CN103965061A - Solvent-free synthesis method of myristyl methyl dihydroxyethyl ammonium bromide - Google Patents
Solvent-free synthesis method of myristyl methyl dihydroxyethyl ammonium bromide Download PDFInfo
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- CN103965061A CN103965061A CN201410019264.1A CN201410019264A CN103965061A CN 103965061 A CN103965061 A CN 103965061A CN 201410019264 A CN201410019264 A CN 201410019264A CN 103965061 A CN103965061 A CN 103965061A
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Abstract
A solvent-free synthesis method of myristyl methyl dihydroxyethyl ammonium bromide is characterized by comprising the following steps: N-MEDA (methyldiethanolamine) and bromotetradecane are placed in a reaction vessel for a reaction at certain temperature, stirring is performed continuously, a solvent is added for recrystallization after the reaction is finished, a product is obtained through suction filtration, and bright white crystals are obtained and subjected to vacuum drying to obtain pure myristyl methyl dihydroxyethyl ammonium bromide. Compared with the prior art, the solvent-free synthesis method has the advantages that bromotetradecane and N-MEDA are taken as the raw materials and synthesized without a solvent, the whole process is simple to operate, pollution-free, environment-friendly and feasible, and the product has higher conversion rate and purity via detection.
Description
Technical field
The present invention relates to a kind of tetradecyl methyl dihydroxy ethyl brometo de amonio preparation method, tetradecyl methyl dihydroxy ethyl brometo de amonio can be used as tensio-active agent and is applied to weaving and the technical field such as antibacterial.
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.This experiment is the research to the long chain alkyl ammonium salt with two hydroxyls in conjunction with seminar, is synthesizing on the working foundation of long chain quaternary of 12 carbon and 18 carbon, then develops the quaternary ammonium salt of four carbonatomss of putting the palms together before one.Carbon chain lengths difference must have different impacts to its performance, will be conducive to the impact of backward more deep research structure on performance etc. for the research of this novel quaternary ammonium salt.
Environmental protection more and more becomes all trades and professions to be paid attention to, and Chemical Manufacture is required to reduce or is stopped and pollute as target, and most organic reaction is all to react in the presence of solvent, and how harmful organic solvent is and reclaim difficult.Solvent-freely synthetic do not use organic solvent, not only can accelerate reaction efficiency and reduce pollution that solvent brings and the cost of recovery.
Summary of the invention
Technical problem to be solved by this invention is the synthetic method that a kind of simple to operate, tetradecyl methyl dihydroxy ethyl brometo de amonio solventless method that environmental protection is feasible is provided for the above-mentioned state of the art.
Technical problem to be solved by this invention is the synthetic method that the tetradecyl methyl dihydroxy ethyl brometo de amonio solventless method that a kind of transformation efficiency and purity are high is provided for the above-mentioned state of the art.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of synthetic method of tetradecyl methyl dihydroxy ethyl brometo de amonio solventless method, is characterized in that comprising the steps:
N methyldiethanol amine and bromotetradecane are placed in reaction vessel and react, and, constantly stirring, its reaction formula is as follows
Reaction finishes, and carries out, after recrystallization, obtaining product, and suction filtration, obtains brilliant white crystal, is pure tetradecyl methyl dihydroxy ethyl brometo de amonio after vacuum-drying.
As preferably, described bromotetradecane and N methyldiethanol amine mol ratio are 0.9:1～1.2:1.
As preferably, described reaction is heated and is carried out in oil bath pan, and heating and temperature control is at 90～120 DEG C.
As preferably, the described reaction times is 15～120min.
Further, described recrystallization adopts ethyl acetate and dehydrated alcohol mixed solution, and ethyl acetate and dehydrated alcohol volume ratio are 8:1.
Described reaction vessel can be reactor or there-necked flask.
Further, described vacuum-drying temperature is 50 DEG C.
As the best, described bromotetradecane and N methyldiethanol amine mol ratio are 1.1:1, and described reaction is heated and carried out in oil bath pan, and heating and temperature control is at 110 DEG C, and the described reaction times is 110min.
Compared with prior art, the invention has the advantages that: taking bromotetradecane and N methyldiethanol amine (MDEA) as raw material, by solvent-free synthetic, whole flow operations is simple, pollution-free, and environmental protection is feasible, and, products therefrom after testing transformation efficiency and purity all higher.
Brief description of the drawings
Fig. 1 is the infrared absorption spectrum graphic representation 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 the influence curve figure of reaction times to MDEA transformation efficiency.
Fig. 5 is optical density(OD) and benzene relation with contents figure.
Embodiment
Below in conjunction with accompanying drawing, embodiment is described in further detail the present invention.
1.1 reagent and instrument
N methyldiethanol amine (, CR, Period In Maoming crowd and Hua Su company limited; Bromotetradecane, CR, Period In Maoming crowd and Hua Su company limited; 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 Chemical Co., Ltd.; All the other reagent are AR.
Fourier infrared spectrograph, TENSOR27, French BRUKER company; Vacuum drying oven, DZG-6050SA, the gloomy reliable Instrument Ltd. that tests in Shanghai; Heat collecting type constant-temperature heating magnetic stirring apparatus, DF-101S, Yuhua Instrument Co., Ltd., Gongyi City; Circulating water type vacuum pump, SHZ-D(III), Ying Yu Yu Hua instrument plant of Gongyi City.The full-automatic interfacial tensimeter of BZY-1, Zibo Boshan Hai Fen instrument plant; WRS-1B type numeral melting point instrument, Shanghai Precision Scientific Apparatus Co., Ltd.
1.2 method
1.2.1 synthesis step
Take a certain amount of N methyldiethanol amine and bromotetradecane be placed in be furnished with mechanical stirrer, the there-necked flask of reflux condensing tube, thermometer, be studied in its synthesis condition of oil bath pan reacting by heating.Its reaction formula is as follows
Adopt ethyl acetate and dehydrated alcohol mixed solution by after crude product recrystallization 3 times, wherein, in ethyl acetate and dehydrated alcohol mixed solution, volume ratio is 8:1, and suction filtration obtains brilliant white crystal, is pure product after 50 DEG C of vacuum-drying.Recording its fusing point is 120.09～121.03 DEG C.
1.3 product analysis method
Adopt hydrochloric acid-ethanol volumetry to carry out the transformation efficiency of N methyldiethanol amine in determination test.Adopt thin layer chromatography initial analysis product to generate, utilize in the legal property of tetrabromophenol sulfonphthalein product and have cation activity thing to exist.The purity that adopts two-phase titration to measure purified product is greater than 99%.
Product is carried out to IR(KBr compressing tablet),
1hNMR(CD3SOCD3) and the positive ion mode of electrospray ionization mass spectrum (ESI+/ES) analyze, identified product structure and molecular weight.
1.4 performance test
Measurement of surface tension: product is mixed with to 0.1% the aqueous solution, adopts platinum loop method to measure the surface tension of quaternary ammonium salt.
Krafft's point test: product is mixed with to 0.1% the aqueous solution, puts into temperature lower than the saturated aqueous common salt of 0 DEG C, 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 and does not allow the aqueous solution of concentration to increase the dissolving power of benzene at distilled water, and when the content of benzene arrives when a certain amount of, system just can produce muddiness and layering.When the optical density(OD) of measuring system with ultraviolet-visible pectrophotometer is that optical density(OD) can obviously rise, and can measure thus the solubilising of product.In the liquid to be measured that is 0.002mol/L toward 50ml concentration respectively, add nine samples of 0～0.4mL benzene, place and test its absorbancy after 24 hours.
Emulsifying power performance measurement: adopt quantitative method GB11543-1989 to measure.
2 results and discussion
The analysis and characterization of 2.1 products
2.1.1 infrared absorption spectrum
As shown in Figure 1, be 3294cm at wavelength
-1place is-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
-1place is C-N key, and 1164cm-1 place is methylene radical shearing absorption peak, 1050cm
-1place is methyl shearing absorption peak, last 628cm
-1be-(CH2) n-absorption peak.Tentatively can be defined as thus desired product.
2.1.2 nuclear magnetic resonance map
By Fig. 2 Tu Ke get, numbers of hydrogen atoms is 42, and product structure is identical with setting.Can show that by Fig. 2 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 and synthesize this product.
2.1.3 mass spectroscopy
Product is scanned with mass spectrograph, 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.
2.2 optimization of synthesis
2..2.1 the impact of temperature of reaction on MDEA transformation efficiency
Claim 40.0g bromotetradecane and 17.184g MDEA(N-methyldiethanolamine) in Florence flask, stir with mechanical stirrer, be 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C in temperature of reaction respectively, under the condition that reactant molar ratio is 1.1:1, test, the reaction times is 110min.Experimental result is as following table:
The impact of table 1 temperature of reaction on MDEA transformation efficiency
As can be seen from Table 1, along with the rising of temperature of reaction, the transformation efficiency of MDEA increases gradually, but after exceeding 110 DEG C, the growth of the transformation efficiency of MDEA is not obvious.This is because higher temperature is conducive to the nucleophilic addition(Adn) of bromotetradecane and MDEA, and accelerated reaction is carried out toward positive dirction.But from product color and luster can find out temperature cross product color deepen, this is due to the generation of by product and the aerial oxygenizement of MDEA, thus high temperature energy consumption strengthen this reaction optimal conditions choose 110 DEG C.
2..2.2 the impact of reactant molar ratio on MDEA transformation efficiency
Be 110 DEG C in temperature of reaction, MDEA reacts 110min with bromotetradecane.Respectively at n(bromotetradecane): 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 2:
The impact of table 2 reactant molar ratio on MDEA transformation efficiency
Table2Effect of reactant molar ratio on conversion rate of MDEA
As can be seen from Table 2, along with n(bromotetradecane): 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, because reaction still has remaining MDEA to exist after reaching balance, but mol ratio during higher than 1.1:1.0 transformation efficiency improve and not obvious, comparatively speaking, adopt bromotetradecane excessive slightly can be conducive to react toward positive dirction carry out.
2.2.3 the impact of time on transformation efficiency
Be 110 DEG C in temperature of reaction, n(bromotetradecane): n(MDEA) under the condition for 1.1:1, react, be determined at 15,30,45,60,75,90,105, the transformation efficiency of MDEA under 120min.As can be seen from Figure, the transformation efficiency of MDEA rises along with the increase in reaction times, and after reaction times 110min, the transformation efficiency of MDEA increases progressively and tends towards stability, and is 110min so select the most suitable reaction times.
2.2.4 Optimization Technology is heavily tested
Determine with 110 DEG C of temperature of reaction, n(bromotetradecane by experiment of single factor result): n(MDEA)=1.1:1, the reaction times is 110min, carries out repeating for three times experiment, result is as shown:
Table 3 Optimization Technology repeats experimental result
Can be found out by table, under optimal conditions, repeat 3 experiments, MDEA transformation efficiency is all more than 96%, and this condition circulation ratio is better, can be used as Optimizing Technical.
2.2.4 amplification test
Determine optimum process condition by experiment of single factor, adopt amplification method step by step to carry out amplification test, along with the increase of magnification, the transformation efficiency of MDEA decreases.This is due to along with amplification, the temperature distribution difference of material, and mixing effect is inhomogeneous, causes transformation efficiency to be not so good as little test result.Amplifying 40 times of experiments, transformation efficiency still reaches on 90%, illustrates that this synthesis technique has the possibility of further raising output.
Table 4 amplification test result
Some problems that occur in amplification process need be adjusted reaction conditions.When be amplified to 40 times while carrying out in 10 liters of reactors, because quaterisation belongs to thermopositive reaction, the heat that iodine produces can not distribute rapidly and cause temperature fast rise, and the rising of temperature is conducive on the one hand the carrying out of reaction but also causes the production of by product, causes product color and luster dark.And along with reaction is carried out, the viscosity of reaction system increases gradually, and product becomes more and more thickness, cause the mixing of stirring inhomogeneous raw material to be affected.For this reason, in the time that magnification is larger, temperature of reaction should be adjusted into 95～100 DEG C, stirring velocity is by changing to low speed fast at the beginning.Also raw material MDEA can be added in addition in batches, can effectively avoid the play liter of temperature also can improve stirring problem of non-uniform.
2.2 performance test
2.2.1 surfactivity
Surface tension: the surface tension that experiment records product water solution is 24.8Nm
-1, the surface tension of water is from 71.5Nm
-1obviously be reduced to 24.8mNm
-1, known product has good surfactivity, is the good new surface active agents of a kind of surface property.
Krafft point: the aqueous solution is cooled to below 0 DEG C, separates out without any material, shows that below 0 DEG C thus at Krafft o'clock of product.
2.2.2 product foaming properties
Tetradecyl methyl dihydroxy ethyl brometo de amonio performance (TMDAB), dialkyl group ester group hydroxyethyl methylsulfuric acid ammonium methyl (EQ) and the contrast of octadecyl alkyl dimethyl ammonium chloride (DODMAC) foaming properties, can find out the tensio-active agent that the market of comparing is conventional, this experimental product has good foaming power but the ability of surely steeping is general, after 5min, foam height declines obviously, and it is as shown in the table for result:
The foaming properties of table 5 tensio-active agent
2.2.2 product is to benzene characteristic of solubilizing
Measure the solution containing different concns benzene, Fig. 5 is the absorbance data figure that different concns solution is corresponding.
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, illustrate at this kind of tensio-active agent of low concentration and can reach micelle-forming concentration, consumption can reach good solute effect less, under comparatively low concentration, oil can be distributed in the aqueous solution, solubilizing effect is better.
2.2.3 the emulsifying property performance of product
The emulsifying property of measuring tetradecyl methyl dihydroxy ethyl brometo de amonio (TMDAB) and commercial surfactant EQ and D1821, result is as following table, and TMDAB has very strong emulsifying capacity.All be better than other two kinds of tensio-active agents at turps-water and coal oil-water system, and benzene-aqueous systems is inferior a little.
The emulsifying property of table 6 tensio-active agent
3 conclusions
(1) taking bromotetradecane and N methyldiethanol amine as raw material, adopt solvent-free synthetic synthesis method to synthesize tetradecyl methyl dihydroxy ethyl brometo de amonio.Analyzing optimum synthesis condition by single-factor influence is: n(bromotetradecane): n(MDEA)=1.1:1, the reaction times is 110min, temperature of reaction is 110 DEG C.With this understanding, peak rate of conversion is 96.78%.Carry out amplification test at 10L reactor, record MDEA transformation efficiency more than 90%.
(2) adopt recrystallization method to obtain the crystal that purity is high, the product purity that adopts two-phase titration to measure after recrystallization is greater than 99%.By IR,
1h NMR spectrogram has been identified the structure of product, and the compound of determining synthesized is target product tetradecyl methyl dihydroxy ethyl brometo de amonio.
(3) integrated survey product properties, recording product surface tension is 24.8mNm
-1, there is good characteristic of solubilizing, foaming properties and emulsifying property simultaneously.
Claims (8)
1. a synthetic method for tetradecyl methyl dihydroxy ethyl brometo de amonio solventless method, is characterized in that comprising the steps:
N methyldiethanol amine and bromotetradecane are placed in reaction vessel and react, and, constantly stirring, its reaction formula is as follows
Reaction finishes, and carries out, after recrystallization, obtaining product, and suction filtration, obtains brilliant white crystal, is pure tetradecyl methyl dihydroxy ethyl brometo de amonio after vacuum-drying.
2. synthetic method according to claim 1, is characterized in that described bromotetradecane and N methyldiethanol amine mol ratio are 0.9:1～1.2:1.
3. synthetic method according to claim 1, the reaction described in it is characterized in that is heated and is carried out in oil bath pan, and heating and temperature control is at 90～120 DEG C.
4. synthetic method according to claim 1, is characterized in that the described reaction times is 15～120min.
5. synthetic method according to claim 1, it is characterized in that described recrystallization adopts ethyl acetate and dehydrated alcohol mixed solution, and, ethyl acetate and dehydrated alcohol volume ratio are 8:1, temperature is 80～85 DEG C makes solution boiling, treats that solution becomes thorough clarification to stop heating, leaves standstill to normal temperature, suction filtration, obtains brilliant white crystal.
6. synthetic method according to claim 1, is characterized in that described reaction vessel is reactor or there-necked flask.
7. synthetic method according to claim 1, is characterized in that described vacuum-drying temperature is 50 DEG C.
8. synthetic method according to claim 1, is characterized in that described bromotetradecane and N methyldiethanol amine mol ratio are 1.1:1, and described reaction is heated and carried out in oil bath pan, and heating and temperature control is at 110 DEG C, and the described reaction times is 110min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104817463A (en) * | 2015-03-16 | 2015-08-05 | 广州大学 | Preparation method for tetradecyl methyldihydroxyethyl ammonium bromide |
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| CN102816089A (en) * | 2012-07-06 | 2012-12-12 | 华南理工大学 | Quaternary ammonium salt and carbamate structure containing antibacterial methyl acrylate monomer, its preparation method and application thereof |
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Application publication date: 20140806 |