CN103524754A - PAMAM (polyamidoamine) dendrimer supported Schiff base compound as well as preparation method and application thereof - Google Patents
PAMAM (polyamidoamine) dendrimer supported Schiff base compound as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a PAMAM dendrimer supported Schiff base compound as well as a preparation method and an application thereof. According to the preparation method, ethylenediamine is taken as a kernel, a Micheal addition reaction and an amidation of ester between the ethylenediamine and methyl acrylate are performed repeatedly to obtain a branch, and a Schiff base compound is grafted on the tail end of branch to obtain the PAMAM dendrimer supported Schiff base compound. The prepared PAMAM dendrimer supported Schiff base compound has the characteristics of large adsorption quantity and high adsorption capacity for heavy metal in smoke, the effect of reduction of the release amount of the heavy metal in main stream smoke of cigarettes can be effectively realized if a few compounds are added to cigarette filter sticks, and the compound is simple in preparation process and suitable for industrial production.
Description
Technical field
The present invention relates to a kind of polyamide-amide type dendrimer load Schiff alkali cpd and its preparation method and application, belong to new cigarette flue gas 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 polyamide-amide type dendrimer load Schiff alkali to there is not yet bibliographical information for removing the objectionable impuritiess such as heavy metal ion of flue gas.
Summary of the invention
The technology that the present invention is directed to heavy metal content in existing reduction cigarette smoke exists heavy metal content to reduce DeGrain, the defect that sorbent material usage quantity is large, object is to be to provide a kind of, polyamide-amide type dendrimer load Schiff alkali cpd that adsorptive capacity large strong to heavy metal adsorption in cigarette smoke.
Second object of the present invention is the application that is to provide described polyamide-amide type dendrimer load Schiff alkali cpd, adds on a small quantity using it as sorbent material in cigarette filter rod, just can effectively reduce the burst size of heavy metal in cigarette smoke.
The 3rd object of the present invention is the preparation method who is to provide a kind of described polyamide-amide type dendrimer load Schiff alkali cpd, and the method can strictly be controlled the molecular structure of macromolecular compound, and preparation process is simple, can suitability for industrialized production.
The invention provides a kind of polyamide-amide type dendrimer load Schiff alkali cpd, this compound is the compound with formula 1 structure that the Schiff alkali by polyamide-amide type dendrimer grafting formula 2 structures obtains;
R is
or
a kind of in substituted radical;
M is the Schiff alkali number of load;
R
1, R
2and R
3be selected from independently of one another in hydrogen atom, methyl or the tertiary butyl a kind of;
Described polyamide-amide type dendrimer comprises G1, G2 or G3, wherein,
G1 is
g2 is
G3 is
Preferred polyamide-amide type dendrimer load Schiff alkali cpd, R
1and R
2for identical substituting group.
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 polyamide-amide type dendrimer load Schiff alkali cpd, and this application is that described polyamide-amide type dendrimer load Schiff alkali cpd is added on to the burst size that is applied to heavy metal in selectivity reducing cigarette main flume in cigarette filter rod as sorbent material.
The addition of described polyamide-amide type dendrimer load Schiff alkali cpd in cigarette filter rod is that 1～10mg/ props up; Being preferably 2～8mg/ props up.
Described 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 polyamide-amide type dendrimer load Schiff alkali cpd, this preparation method 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 by substitution reaction, the Schiff alkali of formula 2 structures is grafted to the end of gained branch, obtain.
Described Schiff alkali by diamines first with 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 preparation method, preferred 3, the disubstituted salicylic aldehyde of 5-, R
1and R
2for identical substituting group.
Preferred preparation method is: first by quadrol, reacted and obtain G0.5 with mol ratio 1:4 with methyl acrylate, G0.5 and quadrol react with mol ratio 1:4, obtain G1, G1, with mol ratio 1:4 grafting Schiff alkali, obtains the first 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 quadrol react with mol ratio 1:8, obtain G2, G2, with mol ratio 1:8 grafting Schiff alkali, obtains the second 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 quadrol react with mol ratio 1:16, obtain G3, G3, with mol ratio 1:16 grafting Schiff alkali, obtains the third polyamide-amide type dendrimer load Schiff alkali cpd.
The concrete preparation of polyamide-amide type dendrimer load Schiff alkali cpd of the present invention comprises the following steps:
(1) the polyamide-amide type dendrimer compound of synthetic different algebraically:
First by quadrol and methyl acrylate, with mol ratio 1:4, Micheal addition reaction occurs and obtain G0.5, the amidate action that G0.5 and quadrol, with mol ratio 1:4, ester occurs, obtains G1;
Further by G1 and methyl acrylate, with mol ratio 1:8, Micheal addition reaction occurs and obtain G1.5, the amidate action that G1.5 and quadrol, with mol ratio 1:8, ester occurs, obtains G2;
Further by G2 and methyl acrylate, with mol ratio 1:16, Micheal addition reaction occurs again and obtain G2.5, the amidate action that G2.5 and quadrol, with mol ratio 1:16, ester occurs, obtains G3;
Synthetic route is as follows:
(2) Schiff alkali is synthetic:
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;
(3) synthesizing polyamides-amine type dendrimer load Schiff alkali cpd: the resulting G1 of step (1), G2 and G3 are refluxed in THF with the Schiff alkali that step (2) makes respectively, there is substitution reaction, obtain respectively the compound of three kinds of polyamide-amide type dendrimer load Schiff alkali: 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 polyamide-amide type dendrimer load Schiff alkali cpd of novel texture, and using it as sorbent material, be added on the burst size that can effectively reduce main flume heavy metal in cigarette.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 at branch end, introduce the Schiff alkali containing bis-phenol that density is larger, these Schiff alkali counterweight metals have good coordination sequestering action, form more stable complex compound, on macromolecular compound branch, also there is a large amount of amide groups and nitrogen-atoms simultaneously, these groups have abundant electronics, the ability with certain chelating heavy metal, also play the effect of assisting Schiff alkali chelating heavy metal simultaneously, make such polyamide-amide type dendrimer load Schiff alkali cpd large especially to the adsorptive capacity of heavy metal, high adsorption capacity, can in the situation that consumption is little, effectively reduce the burst size of heavy metal in main flume, particularly obvious especially to the adsorption of Cd, Pb and As, experimental results show that: polyamide-amide type dendrimer load Schiff alkali cpd of the present invention is propped up and is added in cigarette with 8mg/, 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 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 the G1 of the embodiment of the present invention 1 preparation and the infrared comparison diagram of G1 load Schiff alkali: a is G1; B is G1.0 grafting Schiff alkali cpd.
Embodiment
Following examples are intended to further illustrate the present invention, rather than limit protection scope of the present invention.
Embodiment 1
(1) first-generation (G1.0) polyamide-amide type dendrimer carrier 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 after 72h, rotary evaporation reduces pressure solution at 70 ℃, when solvent is spin-dried for, be cooled to room temperature, in system, add dissolve with methanol, then the rotary evaporation that reduces pressure at 70 ℃, 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.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, mixture at room temperature reacts after 72h, 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, obtain yellow viscous liquid, be the first-generation (G1.0) polyamide-amide type dendrimer.
(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 500mL 10% 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.
1H?NMR(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 (G1.0) polyamide-amide type dendrimer load 5-methylene radical-3-tertiary butyl-3 ', the preparation of 5 '-di-t-butyl Schiff alkali
By the synthetic first-generation (G1.0) polyamide-amide type dendrimer (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 the first-generation (G1.0) polyamide-amide type dendrimer load, 5 '-di-t-butyl Schiff alkali, the first-generation (G1.0) polyamide-amide type dendrimer 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, in Fig. 1 (b) 1632, and 1546cm
-1wave number band is the infrared signature absorption peak of Schiff alkali, proves that Schiff alkali is successfully grafted on polyamide-amide type 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) s-generation (G2.0) polyamide-amide type dendrimer carrier is synthetic
At 25 ℃, synthetic 1.0G dendrimer (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.By G1.5(4.816g, the ester group of 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, rotary evaporation reduces pressure solution 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, product, 50 ℃ of vacuum-dryings, is obtained to yellow viscous liquid, be the s-generation (G2.0) polyamide-amide type dendrimer.
(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 (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 '-dimethyl Schiff alkali.
(4) s-generation (G2.0) polyamide-amide type dendrimer load 5-methylene radical-3-tertiary butyl-3 ', the preparation of 5 '-dimethyl Schiff alkali
By 5-chloromethyl-3-tertiary butyl-3 ' of the synthetic s-generation (G2.0) polyamide-amide type dendrimer (1mmol) and 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 the s-generation (G2.0) polyamide-amide type dendrimer load, 5 '-dimethyl Schiff alkali.To 5-methylene radical-3-tertiary butyl-3 ' of the s-generation (G2.0) polyamide-amide type dendrimer load of preparation, 5 '-dimethyl Schiff alkali has carried out infrared spectrum characterization, and wherein 1630,1613 and 1580cm
-1wave number band is the infrared signature absorption peak of Schiff alkali, proves that Schiff alkali is successfully grafted on polyamide-amide type 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) third generation (G3.0) polyamide-amide type dendrimer carrier is synthetic
At 25 ℃, synthetic 2.0G dendrimer (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.By G2.5(2.804g, the ester group of 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, rotary evaporation reduces pressure solution 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, product, 50 ℃ of vacuum-dryings, is obtained to yellow viscous liquid, be the third generation (G3.0) polyamide-amide type dendrimer.
(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) preparation of the third generation (G3.0) polyamide-amide type dendrimer load 5-methylene radical-3-tertiary butyl Schiff alkali
The synthetic third generation (G3.0) polyamide-amide type dendrimer (1mmol) and the above-mentioned synthetic 5-chloromethyl-3-tertiary butyl Schiff alkali (16mmol) containing cyclohexanediamine are placed in to 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 the third generation (G3.0) polyamide-amide type dendrimer load.5-methylene radical-3-tertiary butyl Schiff alkali of the third generation (G3.0) polyamide-amide type dendrimer load to preparation has carried out infrared spectrum characterization, and wherein 1630,1615 and 1582cm
-1wave number band is the infrared signature absorption peak of Schiff alkali, proves that Schiff alkali is successfully grafted on polyamide-amide type 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) s-generation (G2.0) polyamide-amide type dendrimer is synthetic
Synthesizing with embodiment 2 of the s-generation (G2.0) polyamide-amide type dendrimer
(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.
At the bottom of 100mL garden, in flask, adding (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 quadrol (10mmol); add 30mL dehydrated alcohol; logical argon shield; be placed in ice-water bath cooling; magnetic agitation; the HCl/ diethyl ether solution (10mmol) that slowly drips 2mmol/L with constant pressure funnel, dripped in 1 hour, and a large amount of white precipitates appear 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 '-tri-tert salicylic aldehyde 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 (G2.0) polyamide-amide type dendrimer load 5-methylene radical-3-methyl-3 ', the preparation of 5 '-di-t-butyl Schiff alkali
By 5-chloromethyl-3-methyl-3 ' of the synthetic s-generation (G2.0) polyamide-amide type dendrimer (1mmol) and 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 the s-generation (G2.0) polyamide-amide type dendrimer load, 5 '-dimethyl Schiff alkali.
Embodiment 5
(1) third generation (G3.0) polyamide-amide type dendrimer is synthetic
Synthesizing with embodiment 3 of the third generation (G3.0) polyamide-amide type dendrimer
(2) synthetic 5-chloromethyl salicylaldehyde
At the bottom of 100mL garden, in flask, adding (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 the third generation (G3.0) polyamide-amide type dendrimer load 5-methylene radical Schiff alkali
The synthetic third generation (G3.0) polyamide-amide type dendrimer (1mmol) and the above-mentioned synthetic 5-chloromethane fundamental mode Schiff alkali (16mmol) containing O-Phenylene Diamine are placed in to 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 the third generation (G3.0) polyamide-amide type dendrimer load.
Embodiment 6
(1) third generation (G3.0) polyamide-amide type dendrimer is synthetic
Synthesizing with embodiment 3 of the third generation (G3.0) polyamide-amide type dendrimer
(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 (G3.0) polyamide-amide type dendrimer load 5-methylene radical-3-methyl-3 ', the preparation of 5 '-dimethyl-5-chloromethane fundamental mode Schiff alkali
By the synthetic third generation (G3.0) polyamide-amide type dendrimer (1mmol) and the above-mentioned synthetic 5-methylene radical-3-methyl-3 ' containing quadrol, 5 '-dimethyl-5-chloromethane fundamental mode 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 the third generation (G3.0) polyamide-amide type dendrimer load, 5 '-dimethyl-5-chloromethane fundamental mode Schiff alkali.
Embodiment 7
The Schiff alkali solid abrasive of the first-generation that embodiment 1 is made (G1.0) polyamide-amide type dendrimer load, sieve, get 40-60 order, 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), 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
The Schiff alkali solid abrasive of the s-generation that embodiment 2 is made (G2.0) polyamide-amide type dendrimer load, sieve, get 40-60 order, 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), 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
The Schiff alkali solid abrasive of the third generation that embodiment 3 is made (G3.0) polyamide-amide type dendrimer load, sieve, get 40-60 order, 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), 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
The Schiff alkali solid abrasive of the s-generation that embodiment 4 is made (G2.0) polyamide-amide type dendrimer load, sieve, get 40-60 order, 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), 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
The Schiff alkali solid abrasive of the third generation that embodiment 5 is made (G3.0) polyamide-amide type dendrimer load, sieve, get 40-60 order, 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), 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
The Schiff alkali solid abrasive of the third generation that embodiment 6 is made (G3.0) polyamide-amide type dendrimer load, sieve, get 40-60 order, 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), 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 (10)
1. a polyamide-amide type dendrimer load Schiff alkali cpd, is characterized in that, the compound with formula 1 structure being obtained by the Schiff alkali of polyamide-amide type dendrimer grafting formula 2 structures;
R is
or
a kind of in substituted radical;
M is the Schiff alkali number of load;
R
1, R
2and R
3be selected from independently of one another in hydrogen atom, methyl or the tertiary butyl a kind of;
Described polyamide-amide type dendrimer comprises G1, G2 or G3, wherein,
G1 is
G2 is
G3 is
2. polyamide-amide type dendrimer load Schiff alkali cpd as claimed in claim 1, is characterized in that described R
1and R
2for identical substituting group.
3. polyamide-amide type dendrimer load Schiff alkali cpd as claimed in claim 1, is characterized in that, described m is 4,8 or 16.
4. the application of a polyamide-amide type dendrimer load Schiff alkali cpd as described in claim 1～3 any one, it is characterized in that, described polyamide-amide type dendrimer load Schiff alkali cpd is added on to the burst size that is applied to heavy metal in selectivity reducing cigarette main flume in cigarette filter rod as sorbent material.
5. application as claimed in claim 4, is characterized in that, the addition of described 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 polyamide-amide type dendrimer load Schiff alkali cpd in cigarette filter rod is that 2～8mg/ props up.
7. application as claimed in claim 4, is characterized in that, described 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 a polyamide-amide type dendrimer load Schiff alkali cpd as described in claim 1～3 any one, it is characterized in that, 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 by substitution reaction, the Schiff alkali of formula 2 structures is grafted to the end of gained branch, obtain;
R is
or
a kind of in substituted radical;
R
1, R
2and R
3be selected from independently of one another in hydrogen atom, methyl or the tertiary butyl a kind of.
9. preparation method as claimed in claim 8, it is characterized in that, described Schiff alkali by diamines first with 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 quadrol react with mol ratio 1:4, obtain G1, G1, with mol ratio 1:4 grafting Schiff alkali, obtains the first 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 quadrol react with mol ratio 1:8, obtain G2, G2, with mol ratio 1:8 grafting Schiff alkali, obtains the second 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 quadrol react with mol ratio 1:16, obtain G3, G3, with mol ratio 1:16 grafting Schiff alkali, obtains the third polyamide-amide type dendrimer load Schiff alkali cpd.
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| CN109052655A (en) * | 2018-07-04 | 2018-12-21 | 合肥帧讯低温科技有限公司 | A kind of disinfection oxygenation agent used for aquiculture |
| CN110483770A (en) * | 2019-08-23 | 2019-11-22 | 南京大学 | A kind of hydrophobic grouping modifies the preparation method and applications of without phosphorus dendritic |
| CN112624358A (en) * | 2020-12-17 | 2021-04-09 | 泉州博银信息科技有限公司 | Environment-friendly water treatment agent and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109052655A (en) * | 2018-07-04 | 2018-12-21 | 合肥帧讯低温科技有限公司 | A kind of disinfection oxygenation agent used for aquiculture |
| CN110483770A (en) * | 2019-08-23 | 2019-11-22 | 南京大学 | A kind of hydrophobic grouping modifies the preparation method and applications of without phosphorus dendritic |
| CN110483770B (en) * | 2019-08-23 | 2021-08-27 | 南京大学 | Preparation method and application of hydrophobic group modified phosphorus-free dendritic polymer |
| CN112624358A (en) * | 2020-12-17 | 2021-04-09 | 泉州博银信息科技有限公司 | Environment-friendly water treatment agent and preparation method thereof |
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