CN101205212B - Gemini nicotinate quaternary ammonium salt and method for making same - Google Patents
Gemini nicotinate quaternary ammonium salt and method for making same Download PDFInfo
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- CN101205212B CN101205212B CN200710050305.3A CN200710050305A CN101205212B CN 101205212 B CN101205212 B CN 101205212B CN 200710050305 A CN200710050305 A CN 200710050305A CN 101205212 B CN101205212 B CN 101205212B
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Abstract
The invention relates to a gemini nicotinic acid ester quaternary ammonium salt, namely a bromide bi-N-alkyl nicotinic acid athylene glycol/diethylene glycol/triethylene glycol, the preparation method of which is given as follows: (1) the nicotinic acid and the thionyl chloride are added in a reaction bottle in a molar ratio of the nicotinic acid to the thionyl chloride ranging from 1:3 to 1:6; after the reaction between the nicotinic acid and the thionyl chloride lasts for 2 to 4 hours, the nicotinic acid acyl chloride which is in a white needle-shaped crystal is obtained; (2) the nicotinic acid acyl chloride is dissolved in the dried chloroform and then the alcohol with a molar ratio to the nicotinic acid of 1:2 is dropped slowly in the mixtures of the nicotinic acid acyl chloride; the alcohols can be ethylene glycol, diethylene glycol or teg; the alcohols are dissolved by adding a proper amount of water and the nicotinates which are the products of the alcoholysis are subject to the pumping filtration and drying; (3) the nicotinate and the alkyl bromide are added in the reaction bottle in a molar ratio of the nicotinate to the alkyl bromide ranging from 1:2 to 1:6; the number of the carbon atoms of the alkyl bromide is 8, 10, 12, 14 or 16; the anhydrous acetonitrile is used as the solvent and the mixtures in the reaction bottle are heated and refluxed for 30 to 40 hours; after the mixtures are subject to the washing and pumping filtration, the products, gemini nicotinic acid ester quaternary ammonium salts, are obtained. The gemini nicotinic acid ester quaternary ammonium salt has very high surface activity and very strong bactericidal performances and corrosion inhibition, the preparation method of the invention is simple, convenient and feasible, is easy to be operated, delivers high yield and causes no environmental contaminations.
Description
Technical field
The present invention relates to a kind of Gemini nicotinate quaternary ammonium salt and preparation method thereof.
Background technology
Tensio-active agent has become indispensable chemical of moment in national economy and human daily life.In fields such as energy mining industry, metal processing, light textile, daily-use chemical industry, food pharmaceuticals purposes is widely arranged all.Nineteen thirty-five Domagk has found that cats product has sterilizing ability, and representative wherein is the tensio-active agent of quaternary, also has pyridinium salt, imidazoline salt, isoquinoline 99.9 salt etc. in addition.The gemini quaternary ammonium salt compound with its low toxicity, efficient, broad-spectrum antimicrobial and have excellent properties such as wide biological activity (Nagamune H et al.Evaluation of the Cytotoxic Effectsof Bis-quaternary Ammonium Antimicrobial Reagents on HumanCells[J] .Toxicology in Vitro, 2000,14:139-147), fields such as medical science, food, makeup, weaving and Treatment of Industrial Water have been widely used in.These cats products have wide spectrum and kill bacteriostasis and odorless, water-soluble big, bland advantage, and the bacteriocidal concentration as 1227 is low, good water solubility, toxicity and pungency are little, but the price height, serum also has certain influence to its sterilization effect.Also find a kind of tensio-active agent of long-time use in same system in actual applications, the resistance of microorganisms makes its result of use (Huang Qiran that obviously descends, Tang Xiaoyan, Chen Xiaodan. the synthetic and bactericidal property research [J] of novel biquaternary ammonium salts bactericides. the Guangdong chemical industry, 2007,34 (3): 9-10), as sulfatereducting bacteria in 1227 pairs of oil field reinjection waters kill consumption by 30mg/L to 100mg/L, so necessaryly seek new sterilant.
Corrosive harm is very huge, and rationally using inhibiter is to prevent that metal and alloy from the corrosive effective ways taking place in surrounding medium.The kinds of surfactants that can be used as metal inhibitor is a lot, but applied research is maximum is cats product, nonionogenic tenside and contains multi-functional tensio-active agent, particularly quaternary ammonium salt cationic surfactant is used very extensive aspect inhibition.Because the gemini quaternary ammonium salt tensio-active agent has higher surfactivity than traditional list quaternary surfactant, has lower critical micelle concentration (cmc), better water-solubility is arranged, when mixing, show better synergistic effect etc., be expected it and play a significant role in metallic corrosion and corrosion-resistant field with other materials.
Summary of the invention
The object of the present invention is to provide a kind of Gemini nicotinate quaternary ammonium salt, it is bromination two-N-alkyl nicotinic acid ethylene glycol/glycol ether/triethyleneglycol ester, this quaternary ammonium salt has very high surfactivity and very strong bactericidal property and corrosion inhibition, the present invention also provides its preparation method, this method is simple and feasible, easy handling, yield is higher, and non-environmental-pollution.
For reaching above technical purpose, the invention provides following technical scheme.
A kind of Gemini nicotinate quaternary ammonium salt, i.e. bromination two-N-alkyl nicotinic acid ethylene glycol/glycol ether/triethyleneglycol ester, its structural formula is as follows:
m＝0，1，2；n＝8，10，12，14，16
This Gemini nicotinate quaternary ammonium salt is noted the n-m-n into EQ by abridging.
Preparation bromination two-N-alkyl nicotinic acid ethylene glycol/glycol ether/triethyleneglycol ester is to be raw material with natural product nicotinic acid, obtains target product through acidylate, alcoholysis, quaternized three-step reaction, and its reaction formula is as follows:
The first step: acidylate
Second step: alcoholysis
The 3rd step: quaternized
m＝0，1，2；n＝8，10，12，14，16
Preparation bromination two-N-alkyl nicotinic acid ethylene glycol/glycol ether/triethyleneglycol ester mainly comprises:
1) preparation of nicotinate:
With nicotinic acid and sulfur oxychloride by 1: 3-1: 6 mol ratio joins in the reaction flask, stirring and refluxing, NaOH solution absorption tail gas.Behind the reaction 2-4h, cooling, decompression is spin-dried for the excess chlorination sulfoxide, gets white needle-like crystals.Make solvent with dry chloroform, slowly splashing into the nicotinic acid mol ratio is 1: 2 alcohol, NaOH solution absorption tail gas, backflow 4-10h.Be spin-dried for solvent after the cooling, add the suitable quantity of water dissolving, use saturated Na
2CO
3The aqueous solution is regulated PH to neutrality or weakly alkaline, handles with diverse ways according to the state of alcoholysis products therefrom that (solid then filters, oven dry; Liquid is crossed post).The productive rate of alcoholysis product is all more than 90%.
2) bromination two-preparation of N-alkyl nicotinate:
Ester that alcoholysis is obtained and long-chain bromoalkane are by 1: 2-1: 6 mol ratio joins in the reaction flask, and anhydrous acetonitrile is made solvent, reflux 30-40h.Reaction is spin-dried for solvent after finishing, and with the anhydrous propanone washing, filters, and then further does recrystallization with ethanol and sherwood oil if product is impure.Products therefrom is white solid, and the productive rate major part is more than 50%, even up to 80%.Through tetrabromophenol sulfonphthalein method qualitative detection product is quaternary ammonium salt, and product structure also confirms through collection of illustrative plates.
In sum, a kind of preparation method of Gemini nicotinate quaternary ammonium salt may further comprise the steps successively:
(1) with nicotinic acid and sulfur oxychloride by 1: 3-1: 6 mol ratio joins in the reaction flask, stirring and refluxing, NaOH solution absorption tail gas, behind the reaction 2-4h, cooling, decompression is spin-dried for the excess chlorination sulfoxide, white needle-like crystals nicotinic acid acyl chlorides;
(2) the nicotinic acid acyl chlorides is dissolved in the dry chloroform, slowly splashing into the nicotinic acid mol ratio is 1: 2 alcohol, and alcohol is ethylene glycol, glycol ether or triglycol, NaOH solution absorption tail gas, and backflow 4-10h is spin-dried for solvent after the cooling, add the suitable quantity of water dissolving, uses saturated Na
2CO
3The aqueous solution is regulated PH to neutrality or weakly alkaline, and the alcoholysis product nicotinate is filtered oven dry;
(3) with nicotinate and bromoalkane by 1: 2-1: 6 mol ratio joins in the reaction flask, the carbonatoms of bromoalkane is 8,10,12,14 or 16, anhydrous acetonitrile is made solvent, reflux 30-40h, reaction is spin-dried for solvent after finishing, with the anhydrous propanone washing, filter, the gained white solid is the product Gemini nicotinate quaternary ammonium salt.
Bromination two-N-alkyl nicotinic acid ethylene glycol/glycol ether of the present invention/triethyleneglycol ester has very high surfactivity and very strong broad-spectrum sterilization performance and corrosion inhibition, streptococcus aureus, intestinal bacteria, bacillus subtilis black variety bud cell, Candida albicans all there are very strong killing action, metal is had very strong slow-release capability.In addition a little less than this compounds whipability, the not foaming that has.Multiple function such as therefore should the series Gemini nicotinate quaternary ammonium salt be expected to have sterilization, anticorrosion can be widely used in fields such as petrochemical complex, articles for washing, light textile, pharmacy.
Description of drawings
Fig. 1 is the hydrogen spectrogram of EQ16-0-16
Fig. 2 is the hydrogen spectrogram of EQ16-1-16
Fig. 3 is the hydrogen spectrogram of EQ16-2-16
Fig. 4 is the graph of a relation of EQ Gemini surface active agent solution surface tension and its concentration
Embodiment
The preparation of bromination two-N-alkyl nicotinic acid ethylene glycol/glycol ether/triethyleneglycol ester (EQn-m-n)
EQ16-2-16's is synthetic
The adding mol ratio is 1: 5 nicotinic acid and a sulfur oxychloride in reaction flask, stirring and refluxing, NaOH solution absorption tail gas.Behind the reaction 4h, cooling, decompression is spin-dried for the excess chlorination sulfoxide, gets white needle-like crystals.Make solvent with dry chloroform, slowly splashing into the nicotinic acid mol ratio is 1: 2 triglycol, NaOH solution absorption tail gas, backflow 10h.Be spin-dried for solvent after the cooling, add the suitable quantity of water dissolving, use saturated Na
2CO
3The aqueous solution is regulated PH to weakly alkaline, tells organic phase, and water ethyl acetate extraction 2-3 time merges organic phase, is spin-dried for the back and crosses post with ethyl acetate, and products therefrom is a weak yellow liquid, productive rate 92%.
Triethyleneglycol ester that alcoholysis is obtained and bromohexadecane join in the reaction flask by 1: 4 mol ratio, and anhydrous acetonitrile is made solvent, reflux 40h.Reaction is spin-dried for solvent after finishing, and does recrystallization to pure with ethanol and sherwood oil.Products therefrom is a white solid, productive rate 39%.
EQ12-1-12's is synthetic
The adding mol ratio is 1: 5 nicotinic acid and a sulfur oxychloride in reaction flask, stirring and refluxing, NaOH solution absorption tail gas.Behind the reaction 4h, cooling, decompression is spin-dried for the excess chlorination sulfoxide, gets white needle-like crystals.Make solvent with dry chloroform, slowly splashing into the nicotinic acid mol ratio is 1: 2 glycol ether, NaOH solution absorption tail gas, backflow 10h.Be spin-dried for solvent after the cooling, add the suitable quantity of water dissolving, use saturated Na
2CO
3The aqueous solution is regulated PH to weakly alkaline, and suction filtration is used distilled water wash during suction filtration, oven dry.Products therefrom is a white solid, productive rate 91%, fusing point 118-119 ℃.
Glycol ester that alcoholysis is obtained and bromododecane join in the reaction flask by 1: 4 mol ratio, and anhydrous acetonitrile is made solvent, reflux 40h.Reaction is spin-dried for solvent after finishing, and adds the anhydrous propanone washing, and suction filtration will detect through TLC with anhydrous propanone repetitive scrubbing several back products therefrom during suction filtration and be essentially a point.Product is a white solid, productive rate 50%.
EQ8-0-8's is synthetic
The adding mol ratio is 1: 3 nicotinic acid and a sulfur oxychloride in reaction flask, stirring and refluxing, NaOH solution absorption tail gas.Behind the reaction 4h, cooling, decompression is spin-dried for the excess chlorination sulfoxide, gets white needle-like crystals.Make solvent with dry chloroform, slowly splashing into the nicotinic acid mol ratio is 1: 2 ethylene glycol, NaOH solution absorption tail gas, backflow 10h.Be spin-dried for solvent after the cooling, add the suitable quantity of water dissolving, use saturated Na
2CO
3The aqueous solution is regulated PH to weakly alkaline, and suction filtration is used distilled water wash during suction filtration, oven dry.Products therefrom is a white solid, productive rate 90%.
Glycol ester that alcoholysis is obtained and bromooctane join in the reaction flask by 1: 4 mol ratio, and anhydrous acetonitrile is made solvent, reflux 40h.Reaction is spin-dried for solvent after finishing, and adds the anhydrous propanone washing, and suction filtration will detect through TLC with anhydrous propanone repetitive scrubbing several back products therefrom during suction filtration and be essentially a point.Product is a white powder, productive rate 45%.Fusing point 52-54 ℃.
The structural characterization of bromination two-N-alkyl nicotinic acid ethylene glycol/glycol ether/triethyleneglycol ester (EQn-m-n)
The structural characterization of EQ16-0-16
Referring to Fig. 1, Fig. 1 is the hydrogen spectrogram of EQ16-0-16, according to spectrogram chemical shift and the correlation parameter of EQ16-0-16 is listed in the table below 1:
Table 1EQ16-0-16's
1The HNMR parameter
As known from Table 1: 1,2,3,4 groups is the pyridine ring hydrogen, and 5 groups is the methylene radical hydrogen that directly links to each other with nitrogen, 6 groups be with ester group on the methylene radical hydrogen that directly links to each other of oxygen, 7,8 groups is the methylene radical hydrogen on the long chain alkane, 9 groups is the methyl hydrogen of long chain alkane end.Hydrogen atom adds up to half of target product molecular hydrogen atomicity, infers that thus the molecular structure symmetry conforms to the target product structure.
The structural characterization of EQ16-1-16
Referring to Fig. 2, Fig. 2 is the hydrogen spectrogram of EQ16-1-16, according to spectrogram chemical shift and the correlation parameter of EQ16-1-16 is listed in the table below 2:
Table 2E16-1-16's
1The HNMR parameter
*: this group hydrogen is solvent peak
As known from Table 2: 1,2,3,4 groups is the pyridine ring hydrogen, 5 groups is the methylene radical hydrogen that directly links to each other with nitrogen, and 6,7 groups is the methylene radical hydrogen on the EO, and 8 groups is solvent peak, 9,10,11 groups is the methylene radical hydrogen on the long chain alkane, and 12 groups is the methyl hydrogen of long chain alkane end.Remove solvent peak, hydrogen atom adds up to half of target product molecular hydrogen atomicity, infers that thus the molecular structure symmetry conforms to the target product structure.
The structural characterization of EQ16-2-16
Referring to Fig. 3, Fig. 3 is the hydrogen spectrogram of EQ16-2-16, according to spectrogram chemical shift and the correlation parameter of EQ16-2-16 is listed in the table below 3:
Table 3EQ16-2-16's
1The HNMR parameter
*: this group hydrogen is solvent peak
As shown in Table 3: 1,2,3,4 groups is the pyridine ring hydrogen, 5 groups is the methylene radical hydrogen that directly links to each other with nitrogen, and 6,7,8 groups is the methylene radical hydrogen on the EO, and 9 groups is solvent peak, 10,11,12 groups is the methylene radical hydrogen on the long chain alkane, and 13 groups is the methyl hydrogen of long chain alkane end.Remove the peak that solvent effect produces, hydrogen atom adds up to half of target molecule number, and hence one can see that, and the molecular structure symmetry conforms to the target compound molecular structure.
Embodiment 3
The surfactivity research of bromination two-N-alkyl nicotinic acid ethylene glycol/glycol ether/triethyleneglycol ester (EQn-m-n)
The tensio-active agent of required mensuration is mixed with the certain density serial aqueous solution with redistilled water, under 20 ℃, adopts the suspension ring method to measure the surface tension of water phase surfactant mixture.Measurement result is shown in Fig. 4 and table 4.
From seen in fig. 4, along with this series of surfactants adds, water surface tension sharply descends, and concentration increases, and surface tension descends and slows down, and tends towards stability at last.Alkyl chain increases, and surfactivity increases.
The cmc of several tensio-active agents of table 4, γ
CmcAnd C
20
Annotate: C
20Required surfactant concentrations when representative reduces water surface tension 20mN/m.CTAB and CPB are respectively two kinds of common cats product cetyl trimethylammonium bromides and bromohexadecane yl pyridines
As can be seen from Table 4,10 kinds of compounds of our institute's synthetic are except EQ08-0-08 and EQ10-0-10, and the cmc of other compounds all cmc than two kinds of common cats products is low.C
20C than CTAB and CPB
20Low one to two order of magnitude (except that EQ08-0-08), it is more much higher than CTAB and CPB to illustrate that the synthetic EQ of institute series quaternary ammonium salt reduces capillary efficient.As seen the synthetic EQ of institute series quaternary surfactant has good DEVELOPMENT PROSPECT.
The bactericidal property research of bromination two-N-alkyl nicotinic acid ethylene glycol/glycol ether/triethyleneglycol ester (EQn-m-n)
Indicator: streptococcus aureus (ATCC 6538), intestinal bacteria (8099), bacillus subtilis black variety bud cell (ATCC 9732), Candida albicans (ATCC 10231).
Substratum compound method: press the microbial culture based formulas: in the 100g water, add the beef extract of 0.3%-0.5%, 1% peptone, 0.5% NaCl, 1.3% agar powder carries out weighing, and heating is dissolved, and regulates pH value to 7-7.5, be sub-packed in the test tube, jump a queue, the wet-heating sterilization, standby.
Sterilising method: 1), various instruments, substratum, distilled water are put in the electric heating portable steam sterilizer, sterilized 30 minutes; 2), inoculating tool, sterilize with the method for calcination; 3), experimental implementation is all carried out at Bechtop.
The mensuration of sterilant fungicidal activity:
1), sterilant is made into the solution of 30ppm concentration.
2), bacterium liquid is carried out live bacterial count, and to be diluted to bacteria containing amount with sterile distilled water be 5 * 10
5-6 * 10
6The bacteria suspension of cfu/ml is made as original bacteria liquid, do 10 times increase progressively the dilution be 10
-3, 10
-4, 10
-5The diluent of 3 kinds of concentration is drawn 0.5ml in different sterilization plates with valinche respectively, and each each extent of dilution is made two plates, in time pours cold to 45 a ℃ left and right sides meat soup protein culture medium into plate about 7ml then, and forwards plate to and make it to mix.After treating that agar solidifies, the upset plate, put 37 ℃ down cultivate 24h after, calculate dull and stereotyped in the bacterium colony number, multiply by extension rate, multiply by 2 again, promptly get the total number of bacterial colony among every ml, always represent with N.
3), get microbicide solution that 4ml prepared in test tube, add the 1ml original bacteria liquid, mix, act on to the specified time (1h), take out an amount of bacterium soup, do suitably dilution, get 0.5ml in aseptic plate,, add substratum by the method in above-mentioned (2), cultivate the back counting, bacterium colony number in dull and stereotyped multiply by extension rate, multiply by 10 again, promptly get the colony number of surviving in every ml bacterium soup, use N
LiveExpression.
4), sterilizing rate calculation formula:
Table 5EQ germicide series is to the sterilization effect of Bacillus subtilus
Table 6EQ germicide series is to colibacillary sterilization effect
Table 7EQ germicide series is to the sterilization effect of streptococcus aureus
Table 8EQ germicide series is to the oidiomycetic sterilization effect of white
Consolidated statement 5-table 8 as can be seen, along with concentration of sterilant increases, sterilizing rate is all in rising trend.Connect basicly when identical, along with alkyl chain length increases, fungicidal activity increases; When alkyl chain length is identical, increase along with connecting basic EO radix order, fungicidal activity decreases.
The minimal inhibitory concentration (MIC) of table 9EQ germicide series (mg/l)
The minimal bactericidal concentration (MBC) of table 10EQ germicide series (mg/l)
From table 9 with 10 as can be seen: connect basicly when identical, MIC and MBC are along with the increase of alkyl chain length has in various degree reduction; When alkyl chain length was identical, along with the increase that connects basic EO number, except part MIC and MBC data decrease, other data variation were little.To Bacillus subtilus, except the MIC of EQ08-0-08 is 40mg/l, MBC is 100mg/l, and all below 25mg/l, MBC is below 80mg/l for the MIC of other sterilant; To intestinal bacteria, the MIC of EQ germicide series is no more than 15mg/l, and MBC also is no more than 50mg/l; For streptococcus aureus and Candida albicans, except the MIC of EQ08-0-08 and indivedual sterilant and MBC were higher, the MIC of other sterilant was all less than 10mg/l, and MBC is all less than 20mg/l.
In sum, the EQ series compound has shown good fungicidal activity on the whole as sterilant, particularly to streptococcus aureus and Candida albicans, promptly can reach higher sterilizing rate under very low concentration.
The sustained release performance of bromination two-N-alkyl nicotinic acid ethylene glycol/glycol ether/triethyleneglycol ester (EQn-m-n) is measured
The sustained release performance of bromination two-N-hexadecyl nicotinic acid glycol ester (EQ16-0-16) is measured
A
3The rectangular parallelepiped carbon steel coupon, it is of a size of 30mm * 15mm * 2mm.Its chemical constitution is: 98.53%Fe, 0.27%C, 0.10%Cr, 0.05%Ni, 0.02%Mo, 0.05%Cu, 0.22%Si, 0.61%Mn, 0.15%S.Corrosive medium is 20% hydrochloric acid soln.
1) lacing film pre-treatment:
A
3Steel disc sample abrasive paper for metallograph 200#, 600#, 800# polish step by step to each the surface and corner angle be mirror-smooth, use distilled water flushing then, acetone and dehydrated alcohol oil removing, at last with under filter paper packet room temperature fortunately in moisture eliminator drying for standby.
2) lacing film experiment
The hydrochloric acid soln of 100mL 20% is placed 100mL ground Erlenmeyer flask, and in bottle, add the quaternary ammonium salt of different concns respectively, measure A with vernier callipers then
3The size of rectangular parallelepiped carbon steel coupon is calculated its area.Electronic balance weighs up its weight.With the cord of carrying out mark with A
3Steel disc hangs in the 100mL ground Erlenmeyer flask, and carbon steel coupon hangs on the middle part of solution, does blank assay (not being added with blank 20% hydrochloric acid soln of inhibiter) simultaneously.The ground Erlenmeyer flask is placed water bath with thermostatic control, under certain temperature, soak 3h.
3) lacing film aftertreatment
Experiment finishes the back and takes out carbon steel coupon from solution, and distilled water flushing is then with the soaked in absolute ethyl alcohol cleaning of dewatering in 5 minutes.Carbon steel coupon after the dehydration is put into the acetone oil removing, dry up with cold wind then, dry and weigh under the room temperature.By A
3Weight loss before and after the rectangular parallelepiped carbon steel coupon soaks in solution calculates its corrosion speed V (g/cm in hydrochloric acid
2H) and inhibition efficiency IE%.
4) calculating of erosion rate:
According to the weightlessness of test piece, can calculate the inhibition efficiency of absolute erosion rate and quaternary ammonium salt:
V＝(W
0-W)/St
W in the formula
0, the weight (g) before and after the W-test piece experiment;
Surface-area (the m of S-test piece
2);
T-inhibition experimental period (h);
V-erosion rate (g/m
2H)
The calculating of corrosion inhibition rate:
V in the formula
0-do not add the absolute erosion rate (g/m of the A3 carbon steel of quaternary ammonium salt
2H)
V-is added with the absolute erosion rate (g/m of the A3 carbon steel of quaternary ammonium salt
2H)
The inhibition efficiency of IE%-quaternary ammonium salt
IE％＝(V
0-V)/V
0×100％
The test of table 11 corrosion inhibition
| C(mg/L) | ΔW(g) | V(g/cm 2h×10 -3) | |
| 0 | 0.8756 | 282.4176499 | 0 |
| 10 | 0.6794 | 225.4754765 | 20.16 |
| 25 | 0.0511 | 16.90230665 | 94.02 |
| 50 | 0.0203 | 6.74905972 | 97.61 |
| 75 | 0.0199 | 6.5493135 | 97.68 |
| 100 | 0.032 | 10.36274799 | 96.33 |
Along with the concentration increase of EQ16-0-16, to the corrosion inhibition rate increase of A3 steel, when its concentration reached 50mg/l, corrosion inhibition rate reached 97%, illustrated that the sustained release performance of this inhibiter is fine.
The foaming properties research of bromination two-N-alkyl nicotinic acid ethylene glycol/glycol ether/triethyleneglycol ester (EQn-m-n)
In the identical 100ml tool plug graduated cylinder of specification, be respectively charged into the solution 10ml to be measured that concentration is cmc, shake under the speed in the maximum of shaking table simultaneously and vibrated 1 minute, in the foam height when just stopping as elemental height, foam height when measuring 5min and initial foam height liken measuring to for its stability.Foam height is that half time of original height is as the foamy transformation period.Every kind of solution repeats 3 times, averages, and experimental temperature is 20 ℃.Experimental result sees Table 12.
The whipability of table 12EQ series part of compounds
Data from table 12 as can be seen, the whipability of EQ Gemini surface active agent is very poor, so such tensio-active agent may use as defoamer.
Claims (2)
1. Gemini nicotinate quaternary ammonium salt, i.e. bromination two-N-alkyl nicotinic acid ethylene glycol/glycol ether/triethyleneglycol ester, its structural formula is as follows:
m＝0，1，2；n＝8，10，12，14，16。
2. the preparation method of Gemini nicotinate quaternary ammonium salt as claimed in claim 1 may further comprise the steps successively:
(1) with nicotinic acid and sulfur oxychloride by 1: 3-1: 6 mol ratio joins in the reaction flask, stirring and refluxing, NaOH solution absorption tail gas, behind the reaction 2-4h, cooling, decompression is spin-dried for the excess chlorination sulfoxide, white needle-like crystals nicotinic acid acyl chlorides;
(2) the nicotinic acid acyl chlorides is dissolved in the dry chloroform, slowly splashing into the nicotinic acid mol ratio is 1: 2 alcohol, and alcohol is ethylene glycol, glycol ether or triglycol, NaOH solution absorption tail gas, and backflow 4-10h is spin-dried for solvent after the cooling, add the suitable quantity of water dissolving, uses saturated Na
2CO
3The aqueous solution is regulated pH to neutrality or weakly alkaline, and alcoholysis product nicotinate suction filtration is dried;
(3) with nicotinate and bromoalkane by 1: 2-1: 6 mol ratio joins in the reaction flask, the carbonatoms of bromoalkane is 8,10,12,14 or 16, anhydrous acetonitrile is made solvent, reflux 30-40h, reaction is spin-dried for solvent after finishing, with anhydrous propanone washing, suction filtration, the gained white solid is the product Gemini nicotinate quaternary ammonium salt.
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| CN1557535A (en) * | 2004-01-13 | 2004-12-29 | ����ʦ����ѧ | Gemini quaternary surfactant containing pyridine rings and preparing method thereof |
| WO2007056284A2 (en) * | 2005-11-07 | 2007-05-18 | Stepan Company | Polycationic viscoelastic compositions |
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| CN1557535A (en) * | 2004-01-13 | 2004-12-29 | ����ʦ����ѧ | Gemini quaternary surfactant containing pyridine rings and preparing method thereof |
| WO2007056284A2 (en) * | 2005-11-07 | 2007-05-18 | Stepan Company | Polycationic viscoelastic compositions |
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| 黄奇然等.新型双季铵盐杀菌剂的合成和杀菌性能研究.广东化工34 3.2007,34(3),9、10、19. * |
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