CN102180803A - Solvent-free synthesis method of dodecyl bis(2-hydroxyethyl)methylammonium bromide - Google Patents
Solvent-free synthesis method of dodecyl bis(2-hydroxyethyl)methylammonium bromide Download PDFInfo
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Abstract
The invention relates to a solvent-free synthesis method of dodecyl bis(2-hydroxyethyl)methylammonium bromide. The method comprises the following steps of: mixing N-methyl diethanolamine with bromododecane in the molar ratio of 1:1-1:1.4; and reacting at the temperature of 90-120 DEG C at the reaction speed of 100-300 r.min<-1> for 120-240 minutes, wherein the reaction transformation ratio is over 80 percent. Meanwhile, the invention further provides the application of the solvent-free synthesis method of dodecyl bis(2-hydroxyethyl)methylammonium bromide to industrial production. The defects of the conventional organic synthesis method are overcome. The synthesis method has the characteristics of easiness and novelty. Solvent is not taken as a medium, so that the synthesis method has the advantages of low cost and short reaction time, and is an environmentally-friendly chemical synthesis method.
Description
Technical field
The present invention relates to the no-solvent synthesis process of organic compound, relate more specifically to the no-solvent synthesis process of dodecyl dihydroxy ethyl methyl brometo de amonio.
Background technology
Chemical in recent years boundary has proposed notions such as Green Chemistry, environmental friendliness chemistry, Sustainable development chemistry, clean technology, and this is fresh target, new direction and the new challenge that traditional chemical is proposed.
In our traditional view, an organic chemical reactions must carry out under solvent, because organic solvent can dissolve organic reactant well, makes reactant molecule homodisperse in solution, stably carries out energy exchange.But simultaneously toxicity, the volatility of organic solvent, be difficult to reclaim and make it become environmentally harmful factor again.Therefore, in the 90's of 20th century, scholars propose solvent-free organic synthesis notion clearly, and propose solvent-free organic synthesis and will become development green synthetic important channel.
Over past ten years, particularly in recent years, organic chemist put forward to carry out particular study with the organic chemical reactions under the condition of no solvent.The experimental results proves that many organic chemical reactionses can carry out under solvent-free, particularly the solvent-free reaction of those solid phases has been obtained pleasurable result.Compare with the organic reaction under solvent condition is arranged, the organic reaction under the condition of no solvent has simple, the novel features of method, owing to do not use solvent to do medium, and the short feature that himself is arranged of cost low reaction time.
Solvent-free organic reaction is meant the organic reaction of not adopting solvent, and it can be the solid state reaction between the solid material, the liquid phase reaction between the liquid starting material, also can be the reaction of raw material under molten state, or the inhomogeneous reaction between the different phase raw material.Solvent-free reaction is actually and carries out under novel chemical environment, and the collision between the reactant molecule is more direct, effectively.
All the time, Chinese scholars all biases toward solid state reaction to the research of solvent-free reaction, has also obtained certain breakthrough.At present, successfully realize a series of reaction such as generation, rearrangement reaction, elimination reaction, hydrolysis reaction, protective reaction, protective reaction of generation, the itrogen-to-nitrogen bonds of generation, the carbon-halogen bond of generation, the carbon phosphorus key of generation, the carbon-sulfur bond of generation, the carbon-oxygen bond of generation, the carbonnitrogen bond of solvent-free reduction reaction, oxidizing reaction, carbon-carbon bond.The general operation method of solid phase solvent-free reaction has: under (1) room temperature, can react with mortar abrasive solid reaction raw materials.(2) solid material is mixed after the heating or leave standstill.(3) with powerful mechanical means such as ball mill or vibration at high speed pulverizing.(4) host-guest method, with the reaction substrate is object, with the suitable molecule of a certain proportion of another kind is that main body forms inclusion compounds, and then manage to make substrate to react, at this moment Fan Ying location selectivity or optical selective etc. all can change to some extent because of the effect of main body or improve, even become and have only a kind of selection.(5) microwave exposure method is comprising direct microwave method, phase-transfer catalysis microwave method, load microwave method.Utilize after the aforesaid method reaction, according to the solubility property of raw material and product, select appropriate solvent again, product is reflected from mixture or the raw material that unreacted is intact is removed, get final product purer product.
Research to the liquid phase solvent-free reaction is less.People such as Zhu Xinhai utilize the Pall-Knorr reaction to synthesize pyrrole derivative under the catalytic room temperature solvent-free condition of formic acid, and the reaction times is 0.5-6h.People such as Zhao Hui have finished mercaptal to the liquid phase reaction thing and have contracted the thioketones reaction under the condition of solvent-free heated and stirred.
In the last few years since population increase the production of serious day by day wherein many problems of pollution that production development mankind's activity aggravation is subjected to ball ecological environment and human synthetic chemical substance and use relevant.This just requires chemist to focus onto from source solution generation of waste materials, both be devoted to the strategy reform of synthesizing mean, allow chemistry when 21 century continues as the national economy sustainable development service, avoid again environment is produced adverse influence, thereby improve the utilization ratio of resource, this is a very significant job.Various countries chemical worker is seeking the method for Green Chemistry chemical industry from various approach, which kind of method is more green on earth, draws a conclusion after should making comprehensive assessment according to the appraisal procedure of Green Chemistry chemical industry again.
In the comparatively gentle reaction of solvent-free reaction down, solvent-free reaction may be to select preferably for those.Organic reaction under the condition of no solvent has simple, the novel features of method, owing to do not use solvent to do medium, and the short feature that himself is arranged of cost low reaction time.
Summary of the invention
The object of the present invention is to provide a kind of method simple, cost is low, and the reaction times is the no-solvent synthesis process of short dodecyl dihydroxy ethyl methyl brometo de amonio.
The present invention achieves the goal by following scheme:
A kind of no-solvent synthesis process of dodecyl dihydroxy ethyl methyl brometo de amonio is characterized in that N methyldiethanol amine and the bromododecane mixed with mol ratio 1:1～1:1.4, stirring reaction 120～240min under 90 ℃～120 ℃ conditions.
The solvent-free interpolation of above-mentioned reaction.
Rotating speed during stirring is 100～300rmin
-1
Rotating speed during stirring is preferably 200rmin
-1
The mol ratio of N methyldiethanol amine and bromododecane is preferably 1:1.
Temperature of reaction is preferably 90 ℃.
Reaction times is preferably 150min.
A kind of according to the application of aforesaid method on industrial production, it is characterized in that the preferred reaction conditions of described application is: with N methyldiethanol amine and bromododecane mixed with mol ratio 1:1, under 90 ℃ of conditions with 200rmin
-1Rotating speed stirring reaction 150min.
Compared with prior art, the present invention has following outstanding effect:
1. the inventive method is simple, novel.
2. cost of the present invention is low, and the reaction times is short.
3. under optimized conditions, the amplification test transformation efficiency is 84.5%, and the product purity that the process crystallization obtains is greater than 90%.
Description of drawings
The 2000mL glass reaction still that Fig. 1 uses for amplification test
Fig. 2 is the infrared absorption spectrum of reaction product
Fig. 3 be the reaction product proton nmr spectra (
1H NMR) figure
Fig. 4 is the influence of temperature to transformation efficiency
Fig. 5 is the influence of time to transformation efficiency
Fig. 6 is the influence of material ratio to transformation efficiency
Fig. 7 is the influence of rotating speed to transformation efficiency.
Embodiment
Embodiment 1:
2.2.1 material and reagent
2.2.2 instrument and equipment
2.2.3 experimental technique
The N methyldiethanol amine bromododecane is joined in the round-bottomed flask the synthetic target product of stirring reaction under the heating condition.And under the peak optimization reaction condition, 596g N methyldiethanol amine 1245g bromododecane is joined in the reactor of 2000mL (as shown in Figure 1), carry out amplification test.The same 2.2.3 of the measuring method of transformation efficiency and product purity.
Result and discussion
3.1 the mensuration of product purity
Adopt two-phase titration that the product behind the recrystallization 5 times is analyzed, record product purity after the crystallization greater than 99%
3.2 the sign of product structure
3.3.1 the results of IR of product
Take a morsel through purified pigment sample with behind the KBr compressing tablet on infrared spectrometer from the interscan of 400～4000cm-1 scope, carry out spectroscopic analysis (as shown in Figure 2).This product of preliminary evaluation is that the chemical formula structure of dodecyl methyl dihydroxy ethyl brometo de amonio conforms to.
Table 4-1 infrared absorption spectrum analytical table
3.3.2 nuclear magnetic resonance spectroscopy
With nuclear magnetic resonance analyser product is scanned (as shown in Figure 3), going out synthetic product according to the analytical results of showing 4-2 also deducibility is dodecyl methyl dihydroxy ethyl brometo de amonio.
Table 4-2
1The analysis and the deduction of H NMR spectrum
.3.3 single factor optimization Test
3.3.1 the influence of temperature of reaction
Under the situation that does not add solvent, 0.1mol N methyldiethanol amine and 0.1mol bromododecane (as raw material) are added in the round-bottomed flask, respectively stirring reaction 2h under 70,80,90,100,110,120 ℃ temperature.The results are shown in Figure 4.
As seen from Figure 4, when temperature of reaction is 70 ℃, transformation efficiency seldom, experimental phenomena is for there being demixing phenomenon.When temperature of reaction rose to 90 ℃, reaction conversion ratio reached 86.7%.Transformation efficiency changes little during elevated temperature again.
3.3.2 the influence in reaction times
Mol ratio by 1:1 is put into round-bottomed flask with raw material, stirring reaction 4h under 90 ℃ temperature, the transformation efficiency of every 30min measured reaction.The results are shown in Figure 5.
As can be seen from Figure 5, 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 fully, and when the reaction times was 150min, productive rate had reached 90.2%.Along with the prolongation in reaction times, reactant just constantly reduces, and transformation efficiency rises no longer obvious.
3.3.3 the influence of material ratio
The raw material of different material ratio is put into round-bottomed flask respectively, the transformation efficiency of stirring reaction 150min measured reaction under 90 ℃ temperature.The results are shown in Figure 6.
As shown in Figure 6, when the N methyldiethanol amine amount, transformation efficiency can reduce significantly.When bromododecane was excessive, transformation efficiency had slight rising.
3.3.4 the influence of rotating speed
Mol ratio by 1:1 is put into round-bottomed flask with raw material, the transformation efficiency of stirring reaction 150min measured reaction under 90 ℃ temperature.The results are shown in Figure 7.
As seen from Figure 7, rotating speed is very little to the influence of this reaction.Rotating speed is not in the limit of consideration of reaction.From energy-conservation angle, should select less rotating speed, and be 200 rmin at rotating speed
-1The time transformation efficiency the highest.Therefore, the rotating speed in the scale-up is decided to be 200 rmin
-1
Amplification test research
3.4.1 amplification test result
Can determine that by single factor experiment the reaction conditions that scale-up adopts is: 90 ℃ of temperature, time 150min, material ratio are 1:1, rotating speed is 200 rmin
-1The amount of raw material is amplified 50 times of reactors that place 2L, according to the optimum reaction condition amplification test.By experiment repeatedly, under optimised process, the transformation efficiency of amplification test is 84.5%.The product population that obtains through crystallization is 1500g, and purity is greater than 90%.
1. thermograde and concentration gradient
The key issue that amplification test exists is the scale effect problem, that is: on macrostate, lab scale and industrialization are as broad as long, and on microstate, in the part, both differences on temperature, concentration are very big sometimes, and this species diversity is exactly scale effect.The key issue that solves scale effect is the problem [79] that solves thermograde and concentration gradient.At this reaction, should be that good stirring will be arranged, make material concentration, temperature uniform distribution.
For thermopositive reaction, heat is from chemical reaction, the mixing owing to really realize ideal, be in the reactor everywhere temperature homogeneous, concentration homogeneous be impossible, in fact chemical reaction is not to take place equably in whole reactor, often concentrates on some zones, this zone is just near dropping liquid point, and the diffusion of dropping liquid needs the regular hour, need a process, thereby dropping liquid point place concentration is higher, temperature is also higher.
2. reaction time
To test amplify 4 times after, experimental period lengthening, this be because: volume is big more on the one hand, and the surface-area of unit volume is more little, the heat transfer area deficiency.The surface-area of unit volume (specific surface area) is:
Wherein, R is a radius of sphericity, is sphere diameter.The diameter that is specific surface area and equipment is inversely proportional to.According to heat transfer rate equation: γ
Conduct heat=KS △ Tm, heat transfer rate is directly proportional with heat interchanging area.So for amplification test, sphere diameter increases, specific surface area diminishes, the corresponding reduction of heat transfer rate, and the reaction times is elongated.
Claims (7)
1. the no-solvent synthesis process of a dodecyl dihydroxy ethyl methyl brometo de amonio is characterized in that N methyldiethanol amine and the bromododecane mixed with mol ratio 1:1～1:1.4, stirring reaction 120～240min under 90 ℃～120 ℃ conditions.
2. according to right 1 described method, it is characterized in that the solvent-free interpolation of described reaction.
3. according to right 1 described method, the rotating speed when it is characterized in that stirring is 100～300rmin
-1
4. according to right 1 described method, the rotating speed when it is characterized in that stirring is 200rmin
-1
5. according to right 1 described method, the mol ratio that it is characterized in that N methyldiethanol amine and bromododecane is 1:1.
6. according to right 1 described method, it is characterized in that temperature of reaction is 90 ℃.
7. according to right 1 described method, it is characterized in that the reaction times is 150min.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109622233A (en) * | 2018-12-12 | 2019-04-16 | 东北大学 | A kind of hematite reverse flotation desilication method |
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| CN109622233A (en) * | 2018-12-12 | 2019-04-16 | 东北大学 | A kind of hematite reverse flotation desilication method |
| CN109622233B (en) * | 2018-12-12 | 2020-08-21 | 东北大学 | Reverse flotation desilication method for hematite |
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