette mainstream flue gas is added in cigarette filter rod, and this preparation of compounds is simple, can suitability for industrialized production.
Description
Technical field
The present invention relates to a kind of polyamidoamine dendrimer load Schiff compound and its preparation method and application, belong to new cigarette flue gas 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 polyamidoamine dendrimer load Schiff to there is not yet bibliographical information for removing the objectionable impuritiess such as heavy metal ion in flue gas.
Summary of the invention
There is heavy metal content and reduce DeGrain in the technology that the present invention is directed to heavy metal content in existing reduction cigarette smoke, the defect that sorbent material usage quantity is large, object there are provided a kind of, polyamidoamine dendrimer load Schiff compound that adsorptive capacity large strong to heavy metal adsorption in cigarette smoke.
Second object of the present invention is the application being to provide described polyamidoamine dendrimer load Schiff compound, it can be used as sorbent material to add in cigarette filter rod on a small quantity, just effectively can reduce the burst size of heavy metal in cigarette smoke.
3rd object of the present invention is the preparation method being to provide a kind of described polyamidoamine dendrimer load Schiff compound, and the method strictly can control the molecular structure of macromolecular compound, and preparation process is simple, can suitability for industrialized production.
The invention provides a kind of polyamidoamine dendrimer load Schiff compound, this compound is the compound with formula 1 structure obtained by the Schiff of polyamidoamine dendrimer grafting formula 2 structure;
R is
or
a kind of in substituted radical;
M is the Schiff number of load;
R
1, R
2and R
3be selected from hydrogen atom, methyl or the tertiary butyl a kind of independently of one another;
Described polyamidoamine dendrimer comprises G1, G2 or G3, wherein,
G1 is
g2 is
G3 is
Preferred polyamidoamine dendrimer load Schiff compound, R
1and R
2for identical substituting group.
More preferably 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 polyamidoamine dendrimer load Schiff compound, this application is that described polyamidoamine dendrimer load Schiff compound is added in cigarette filter rod as sorbent material the burst size being applied to heavy metal in selectivity reducing cigarette main flume.
The described addition of polyamidoamine dendrimer load Schiff compound in cigarette filter rod is that 1 ~ 10mg/ props up; Be preferably 2 ~ 8mg/ to prop up.
Described 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 polyamidoamine dendrimer load Schiff compound, this preparation method take quadrol as core, branch is obtained after repeatedly carrying out the amidate action of Micheal addition reaction and ester by quadrol and methyl acrylate, and by substitution reaction, the Schiff of formula 2 structure is grafted to the end of gained branch, to obtain final product.
Described Schiff first carries out the condensation reaction of amine aldehyde with 3,5-disubstituted salicylic aldehydes of 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 preparation method, preferred 3,5-disubstituted salicylic aldehydes, R
1and R
2for identical substituting group.
Preferred preparation method is: be first obtained by reacting G0.5 by quadrol and methyl acrylate with mol ratio 1:4, G0.5 and quadrol react with mol ratio 1:4, obtain G1, G1, with mol ratio 1:4 grafting Schiff, obtains the first 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 quadrol react with mol ratio 1:8, obtain G2, G2, with mol ratio 1:8 grafting Schiff, obtains the second 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 quadrol react with mol ratio 1:16, obtain G3, G3, with mol ratio 1:16 grafting Schiff, obtains the third polyamidoamine dendrimer load Schiff compound.
The concrete preparation of polyamidoamine dendrimer load Schiff compound of the present invention comprises the following steps:
(1) the 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, and G0.5 and quadrol, with mol ratio 1:4, the amidate action of ester occurs, and obtains G1;
With mol ratio 1:8, Micheal addition reaction occurs by G1 and methyl acrylate further and obtain G1.5, there is the amidate action of ester with mol ratio 1:8 in G1.5 and quadrol, obtains G2;
With mol ratio 1:16, Micheal addition reaction occurs by G2 and methyl acrylate further again and obtain G2.5, there is the amidate action of ester with mol ratio 1:16 in G2.5 and quadrol, obtains G3;
Synthetic route is as follows:
(2) synthesis of Schiff:
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;
(3) synthesizing polyamides-amine type dendrimer load Schiff compound: the Schiff that G1, G2 and G3 of step (1) being obtained obtain with step (2) respectively refluxes in THF, there is substitution reaction, obtain the compound of three kinds of polyamidoamine dendrimer load Schiff respectively: synthetic route is as follows:
Beneficial effect of the present invention: the present invention has synthesized a kind of double-Schiff base containing chloromethyl first, and be grafted on arborescens polymer, synthesize a kind of polyamidoamine dendrimer load Schiff compound of novel texture, and it can be used as sorbent material to be added on the burst size that effectively can reduce main flume heavy metal in cigarette.Polyamidoamine dendrimer load Schiff compound of the present invention is a kind of highly branched, compound with regular structure, and the dendrimer that molecular size is controlled, particularly introduce the larger Schiff containing bis-phenol of density at branch end, these Schiff heavy metal have good coordination sequestering action, form more stable complex compound, also there is a large amount of amide groups and nitrogen-atoms in macromolecular compound branch simultaneously, these groups have abundant electronics, there is the ability of certain chelate heavy metals, also play the effect of assisting Schiff chelate heavy metals simultaneously, make the adsorptive capacity of such polyamidoamine dendrimer load Schiff compound heavy metal large especially, high adsorption capacity, the burst size of heavy metal in main flume effectively can be reduced when consumption is little, particularly obvious especially to the adsorption of Cd, Pb and As, experiment proves: propped up with 8mg/ by polyamidoamine dendrimer load Schiff compound of the present invention and be added in cigarette, and the reduced rate that the reduced rate of Cd can reach 35.3%, Pb can reach 26.1%, the reduced rate of As can reach 28.1%.In addition, this 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
The infrared comparison diagram of G1 and the G1 load Schiff that [Fig. 1] is prepared for the embodiment of the present invention 1: a is G1; B is G1.0 grafting Schiff compound.
Embodiment
Following examples are intended to further illustrate the present invention, instead of limit protection scope of the present invention.
Embodiment 1
(1) synthesis of the first-generation (G1.0) polyamidoamine dendrimer carrier
At 25 DEG C, by quadrol (EDA) (1.202g, 20mmol) as macromolecular core, with methyl acrylate (MA) (6.887g, after 80mmol) reacting 72h in 50mL methanol solution, solution is carried out decompression rotary evaporation at 70 DEG C, when solvent is spin-dried for, be cooled to room temperature, in system, add dissolve with methanol, then carry out decompression rotary evaporation at 70 DEG C, the product obtained afterwards in triplicate, 50 DEG C of vacuum-dryings, obtain 0.5 generation (G0.5) macromole, this macromole end has four ester functional groups.By G0.5(4.042g, the ester group of 40mmol) be dissolved in anhydrous methanol, then, again by EDA(2.4g, 40mmol) dropwise join in system reaction system, after mixture at room temperature reacts 72h, 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 yellow, viscous liquid, be the first-generation (G1.0) polyamidoamine dendrimer.
(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) first-generation (G1.0) the polyamidoamine dendrimer load 5-methylene radical-3-tertiary butyl-3 ', the preparation of 5 '-di-t-butyl Schiff
The first-generation (G1.0) polyamidoamine dendrimer (1mmol) of synthesis and above-mentioned synthesis contained 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 the first-generation (G1.0) polyamidoamine dendrimer load ', 5 '-di-t-butyl Schiff, the first-generation (G1.0) polyamidoamine dendrimer 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, in Fig. 1 (b) 1632, and 1546cm
-1wave number band is the infrared signature absorption peak of Schiff, proves that Schiff is successfully grafted on polyamidoamine dendrimer carrier.FT-IR(KBr):3438,2951,2905,2863,1651,1632,1618,1572,1546,1505,1457,1434,1391,1360,1342,1311,1263,1254,1213,1175,1146,1092,1027,833,785,747,644,610,543cm
-1。
Embodiment 2
(1) synthesis of the s-generation (G2.0) polyamidoamine dendrimer carrier
At 25 DEG C, the 1.0G dendrimer (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.Ester group by G1.5(4.816g, 32mmol) be dissolved in the middle of anhydrous methanol, then, again by quadrol (EDA) (1.92g, 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, decompression rotary evaporation is carried out, in triplicate at 70 DEG C.Finally, by product 50 DEG C of vacuum-dryings, obtain yellow, viscous liquid, be the s-generation (G2.0) polyamidoamine dendrimer.
(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 (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 '-dimethyl Schiff.
(4) s-generation (G2.0) the polyamidoamine dendrimer load 5-methylene radical-3-tertiary butyl-3 ', the preparation of 5 '-dimethyl Schiff
By the s-generation (G2.0) polyamidoamine dendrimer (1mmol) of 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 the s-generation (G2.0) polyamidoamine dendrimer load ', 5 '-dimethyl Schiff.5-methylene radical-3-the tertiary butyl-3 of the s-generation (G2.0) polyamidoamine dendrimer load to preparation ', 5 '-dimethyl Schiff has carried out infrared spectrum characterization, and wherein 1630,1613 and 1580cm
-1wave number band is the infrared signature absorption peak of Schiff, proves that Schiff is successfully grafted on polyamidoamine dendrimer carrier.FT-IR(KBr):3439,2951,2904,2865,1630,1613,1580,1535,1507,1467,1435,1391,1363,1338,1309,1272,1251,1202,1174,1142,1082,1034,980,928,878,836,772,745,731,644,608,545cm
-1。
Embodiment 3
(1) synthesis of the third generation (G3.0) polyamidoamine dendrimer carrier
At 25 DEG C, the 2.0G dendrimer (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.Ester group by G2.5(2.804g, 16mmol) be dissolved in the middle of anhydrous methanol, then, again by quadrol (EDA) (0.96g, 16mmol) 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, decompression rotary evaporation is carried out, in triplicate at 70 DEG C.Finally, by product 50 DEG C of vacuum-dryings, obtain yellow, viscous liquid, be the third generation (G3.0) polyamidoamine dendrimer.
(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) preparation of the third generation (G3.0) polyamidoamine dendrimer load 5-methylene radical-3-tertiary butyl Schiff
5-chloromethyl-3-tertiary butyl Schiff (16mmol) containing cyclohexanediamine of the third generation (G3.0) polyamidoamine dendrimer (1mmol) of synthesis and above-mentioned synthesis is 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 the third generation (G3.0) polyamidoamine dendrimer load.Infrared spectrum characterization is carried out to the 5-methylene radical-3-tertiary butyl Schiff of the third generation (G3.0) polyamidoamine dendrimer load of preparation, wherein 1630,1615 and 1582cm
-1wave number band is the infrared signature absorption peak of Schiff, proves that Schiff is successfully grafted on polyamidoamine dendrimer carrier.FT-IR(KBr):3445,2951,2904,2867,1651,1630,1615,1582,1535,1504,1463,1434,1390,1361,1338,1301,1272,1266,1251,1203,1173,1145,1082,1033,980,930,875,836,773,743,730,645,610,545cm
-1。
Embodiment 4
(1) synthesis of the s-generation (G2.0) polyamidoamine dendrimer
The synthesis of the s-generation (G2.0) polyamidoamine dendrimer 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 flask at the bottom of 100mL garden, 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
Quadrol (10mmol) is added in 100mL three-necked flask; add 30mL dehydrated alcohol; logical argon shield; be placed in ice-water bath cooling; magnetic agitation; slowly drip the HCl/ diethyl ether solution (10mmol) of 2mmol/L with constant pressure funnel, dripping in 1 hour, there is a large amount of white precipitate in solution.Room temperature continues and to continue under condition continuously to stir 12h, then filtration under diminished pressure, and 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 '-tri-tert salicylic aldehyde 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 (G2.0) polyamidoamine dendrimer load 5-methylene radical-3-methyl-3 ', the preparation of 5 '-di-t-butyl Schiff
By the s-generation (G2.0) polyamidoamine dendrimer (1mmol) of 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 the s-generation (G2.0) polyamidoamine dendrimer load ', 5 '-dimethyl Schiff.
Embodiment 5
(1) synthesis of the third generation (G3.0) polyamidoamine dendrimer
The synthesis of the third generation (G3.0) polyamidoamine dendrimer is with embodiment 3
(2) 5-chloromethyl salicylaldehyde is synthesized
(15.2mmol) salicylic aldehyde is added in flask at the bottom of 100mL garden, 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 the third generation (G3.0) polyamidoamine dendrimer load 5-methylene radical Schiff
5-chloromethane fundamental mode Schiff (16mmol) containing O-Phenylene Diamine of the third generation (G3.0) polyamidoamine dendrimer (1mmol) of synthesis and above-mentioned synthesis is 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 the third generation (G3.0) polyamidoamine dendrimer load.
Embodiment 6
(1) synthesis of the third generation (G3.0) polyamidoamine dendrimer
The synthesis of the third generation (G3.0) polyamidoamine dendrimer 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 (G3.0) polyamidoamine dendrimer load 5-methylene radical-3-methyl-3 ', the preparation of 5 '-dimethyl-5-chloromethane fundamental mode Schiff
The third generation (G3.0) polyamidoamine dendrimer (1mmol) of synthesis and above-mentioned synthesis contained the 5-methylene radical-3-methyl-3 of quadrol ', 5 '-dimethyl-5-chloromethane fundamental mode 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 the third generation (G3.0) polyamidoamine dendrimer load ', 5 '-dimethyl-5-chloromethane fundamental mode Schiff.
Embodiment 7
By the Schiff solid abrasive of the first-generation (G1.0) polyamidoamine dendrimer load obtained for embodiment 1, sieve, get 40-60 order, 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), when addition props up with 2mg/ respectively, the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 15.2%, 9.7% and 12.5%; (2) when sorbent material props up with 4mg/ respectively, the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 23.5%, 15.2% and 18.3%; (3) when sorbent material props up with 6mg/ respectively, the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 37.6%, 21.7% and 28.6%; (4) when sorbent material props up with 8mg/ respectively, the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 39.2%, 25.3% and 28.1%.
Embodiment 8
By the Schiff solid abrasive of the s-generation (G2.0) polyamidoamine dendrimer load obtained for embodiment 2, sieve, get 40-60 order, 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), when addition props up with 2mg/ respectively, the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 13.1%, 6.7% and 10.6%; (2) when sorbent material props up with 4mg/ respectively, the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 20.7%, 13.5% and 16.6%; (3) when sorbent material props up with 6mg/ respectively, the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 28.1%, 19.3% and 22.7%; (4) when sorbent material props up with 8mg/ respectively, the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 30.4%, 23.2% and 25.7%.
Embodiment 9
By the Schiff solid abrasive of the third generation (G3.0) polyamidoamine dendrimer load obtained for embodiment 3, sieve, get 40-60 order, 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), when addition props up with 2mg/ respectively, the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 11.5%, 5.2% and 9.8%; (2) when sorbent material props up with 4mg/ respectively, the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 23.2%, 14.3% and 15.7%; (3) when sorbent material props up with 6mg/ respectively, the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 25.4%, 17.6% and 20.6%; (4) when sorbent material props up with 8mg/ respectively, the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 27.5%, 21.3% and 22.5%.
Embodiment 10
By the Schiff solid abrasive of the s-generation (G2.0) polyamidoamine dendrimer load obtained for embodiment 4, sieve, get 40-60 order, 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), when addition props up with 2mg/ respectively, the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 12.6%, 9.8% and 12.5%; (2) when sorbent material props up with 4mg/ respectively, the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 25.1%, 18.7% and 19.0%; (3) when sorbent material props up with 6mg/ respectively, the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 30.4%, 25.2% and 24.3%; (4) when sorbent material props up with 8mg/ respectively, the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 35.3%, 26.1% and 28.4%.
Embodiment 11
By the Schiff solid abrasive of the third generation (G3.0) polyamidoamine dendrimer load obtained for embodiment 5, sieve, get 40-60 order, 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), when addition props up with 2mg/ respectively, the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 9.3%, 5.7% and 11.3%; (2) when sorbent material props up with 4mg/ respectively, the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 21.5%, 15.6% and 18.1%; (3) when sorbent material props up with 6mg/ respectively, the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 27.1%, 18.3% and 23.1%; (4) when sorbent material props up with 8mg/ respectively, the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 30.1%, 21.8% and 25.1%.
Embodiment 12
By the Schiff solid abrasive of the third generation (G3.0) polyamidoamine dendrimer load obtained for embodiment 6, sieve, get 40-60 order, 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), when addition props up with 2mg/ respectively, the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 10.8%, 6.1% and 10.3%; (2) when sorbent material props up with 4mg/ respectively, the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 20.1%, 15.2% and 17.9%; (3) when sorbent material props up with 6mg/ respectively, the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 28.7%, 18.9% and 21.8%; (4) when sorbent material props up with 8mg/ respectively, the reduced rate of flue gas heavy metal Cd, Pb and As is respectively 29.7%, 20.6% and 25.8%.
Claims (11)
1. a polyamidoamine dendrimer load Schiff compound, is characterized in that, the compound with formula 1 structure obtained by the Schiff of polyamidoamine dendrimer grafting formula 2 structure;
R is
a kind of in substituted radical;
M is the Schiff number of load;
R
1, R
2and R
3be selected from hydrogen atom, methyl or the tertiary butyl a kind of independently of one another;
Described polyamidoamine dendrimer comprises G1, G2 or G3, wherein,
G1 is
g2 is
G3 is
2. polyamidoamine dendrimer load Schiff compound as claimed in claim 1, is characterized in that, described R
1and R
2for identical substituting group.
3. polyamidoamine dendrimer load Schiff compound as claimed in claim 1, it is characterized in that, described m is 4,8 or 16.
4. the application of a polyamidoamine dendrimer load Schiff compound as described in any one of claims 1 to 3, it is characterized in that, described polyamidoamine dendrimer load Schiff compound is added in cigarette filter rod as sorbent material the burst size being applied to heavy metal in selectivity reducing cigarette main flume.
5. apply as claimed in claim 4, it is characterized in that, the described addition of 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 polyamidoamine dendrimer load Schiff compound in cigarette filter rod is that 2 ~ 8mg/ props up.
7. apply as claimed in claim 4, it is characterized in that, described 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 a polyamidoamine dendrimer load Schiff compound as described in any one of claims 1 to 3, it is characterized in that, take quadrol as core, branch is obtained after repeatedly carrying out the amidate action of Michael addition reaction and ester by quadrol and methyl acrylate, and by substitution reaction, the Schiff of formula 2 structure is grafted to the end of gained branch, to obtain final product;
R is
a kind of in substituted radical;
R
1, R
2and R
3be selected from hydrogen atom, methyl or the tertiary butyl a kind of independently of one another.
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 3,5-disubstituted salicylic aldehydes of 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 quadrol react with mol ratio 1:4, obtain G1, G1, with mol ratio 1:4 grafting Schiff, obtains the first 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 quadrol react with mol ratio 1:8, obtain G2, G2, with mol ratio 1:8 grafting Schiff, obtains the second 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 quadrol react with mol ratio 1:16, obtain G3, G3, with mol ratio 1:16 grafting Schiff, obtains the third polyamidoamine dendrimer load Schiff compound.
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