CN104817463A - Preparation method for tetradecyl methyldihydroxyethyl ammonium bromide - Google Patents
Preparation method for tetradecyl methyldihydroxyethyl ammonium bromide Download PDFInfo
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Abstract
The invention discloses a preparation method for tetradecyl methyldihydroxyethyl ammonium bromide. The method includes the steps of: mixing bromotetradecane with N-methyldiethanolamine according to a mole ratio of 1:1, dissolving the mixture in n-pentanol, conducting reflux reaction in microwave, at the end of reaction, adding an ethanol-ethyl acetate mixed solvent into the reaction solution to crystallize the product so as to obtain a white solid; and during reflux, always maintaining continuous action of microwave and boiling of the reaction solution. Compared with traditional methods, the method provided by the invention has enhanced target product conversion rate, and the required reaction time is 27% of that of the traditional methods.
Description
Technical field:
The present invention relates to chemical field, specifically, relate to a kind of preparation method of tetradecylmethyl dihydroxy ethyl brometo de amonio.
Background technology:
Quaternary ammonium salt is widely used in dye leveller, anti-static agent, fabric softener and antiseptic-germicide etc. as typical cats product, and has the functions such as fabulous conditioning, moisturizing, thickening, foam enhancing and emulsification.N methyldiethanol amine (MDEA) is a kind of selective desulfurization, decarburization novel dissolvent of excellent property, has the advantages such as selectivity is high, solvent consumption is few, energy-saving effect is remarkable.In addition, MDEA also can be used as intermediate, sterilant, emulsifying agent, the work in-process of textile auxiliaries, the catalyzer, textile auxiliary agent etc. of amidocarbonic acid ester paint of antitumor drug mustine hydrochlcride, and is also a kind of drying promoter of paint.Current MDEA crosses Sheng in the output of China, can carry out further research and probe and exploitation.Chen Yuekai proposes and synthesizes new tensio-active agent tetradecylmethyl dihydroxy ethyl brometo de amonio with MDEA and bromotetradecane in its paper " uninanned platform quaternary ammonium salt tetradecylmethyl dihydroxy ethyl brometo de amonio ", the synthetic method of its optimum is: mixed according to n (bromotetradecane): n (MDEA)=1.1:1.0 with MDEA by bromotetradecane, at temperature of reaction is 110 DEG C, reacts 110min, adopts mixed solvent to carry out recrystallization purification to product.This article also points out that in this synthetic method, temperature of reaction selects 100-110 DEG C to be advisable, and temperature of reaction is lower, and speed of response is slow, and transformation efficiency is not high; Temperature of reaction is too high, easily produces a large amount of by product, and product colour is deepened, and affects outward appearance.
Summary of the invention:
The object of the present invention is to provide a kind of preparation method of high efficiency tetradecylmethyl dihydroxy ethyl brometo de amonio.
The technical scheme that the present invention solves the problems of the technologies described above is:
A kind of preparation method of tetradecylmethyl dihydroxy ethyl brometo de amonio, bromotetradecane is comprised the steps: to mix according to mol ratio 1:1 with N methyldiethanol amine (MDEA), be dissolved in Pentyl alcohol, back flow reaction in microwave, in reaction solution, add EtOH-EtOAc mixed solvent after reaction terminates and make product crystallization, obtain white solid; In reflux course, remain the continuous action of microwave and the boiling of reaction solution.
In above-mentioned preparation method, described Pentyl alcohol consumption is 5% ~ 60% for accounting for reactant mass percent, and reflux temperature is 125 ~ 145 DEG C, and microwave power is 300 ~ 600W, and reflux time is 25 ~ 30min.
In above-mentioned preparation method, optimum scheme is: described Pentyl alcohol consumption is for accounting for reactant mass percent 15%, and reflux temperature 135 DEG C, microwave power is 400W, and reflux time is 30min.The transformation efficiency of the tetradecylmethyl dihydroxy ethyl brometo de amonio under preferred embodiment can reach 91.34%.
In the inventive method, the ratio (volume ratio) of EtOH-EtOAc mixed solvent is preferably 1:4.
The reaction formula of the inventive method is as follows:
In the methods of the invention, remain that the continuous action of microwave and the boiling of reaction solution are one of important features.For different microwave equipments, its mode controlled is different, therefore ensures that the technique means of described back flow reaction condition will depending on different microwave equipments.For conventional Temperature Control Type microwave equipment, the equipment of this type will stop microwave heating automatically once reach design temperature, just can not give full play to the effect of microwave continuous effect in the case.Therefore to carry out back flow reaction, temperature of reaction is set to the boiling temperature of reaction system or a little higher than boiling temperature, can ensure that reaction system keeps boiling like this.
The present invention adopts the synthesis of microwave catalysis tetradecylmethyl dihydroxy ethyl brometo de amonio, and the basis ensureing tetradecylmethyl dihydroxy ethyl brometo de amonio productive rate substantially reduces the reaction times.Compared with the conventional method, the transformation efficiency of target product increases the inventive method, and the required reaction times is 27% of traditional method.Microwave has non-heated effect, compound high-speed rotation can be made to produce efficient molecular impact and cause reducing reaction activity, change reaction kinetics, accelerate chemical reaction process, thus Reaction time shorten; In the range of microwave power that the inventive method specifies, although the temperature of reaction system can up to 140 DEG C, but because microwave has the effect of selectivity heating, microwave heating in this power range is not only conducive to the generation of tetradecylmethyl dihydroxy ethyl brometo de amonio, the generation of side reaction can also be suppressed, therefore can ensure or even improve the productive rate of tetradecylmethyl dihydroxy ethyl brometo de amonio.In addition, the inventive method selects the larger propyl carbinol of polarity as reaction solvent, is conducive to the absorption of microwave, improves reaction efficiency.Condensing reflux reaction under the boiling temperature of single component or polycomponent complex solvent, under guaranteeing the condition that microwave can uninterruptedly heat, ensures the rotation of polar reaction thing molecule and collides, improving speed of reaction.
Accompanying drawing illustrates:
Fig. 1 be in the inventive method different solvents amount to the influence curve figure of transformation efficiency.
Fig. 2 be in the inventive method different microwave to the influence curve figure of transformation efficiency.
Fig. 3 be in the inventive method differential responses temperature to the influence curve figure of transformation efficiency.
Fig. 4 be in the inventive method the differential responses time to the influence curve figure of transformation efficiency.
Fig. 5 is the infrared spectrogram of products therefrom in the inventive method.
Fig. 6 be products therefrom in the inventive method proton nmr spectra (
1h NMR) figure.
Fig. 7 is the mass spectrum of products therefrom in the inventive method.
Fig. 8 be in the inventive method products therefrom to the characteristic of solubilizing graph of a relation of benzene.
Embodiment:
In order to understand the present invention better, technique effect of the present invention will be further illustrated with embodiment by experiment below.
Below experiment and embodiment material used are:
N methyldiethanol amine chemical pure Period In Maoming crowd and petrochemical industry company limited provide
Company limited is moulded in the many combinations of bromotetradecane chemical pure Period In Maoming
Pentyl alcohol analytical pure Tianjin good fortune chemical reagent factory in morning
Dehydrated alcohol analytical pure Tianjin Zhi Yuan chemical reagent company limited
Analysis of ethyl acetate pure Tianjin Zhi Yuan chemical reagent company limited
1, solvent is on the impact of reaction efficiency
N-propyl alcohol, propyl carbinol, Pentyl alcohol, n-hexyl alcohol, nitrogen dimethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO) is selected to carry out the tetradecylmethyl dihydroxy ethyl brometo de amonio building-up reactions of microwave catalysis respectively as solvent herein, reaction conditions is: reactant molar ratio is n (bromotetradecane): n (MDEA)=1.1:1.0, solvent adding amount is 20% of reactant quality, temperature is the boiling point of solvent, extraction time 25min, microwave power 500W.Conversion results is in table 1.
Table 1 different solvents is on the impact of transformation efficiency
| Solvent | N-propyl alcohol | Propyl carbinol | Pentyl alcohol | N-hexyl alcohol | DMF | DMSO |
| Color | Clear, colorless | Clear, colorless | Light yellow | Deep yellow | Vandyke brown | Brown |
| Reflux temperature/DEG C | 110 | 120 | 150 | 170 | 153 | 190 |
| Transformation efficiency/% | 57.50 | 53.31 | 94.36 | — | 90.60 | — |
As can be seen from Table 2, using Pentyl alcohol as solvent time, transformation efficiency is the highest and product colour is best.Due to the reflux temperature of Pentyl alcohol higher (150 DEG C), and microwave heating be a kind of in type of heating, have that rate of heating is fast, homogeneous heating without thermograde, without features such as lag-effects, the polarity of molecule is stronger, and the micro-wave energy of absorption is more.
2, quantity of solvent is on the impact of reaction efficiency
Take Pentyl alcohol as solvent, reactant molar ratio is n (bromotetradecane): n (MDEA)=1.1:1.0, microwave power is 400W, reaction times 25min is carry out microwave backflow building-up reactions under the condition of 5%, 10%, 15%, 20%, 25%, 30%, 40%, 50%, 60% respectively at solvent.Result is as shown in Figure 1: as seen from Figure 1, but when percentage of solvents is 20%, transformation efficiency is the highest.
3, microwave power is on the impact of reaction efficiency
Being 20% with per-cent, the Pentyl alcohol of (account for reactant quality, lower with) is solvent, respectively 300,400,500, carry out backflow under the power of 600W and synthesize 25min.As can be seen from our experimental result (Fig. 2), this reaction is when more than 400W (comprising 400W), and transformation efficiency change is little.
4, temperature of reaction is on the impact of reaction efficiency
Take per-cent as the Pentyl alcohol of 20% be raw material, microwave power is 400w, and the reaction times is 25min, reacts respectively at the temperature of 120 DEG C, 125 DEG C, 130 DEG C, 135 DEG C, 140 DEG C, 145 DEG C, 150 DEG C.As seen from Figure 3, temperature reach 140 DEG C and above time, transformation efficiency remains unchanged substantially, reaches maximum value.
As shown in Figure 4, the reaction times is too short, reacts very insufficient, so productive rate is lower, along with the prolongation in reaction times, reaction is tending towards complete, and when being 30min when reacted, productive rate reaches 96.7%.Along with the prolongation in reaction times, reactant just constantly reduces, and transformation efficiency rises no longer obvious.Therefore the reaction times in the inventive method is advisable with 25 ~ 30min.
Embodiment 1:
1, prepare: by 17gN-methyldiethanolamine and 40g lauryl bromide by being dissolved in 14.3g Pentyl alcohol, it is 135 DEG C in temperature of reaction, microwave power is react 20 minutes in the microwave of 500W, the last EtOH-EtOAc mixed solvent (volume ratio is 1:4) adding 5.4 times of reaction product volume in reaction solution, obtain white crystal, i.e. product.Be indicator with tetrabromophenol sulfonphthalein-ethanol, the transformation efficiency utilizing hydrochloric acid-ethanol volumetry to record target product is 76.6%.
2, gained white crystal is identified as follows:
(1) qualification (Tripotassium iron hexacyanide test) of quaternary ammonium salt
Dissolve 0.1g gained white solid in 50mL water, when adding potassium ferricyanide solution (3g/L) in 10mL solution, generate yellow mercury oxide.
(2) Infrared spectroscopy
(3) to take a morsel after refining pigment sample KBr compressing tablet on infrared spectrometer from 400 ~ 4000cm
-1scope interscan, carries out spectroscopic analysis.Result is as shown in Fig. 5 and table 2.
Table 2 infrared absorption spectra analysis table
As known from Table 2, containing hydroxyl, carbonnitrogen bond primary hydroxyl group and carbonnitrogen bond in crystal, but the C-Br in raw material does not show in spectrogram, can this product of preliminary evaluation be therefore tetradecylmethyl dihydroxy ethyl brometo de amonio by infrared absorption spectrum.
TMDAB nuclear magnetic resonance map (
1h NMR) analyze: can be obtained by Fig. 6, numbers of hydrogen atoms is 42, identical with setting product structure.Can show that on each group, H chemical shift δ is by Fig. 6: R-CH3*, 0.82 ~ 0.84,3H, N+ (CH2) 4-(CH2*) 9-CH3,1.21 ~ 1.23,18H, N+CH2 CH2 (CH2*) 2,1.25 ~ 1.30,4H, CH3N+-CH2-CH2*, 1.70,2H, N+-CH3*, 3.29,3H, N+-CH2-CH2*R, 3.50 ~ 3.52,2H, N-CH2-CH2*-OH, 3.65 ~ 3.93,4H, N-CH2*-CH2-OH, 4.06,4H, OH*, 4.72 ~ 4.74,2H.The chemical shift of product Hydrogen Proton and product structure one_to_one corresponding, therefore can determine to synthesize product TMDAB.
The mass spectroscopy of TMDAB: product is scanned with mass spectrograph, with ESI as ion source, positive ion mode, result as shown in Figure 7,315.9 (M+H)+, be the cationic molecular weight 316 of target product and meet.
3, the performance study of gained solid
(1) surface tension
The quaternary ammonium salt solution of preparation 0.1%, uses the full-automatic interfacial tensimeter of Zibo Boshan Hai Fen instrument plant ZL2100 type, adopts platinum loop method to measure quaternary ammonium salt solution surface tension.
It is 24.8Nm that result records its surface tension
-1, known this tensio-active agent have certain surface active.
(2) TMDAB is to benzene characteristic of solubilizing
Benzole soln and ultraviolet-visible spectrophotometry is adopted to measure.Measure the absorbancy of different concns benzole soln, and drawing data graph of a relation.
Can be drawn by Fig. 8, the solubilising limit A of TMDAB to benzene is 0.2195mL, substitutes into following formulae discovery:
Calculating its solubilising X is 1322mL/mol, the limit has been issued in the situation that concentration is lower, illustrate that this kind of tensio-active agent can reach micelle-forming concentration at low concentration, less consumption just can reach good solute effect, oil well can be distributed in the aqueous solution under comparatively low concentration, solubilizing effect is better.
(3) Krafft's point
Whether the quaternary ammonium salt solution of preparation 1%, as temperature lower than in the saturated aqueous common salt of 0 DEG C, observe and have crystal or solid matter to separate out.
Found that, do not have crystal or solid matter to separate out in quaternary ammonium salt solution, solution clear, illustrates that the Krafft's point of this quaternary ammonium salt is less than 0 DEG C.It can thus be appreciated that this quaternary ammonium salt has good water-soluble, this may be because the alkyl chain of this quaternary ammonium salt is shorter, and also cause containing two hydrophilic hydroxyls in molecular structure.
Embodiment 2 ~ 29:
It is in the Pentyl alcohol of A that N methyldiethanol amine and tetradecyl bromine are dissolved in mass percent, be react in the microwave of 500W at power, the last EtOH-EtOAc mixed solvent (volume ratio is 1:4) adding 5.4 times of reaction product volume in reaction solution, obtains white solid.In reaction each parameter and reaction result as shown in table 3, wherein a, b, A, B, C, D and R represent the degree of the amount of the amount of N methyldiethanol amine, tetradecyl bromine, Pentyl alcohol, reaction times, temperature of reaction and transformation efficiency respectively.
Table 3
Claims (3)
1. the preparation method of a tetradecylmethyl dihydroxy ethyl brometo de amonio, it is characterized in that comprising the steps: bromotetradecane to mix according to mol ratio 1:1 with N methyldiethanol amine, be dissolved in Pentyl alcohol, back flow reaction in microwave, in reaction solution, add EtOH-EtOAc mixed solvent after reaction terminates and make product crystallization, obtain white solid; In reflux course, remain the continuous action of microwave and the boiling of reaction solution.
2. the method for claim 1, it is characterized in that described Pentyl alcohol consumption is 5% ~ 60% for accounting for reactant mass percent, reflux temperature is 125 ~ 145 DEG C, and microwave power is 300 ~ 600W, and reflux time is 25 ~ 30min.
3. the method for claim 1, it is characterized in that described Pentyl alcohol consumption is for accounting for reactant mass percent 15%, reflux temperature 135 DEG C, microwave power is 400W, and reflux time is 30min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101381318A (en) * | 2008-10-22 | 2009-03-11 | 广州大学 | Microwave synthetic method of dodecyl methyl biethoxyl ammonium bromide |
| CN103965061A (en) * | 2014-01-15 | 2014-08-06 | 广州大学 | Solvent-free synthesis method of myristyl methyl dihydroxyethyl ammonium bromide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101381318A (en) * | 2008-10-22 | 2009-03-11 | 广州大学 | Microwave synthetic method of dodecyl methyl biethoxyl ammonium bromide |
| CN103965061A (en) * | 2014-01-15 | 2014-08-06 | 广州大学 | Solvent-free synthesis method of myristyl methyl dihydroxyethyl ammonium bromide |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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