CN103382157A - Process for preparing hexadecyl methyl 2-hydroxyethyl ammonium bromide - Google Patents
Process for preparing hexadecyl methyl 2-hydroxyethyl ammonium bromide Download PDFInfo
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- CN103382157A CN103382157A CN2013103518624A CN201310351862A CN103382157A CN 103382157 A CN103382157 A CN 103382157A CN 2013103518624 A CN2013103518624 A CN 2013103518624A CN 201310351862 A CN201310351862 A CN 201310351862A CN 103382157 A CN103382157 A CN 103382157A
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Abstract
The invention discloses a process for preparing hexadecyl methyl 2-hydroxyethyl ammonium bromide. The process comprises the steps of weighing N-methyldiethanolamine and bromohexadecane to be placed in a three-opening flask provided with a mechanical agitator, a reflux condensing tube and a thermometer, and heating for reaction in an oil bath pan; after reacting fully, using a mixed liquid of ethyl acetate and absolute ethyl alcohol to perform recrystallization on crude products, performing suction filtration to obtain bright white crystals, and performing vacuum drying to obtain the hexadecyl methyl 2-hydroxyethyl ammonium bromide. According to the process, the N-methyldiethanolamine and the bromohexadecane serve as raw materials, a quaternary ammonium salt surfactant of the hexadecyl methyl 2-hydroxyethyl ammonium bromide is synthesized through a solvent-free process, and no solvent is used during preparation, so that pollution caused by organic solvents and the recovery cost are reduced. Prepared products are good in solubilization, foaming property and emulsifying property.
Description
Technical field
The present invention relates to a kind of preparation method of hexadecyl methyl dihydroxy ethyl brometo de amonio.
Background technology
In the world to the existing very long history of the research of cats product, quaternary ammonium salt can be widely used in dye leveller, anti-static agent, fabric softener, antiseptic-germicide etc. as typical cats product, and has the functions such as fabulous conditioning, moisturizing, thickening, foam enhancing and emulsification.
Hexadecyl methyl dihydroxy ethyl brometo de amonio, chemical formula is C21H46BrNO2, structural formula is as shown in the formula (I).
Hexadecyl methyl dihydroxy ethyl brometo de amonio is a kind of important cats product, and existing preparation method reacts in the presence of solvent, and organic solvent is harmful and recovery difficulty mostly.Environmental protection more and more becomes all trades and professions to be paid attention to, and Chemical Manufacture require is reduced or stops pollute as target, does not solvent-freely syntheticly use organic solvent, not only can accelerate reaction efficiency and reduce pollution that solvent brings and the cost of recovery.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of hexadecyl methyl dihydroxy ethyl brometo de amonio of solvent-free participation is provided.
To achieve these goals, the present invention adopts following technical scheme:
A kind of preparation method of hexadecyl methyl dihydroxy ethyl brometo de amonio comprises the steps:
Take N methyldiethanol amine and bromohexadecane be placed in be furnished with mechanical stirrer, the there-necked flask of reflux condensing tube, thermometer, the oil bath pan reacting by heating; Fully after the reaction, adopt ethyl acetate and dehydrated alcohol mixed solution to carry out recrystallization to crude product, suction filtration gets the brilliant white crystal, after vacuum-drying and get final product.
In above-mentioned preparation method, the mol ratio of described bromohexadecane and N methyldiethanol amine is 0.5-3.5:1.Preferred mol ratio is 0.8-1.5:1, and the best is that mol ratio is 1.1:1.
In above-mentioned preparation method, described temperature of reaction is preferably 100-120 ℃, and best temperature is 110 ℃.
In above-mentioned preparation method, the described reaction times is preferably 110min.
In above-mentioned preparation method, the number of times of described recrystallization preferably 3 times.
In above-mentioned preparation method, preferably 50 ℃ of described vacuum drying temperature.
In above-mentioned preparation method, in described ethyl acetate and dehydrated alcohol mixed solution, the volume ratio of ethyl acetate and dehydrated alcohol is 1:1-10.
Compared with prior art, the present invention has following beneficial effect:
The present invention is take N methyldiethanol amine and bromohexadecane as raw material, adopt solventless method to synthesize hexadecyl methyl dihydroxy ethyl brometo de amonio quaternary surfactant, preparation process does not adopt solvent, thereby has reduced pollution that organic solvent brings and the cost of recovery.Prepared product has good characteristic of solubilizing, foaming properties and emulsifying property.
Description of drawings
Fig. 1 is the infrared absorption spectrum of synthetic product;
Fig. 2 is proton nmr spectra (1H NMR) figure of synthetic product;
Fig. 3 is the mass spectrum of synthetic product;
Fig. 4 is that the time is on the impact of MDEA transformation efficiency;
Fig. 5 is optical density(OD) and benzene relation with contents figure.
Embodiment
Reagent and instrument:
N methyldiethanol amine (, CR, company limited is moulded in Period In Maoming crowd and change; Bromohexadecane, CR, company limited is moulded in Period In Maoming crowd and change; Dialkyl group ester group hydroxyethyl methylsulfuric acid ammonium methyl (EQ), AR, Tianjin first photoinitiator chemical company limited; Distearyl dimethyl ammonium chloride (D1821), AR, Yixing Kai Lida chemistry company limited; All the other reagent are AR.
Fourier infrared spectrograph, TENSOR27, French BRUKER company; Vacuum drying oven, DZG-6050SA, the gloomy reliable Instr Ltd. that tests in Shanghai; The heat collecting type constant-temperature heating magnetic stirring apparatus, DF-101S, Yuhua Instrument Co., Ltd., Gongyi City; The circulating water type vacuum pump, the SHZ-D(III), the Ying Yu of Gongyi City gives magnificent instrument plant.The full-automatic interfacial tensimeter of BZY-1, Zibo Boshan sea minute instrument plant; WRS-1B type numeral melting point instrument, Shanghai Precision Scientific Apparatus Co., Ltd.
Embodiment 1:
Take N methyldiethanol amine and bromohexadecane be placed in be furnished with mechanical stirrer, the there-necked flask of reflux condensing tube, thermometer, the mol ratio of bromohexadecane and N methyldiethanol amine is 1.1:1, reaction under the oil bath pan heating, temperature of reaction is 110 ℃.After reaction 110min, after adopting ethyl acetate and dehydrated alcohol mixed solution with crude product recrystallization 3 times, suction filtration gets the brilliant white crystal, after 50 ℃ of lower vacuum-drying and get final product.Recording its fusing point is 120.09 ℃.
Embodiment 2:
Take N methyldiethanol amine and bromohexadecane be placed in be furnished with mechanical stirrer, the there-necked flask of reflux condensing tube, thermometer, the mol ratio of bromohexadecane and N methyldiethanol amine is 1.2:1, reaction under the oil bath pan heating, temperature of reaction is 120 ℃.After reaction 110min, after adopting ethyl acetate and dehydrated alcohol mixed solution with crude product recrystallization 3 times, suction filtration gets the brilliant white crystal, after 50 ℃ of lower vacuum-drying and get final product.Recording its fusing point is 121.03 ℃.
Embodiment 3:
Take N methyldiethanol amine and bromohexadecane be placed in be furnished with mechanical stirrer, the there-necked flask of reflux condensing tube, thermometer, the mol ratio of bromohexadecane and N methyldiethanol amine is 0.9:1, reaction under the oil bath pan heating, temperature of reaction is 100 ℃.After reaction 110min, after adopting ethyl acetate and dehydrated alcohol mixed solution with crude product recrystallization 3 times, suction filtration gets the brilliant white crystal, after 50 ℃ of lower vacuum-drying and get final product.Recording its fusing point is 121 ℃.
Embodiment 4: embodiment 1 products therefrom is identified
Product analysis method: adopt hydrochloric acid-ethanol volumetry to come the transformation efficiency of N methyldiethanol amine in determination test.Adopt thin layer chromatography initial analysis product to generate, utilizing has the cation activity thing to exist in the legal property of tetrabromophenol sulfonphthalein product.Adopt two-phase titration to measure the purity of purified product greater than 99%.
Product is carried out the IR(KBr compressing tablet),
1HNMR(CD
3SOCD
3) and the positive ion mode (ESI of electrospray ionization mass spectrum
+/ ES) analyze, identified product structure and molecular weight.
Measurement of surface tension: product is mixed with 0.1% the aqueous solution, adopts the platinum loop method to measure the surface tension of quaternary ammonium salt.
Krafft's point test: product is mixed with 0.1% the aqueous solution, puts into temperature lower than the saturated aqueous common salt of 0 ℃, observation is to have crystal to separate out.
Foaming power is measured: adopt standard GB/T7462-1994, improved ROSS-Mise measures foaming and steady bubble ability.
Compatibilization ability is measured: product is mixed with the aqueous solution of not allowing concentration increases benzene in the dissolving power of distilled water, when the content arrival of benzene was a certain amount of, system just can produce muddiness and layering.When measuring the optical density(OD) of system with ultraviolet-visible pectrophotometer, optical density(OD) can obviously rise, and can measure thus the solubilising of product.Add nine samples of 0～0.4mL benzene respectively in 50ml concentration is the liquid to be measured of 0.002mol/L, place its absorbancy of test after 24 hours.
Emulsifying power performance measurement: adopt quantitative method GB11543-1989 to measure.Infrared absorption spectrum: as shown in Figure 1, be 3294cm at wavelength
-1The place is-the OH absorption peak, at wavelength 2921cm
-1And 2852cm
-1Be respectively the flexible shock absorbing of the C-H peak of methyl and methylene radical, 1465cm
-1The place is C-N key, 1164cm
-1The place shears absorption peak, 1050cm for methylene radical
-1The place shears absorption peak, last 628cm for methyl
-1Be-(CH2) n-absorption peak.Tentatively can be defined as desired product thus.
Nuclear magnetic resonance map: can be got by Fig. 2, numbers of hydrogen atoms is 42, and product structure is identical with setting.Can be drawn by Fig. 2 that on each group, H chemical shift δ is: R-CH
3*, 0.82～0.84,3H, N+ (CH
2)
4-(CH
2*)
9-CH
3, 1.21～1.23,18H, N+CH
2CH
2(CH
2*)
2, 1.25～1.30,4H, CH
3N+-CH
2-CH
2*, 1.70,2H, N+-CH
3*, 3.29,3H, N+-CH
2-CH
2* R, 3.50～3.52,2H, N-CH
2-CH
2*-OH, 3.65～3.93,4H, N-CH
2*-CH
2-OH, 4.06,4H, OH*, 4.72～4.74,2H.The chemical shift of product hydrogen proton is corresponding one by one with product structure, therefore can determine that embodiment 1 products obtained therefrom is target compound.
Mass spectroscopy: with mass spectrograph, product is scanned, with ESI as ion source, positive ion mode, result as shown in Figure 3,315.9(M+H)+, be the cationic molecular weight 316 of target product and meet.
Embodiment 5: the performance test of embodiment 1 product
Surface tension: the surface tension that experiment records product water solution is 24.8Nm-1, and the surface tension of water is from 71.5Nm
-1Obviously be reduced to 24.8mNm
-1, product has good surfactivity as can be known, is a kind of surface property new surface active agents preferably.
The Krafft point: the aqueous solution is cooled to below 0 ℃, separates out without any material, shows thus at Krafft o'clock of product below 0 ℃.
Product foaming properties: the foaming properties contrast of hexadecyl methyl dihydroxy ethyl brometo de amonio (TMDAB), dialkyl group ester group hydroxyethyl methylsulfuric acid ammonium methyl (EQ) and octadecyl alkyl dimethyl ammonium chloride (DODMAC), can find out the market tensio-active agent commonly used of comparing, this experimental product has preferably foaming power but the ability of surely steeping is general, after 5min, foam height descends obviously, and result is as shown in table 1:
The foaming properties of table 1 tensio-active agent
Product is to the benzene characteristic of solubilizing: measure the solution that contains different concns benzene, Fig. 5 is absorbance data figure corresponding to different concns solution.
Can be drawn by Fig. 5, TMDAB is 0.2195mL to the solubilising limit A of benzene, and the following formula of substitution calculates:
Calculating its compatibilization ability X is 1322mL/mol, the situation lower in concentration has been issued to the limit, explanation can reach micelle-forming concentration at this kind tensio-active agent of low concentration, consumption can reach solute effect preferably less, oil can be distributed to the aqueous solution under comparatively low concentration in, solubilizing effect is better.
The emulsifying property performance of product:
Measure the emulsifying property of hexadecyl methyl dihydroxy ethyl brometo de amonio (TMDAB) and commercial surfactant EQ and D1821, result such as table 2, TMDAB have very strong emulsifying capacity.All be better than other two kinds of tensio-active agents at turps-water and kerosene-aqueous systems, and benzene-aqueous systems is inferior a little.
The emulsifying property of table 2 tensio-active agent
Embodiment 6: the impact of temperature of reaction on the N methyldiethanol amine transformation efficiency
Claim 40.0g bromohexadecane and 17.184g MDEA(N-methyldiethanolamine) in Florence flask, stir with mechanical stirrer, be 90 ℃, 100 ℃, 110 ℃, 120 ℃ in temperature of reaction respectively, reactant molar ratio is to test under the condition of 1.1:1, and the reaction times is 110min.
Experimental result such as following table 3:
The impact of table 3 temperature of reaction on the MDEA transformation efficiency
As can be seen from Table 3, along with the rising of temperature of reaction, the transformation efficiency of MDEA increases gradually, but after surpassing 110 ℃, the growth of the transformation efficiency of MDEA is not obvious.This is because higher temperature is conducive to the nucleophilic addition(Adn) of bromohexadecane and MDEA, and accelerated reaction is carried out toward positive dirction.But can find out that from the product color and luster temperature crosses product color and deepen, this is due to the generation of by product and the aerial oxygenizement of MDEA, and the high temperature energy consumption strengthens, so this reaction optimum temps is 110 ℃.
Embodiment 7: the impact of reactant molar ratio on the MDEA transformation efficiency
Be 110 ℃ in temperature of reaction, MDEA and bromohexadecane reaction 110min.Respectively at the n(bromohexadecane): n(MDEA) be 0.9:1.0,1.0:1.0,1.1:1 reacts under the different proportionings of 1.2:1.0.Then sampling and measuring transformation efficiency.Obtain a result as shown in table 4:
As can be seen from Table 4, along with the n(bromohexadecane): the n(MDEA) rising of ratio, the transformation efficiency of MDEA increases gradually, due to the tertiary amine content in experiment drop reaction system, when MDEA during higher than theoretical addition transformation efficiency not high, still have remaining MDEA to exist due to reaction after reaching balance, but mol ratio during higher than 1.1:1.0 transformation efficiency improve and not obvious, comparatively speaking, adopt bromohexadecane excessive slightly can be conducive to react toward positive dirction carry out.
The impact on the MDEA transformation efficiency of table 4, reactant molar ratio
Embodiment 8: the impact of time on transformation efficiency
Be 110 ℃ in temperature of reaction, n(bromohexadecane): n(MDEA) react under the condition of 1.1:1, be determined at 15,30,45,60,75,90,105, the transformation efficiency of MDEA under 120min.As seen from Figure 4, the transformation efficiency of MDEA rises along with the increase in reaction times, and the transformation efficiency of MDEA increases progressively and tends towards stability after reaction times 110min, is 110min so select the most suitable reaction times.
Embodiment 9: Optimization Technology is heavily tested
Determine with 110 ℃ of temperature of reaction, n(bromohexadecane by the experiment of single factor result): n(MDEA)=1.1:1, the reaction times is 110min, carries out repeated experiments three times, result as: 5:
Table 5 Optimization Technology repeated experiments result
As can be seen from Table 5, repeat 3 experiments under optimal conditions, the MDEA transformation efficiency is all more than 96%, and this condition circulation ratio is better, can be used as Optimizing Technical.
Claims (10)
1. the preparation method of a hexadecyl methyl dihydroxy ethyl brometo de amonio, is characterized in that comprising the steps:
Take N methyldiethanol amine and bromohexadecane be placed in be furnished with mechanical stirrer, the there-necked flask of reflux condensing tube, thermometer, the oil bath pan reacting by heating; Fully after the reaction, adopt ethyl acetate and dehydrated alcohol mixed solution to carry out recrystallization to crude product, suction filtration gets the brilliant white crystal, after vacuum-drying and get final product.
2. preparation method as claimed in claim 1, is characterized in that, the mol ratio of described bromohexadecane and N methyldiethanol amine is 0.5-3.5:1.
3. preparation method as claimed in claim 2, is characterized in that, the mol ratio of described bromohexadecane and N methyldiethanol amine is 0.8-1.5:1.
4. preparation method as claimed in claim 2, is characterized in that, the mol ratio of described bromohexadecane and N methyldiethanol amine is 1.1:1.
5. preparation method as claimed in claim 1, is characterized in that, described temperature of reaction is 80-150 ℃.
6. preparation method as claimed in claim 4, is characterized in that, described temperature of reaction is 110 ℃.
7. preparation method as claimed in claim 1, is characterized in that, the described reaction times is 110min.
8. preparation method as claimed in claim 1, is characterized in that, the number of times of described recrystallization is 3 times.
9. preparation method as claimed in claim 1, is characterized in that, described vacuum drying temperature is 50 ℃.
10. preparation method as claimed in claim 1, is characterized in that, in described ethyl acetate and dehydrated alcohol mixed solution, the volume ratio of ethyl acetate and dehydrated alcohol is 1:1-10.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103965061A (en) * | 2014-01-15 | 2014-08-06 | 广州大学 | Solvent-free synthesis method of myristyl methyl dihydroxyethyl ammonium bromide |
| CN104928919A (en) * | 2015-07-10 | 2015-09-23 | 广州大学 | Soft coordinative antibiosis brush type multi-season ammonium salt textile finishing agent and preparation method thereof |
| CN105176504A (en) * | 2015-09-25 | 2015-12-23 | 西南石油大学 | Multi-hydroxyl organic amine water-based drilling fluid shale inhibitor and preparation method thereof |
| CN110256758A (en) * | 2019-05-16 | 2019-09-20 | 广州大学 | A kind of antibiotic plastic and preparation method thereof based on microwave synthesis quaternary ammonium salt |
| CN110563906A (en) * | 2019-08-15 | 2019-12-13 | 深圳大学 | Shape memory polyurethane and preparation method and application thereof |
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| CN102807510A (en) * | 2012-07-06 | 2012-12-05 | 华南理工大学 | Antibacterial methacrylate monomer containing quaternary ammonium structure and preparation method and application of antibacterial methacrylate monomer |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103965061A (en) * | 2014-01-15 | 2014-08-06 | 广州大学 | Solvent-free synthesis method of myristyl methyl dihydroxyethyl ammonium bromide |
| CN104928919A (en) * | 2015-07-10 | 2015-09-23 | 广州大学 | Soft coordinative antibiosis brush type multi-season ammonium salt textile finishing agent and preparation method thereof |
| CN105176504A (en) * | 2015-09-25 | 2015-12-23 | 西南石油大学 | Multi-hydroxyl organic amine water-based drilling fluid shale inhibitor and preparation method thereof |
| CN110256758A (en) * | 2019-05-16 | 2019-09-20 | 广州大学 | A kind of antibiotic plastic and preparation method thereof based on microwave synthesis quaternary ammonium salt |
| CN110563906A (en) * | 2019-08-15 | 2019-12-13 | 深圳大学 | Shape memory polyurethane and preparation method and application thereof |
| CN110563906B (en) * | 2019-08-15 | 2021-11-16 | 深圳大学 | Shape memory polyurethane and preparation method and application thereof |
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Application publication date: 20131106 |