CN102453000B - Synthetic method of biquaternary ammonium salt - Google Patents
Synthetic method of biquaternary ammonium salt Download PDFInfo
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- CN102453000B CN102453000B CN201010514417.1A CN201010514417A CN102453000B CN 102453000 B CN102453000 B CN 102453000B CN 201010514417 A CN201010514417 A CN 201010514417A CN 102453000 B CN102453000 B CN 102453000B
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Abstract
The invention discloses a synthetic method of biquaternary ammonium salt. In the method, ultrasonic waves are introduced into a reaction system in a dispersing manner, and a biquaternary ammonium pentane-1,5 (methylpyrrolidinium) dibromide can be synthesized under the high temperature and high concentration. In the method, the quantity of the used solvent is fewer, the particles of the biquaternary ammonium salt which is generated by the reaction are smaller, so that the following washing, filtering, recrystallization and other operations are very facilitated.
Description
Technical field
The invention belongs to Minute Organic Synthesis field, specifically, relate to a kind of preparation method of bi-quaternary ammonium salt,
Background technology
Micro porous molecular sieve material due to the well-regulated duct of tool, larger specific surface area and be widely used in the fields such as absorption, separation, chemical industry, catalysis.The preparation majority of micro porous molecular sieve needs the template formed as duct by structure directing agent to synthesize, and the utilization of novel template is the key that preparation has novel texture molecular sieve.
In recent years, bi-quaternary ammonium salt template has the steering capability novel molecular sieve of alternate cell channels showing its uniqueness at the new pore passage structure of design, particularly synthesis.Journal of Catalysis 215 (2003) 151-170, US 5989410, US 5968475, US 6136290 and CN1234012A, CN11406120C have reported a kind of novel molecular sieve IM-5 and synthetic method thereof.The pore passage structure of IM-5 molecular sieve and ZSM-5 is similar, has two-dimentional 10MR alternate cell channels, and thermally-stabilised higher with hydrothermal stability, therefore has stronger catalytic applications prospect.
The template that above-mentioned document and patent synthesize IM-5 molecular sieve used is bi-quaternary ammonium salt pentane-1,5 two (crassitude) bromide, and its molecular formula is:
At present, this bi-quaternary ammonium salt not yet has commercial product, therefore need to prepare voluntarily when synthesizing corresponding IM-5 molecular sieve, common preparation method is: at room temperature, by 1, the backflow of pentamethylene bromide, N-crassitude and solvent, after 0.5-10 days, namely obtains bi-quaternary ammonium salt template by after reaction product washing, filtration, recrystallization.In this reaction, the temperature and concentration of system is two main controling parameters.Speed of response along with temperature of reaction and concentration increase and improve.Temperature of reaction and reaction density higher time, reaction is comparatively violent, and product easily forms firm bulk, has both been unfavorable for shifting out product from reactor, is also unfavorable for follow-up washing, filtration, re-crystallization step.Therefore, the synthesis of current above-mentioned bi-quaternary ammonium salt is generally carried out under low temperature and lower reaction density, now, although less granular disintegration can be generated, be conducive to follow-up washing, filtration, re-crystallization step, because speed of response is comparatively slow, reaction times can reach 3-10 days, the yield of product is lower, and need use a large amount of solvent, adds the difficulty of recycling.
Summary of the invention
For overcoming the deficiencies in the prior art, the invention provides a kind of method of Fast back-projection algorithm bi-quaternary ammonium salt under high temperature and high density.The method quantity of solvent used is less, and the product grain generated is less, is very beneficial for the operations such as follow-up washing, filtration, recrystallization.
The synthetic method of bi-quaternary ammonium salt of the present invention, bi-quaternary ammonium salt is pentane-1,5-bis-(crassitude) bromide, comprises the steps:
(1) at 35 ~ 50 DEG C, by 1, pentamethylene bromide, N-crassitude, organic solvent mix under constantly stirring, then ultrasonic wave is applied to this reaction system, be 20 ~ 150KHZ in ultrasonic frequency, be preferably ultrasonic reaction 0.1 ~ 12.0 hour under the effect of 50 ~ 100KHZ, be preferably 1.0 ~ 12.0 hours;
(2) by the suspension liquid crystallization of step (1) gained, filter;
(3) step (2) obtain solid matter washing, recrystallization, filtration, repeat said process 0 ~ 5 time, obtain bi-quaternary ammonium salt pentane-1,5-bis-(crassitude) bromide of the present invention.
In step (1), mol ratio >=2.0 of N-crassitude/pentamethylene bromide, are preferably 2.0 ~ 2.5.Organic solvent described in step (1) and reaction raw materials have good mutual solubility, and its mutual solubility not with temperature or concentration change and there is considerable change.Simultaneously, the mutual solubility of described solvent and goal response product should be less than the mutual solubility with reaction raw materials, be in particular in, the solubleness of target product in this solvent for temperature or concentration comparatively responsive, should be able to relatively easily crystallization by reducing temperature or improving concentration.Organic solvent described in step (1) be preferably in methyl alcohol, ethanol, acetone, ether one or more, more preferably ethanol.The volume of described N-crassitude and pentamethylene bromide and account for 30% ~ 75% of step (1) gained system cumulative volume, is preferably 50% ~ 65%.
Step (3) described washing organic solvent used is one or more in methyl alcohol, ethanol, acetone, ether, be preferably acetone, one or more in ether, can used organic solvent identical with step (1) identical, also can be different.The wash temperature of step (3) is the atmospheric boiling point temperature of 25 DEG C ~ organic solvent.The amount of organic solvent used should ensure that the solid matter of step (1) gained is dissolved in organic solvent completely.Crystallization and recrystallization can adopt cryogenic freezing crystallization, or make organic solvent evaporation by heating thus the method improving product concentration in organic solvent makes product crystallization, preferred cryogenic freezing crystallization, freezing temp is freezing point temperature ~ 25 DEG C of organic solvent, is preferably-15 ~ 0 DEG C.
The present invention by introducing ultrasonic wave dissemination in reaction system, the aggregation tendency of reaction product effectively can be stoped under high temperature and high density synthesis condition, thus forming the short grained bi-quaternary ammonium salt be suspended in solvent, this small-particle bi-quaternary ammonium salt is conducive to the purification processes such as follow-up washing, filtration, recrystallization process.The cavatition that formed of ultrasonic disperse that the present invention introduces can form microcosmic high-temperature zone, and reactant can rapid reaction in this microcosmic high-temperature zone, can accelerate the W-response speed of reaction system, reduce preparation time.The preparation method of bi-quaternary ammonium salt of the present invention allows reaction to carry out in higher concentrations under hyperacoustic effect simultaneously, can save the quantity of solvent that reaction is used.
Accompanying drawing explanation
The carbon-13 nmr spectra of bi-quaternary ammonium salt pentane-1,5-bis-(crassitude) bromide of Fig. 1 prepared by the embodiment of the present invention 1, with D
2o is solvent.
Embodiment
Embodiment 1
By N-crassitude, 1, pentamethylene bromide, acetone each 40mL, 30mL, 70.5mL are mixed in the there-necked flask of band reflux, again there-necked flask is placed in the ultrasonic wave dispersion water-bath of 50kHz, start ultrasonic disperser, mixture high degree of agitation at 35 DEG C is reacted 8 hours until formed containing a large amount of short grained suspension liquid.This suspension liquid is freezing at-10 DEG C, separate out a large amount of powdered solid thing, then adopt the mode separate solid thing of filtration.At 25 DEG C, solids is put in ether, constantly stir and supplement ether according to dissolution degree, until solids is dissolved in ether completely.Afterwards, freezing at above-mentioned solution is placed in-10 DEG C, separate out a large amount of Powdered solids, then adopt the mode separate solid thing of filtration.To wash above, recrystallization, separating step repeat 3 times, finally obtain the pressed powder of beige, turn out to be bi-quaternary ammonium salt pentane-1,5-bis-(crassitude) bromide of the present invention through carbon-13 nmr spectra, yield is the 95.4mol% of theoretical yield.
Embodiment 2
By N-crassitude, 1, pentamethylene bromide, acetone each 60mL, 27.7mL, 55mL are mixed in the there-necked flask of band backflow, again there-necked flask is placed in the ultrasonic wave dispersion water-bath of 70kHz, start ultrasonic disperser, mixture is reacted 3 hours until formed containing a large amount of short grained suspension liquid 40 DEG C of high degree of agitation.This suspension liquid is freezing at-10 DEG C, separate out a large amount of powdered solid thing, then adopt the mode separate solid thing of filtration.At 25 DEG C, solids is put in ether, constantly stir and supplement ether according to solvability, until solids is dissolved in ether completely.Afterwards, freezing at above-mentioned solution is placed in-10 DEG C, separate out a large amount of powdered solid thing, then adopt the mode separate solid thing of filtration.To wash above, recrystallization, separating step repeat 3 times, finally obtain the pressed powder of beige, turn out to be bi-quaternary ammonium salt pentane-1,5-bis-(crassitude) bromide of the present invention through carbon-13 nmr spectra, yield is the 93.8mol% of theoretical yield.
Embodiment 3
By N-crassitude, 1, pentamethylene bromide, ethanol each 40mL, 24mL, 35.5mL are mixed in the there-necked flask of band backflow, again there-necked flask is placed in the ultrasonic wave dispersion water-bath of 100kHz, start ultrasonic disperser, mixture high degree of agitation at 50 DEG C is reacted 2 hours until formed containing a large amount of short grained suspension liquid.By freezing at this suspension liquid and-5 DEG C, separate out a large amount of powdered solid thing, then adopt the mode separate solid thing of filtration.At 25 DEG C, solids is put in acetone, constantly stir and supplement acetone according to solvability, until solids is dissolved in acetone completely.Afterwards, freezing at above-mentioned solution is placed in-5 DEG C, separate out a large amount of powdered solid thing, then adopt the mode separate solid thing of filtration.To wash above, recrystallization, separating step repeat 3 times, finally obtain the pressed powder of beige, turn out to be bi-quaternary ammonium salt pentane-1,5-bis-(crassitude) bromide of the present invention through carbon-13 nmr spectra, yield is the 97.3mol% of theoretical yield.
Comparative example 1
N-crassitude, pentamethylene bromide, acetone each 40mL, 30mL, 200mL are mixed in the there-necked flask of band reflux, make mixture high degree of agitation at room temperature 20 DEG C react 8 days, formed containing the short grained suspension liquid of part.Successive method is identical with embodiment 1.Products therefrom turns out to be pentane-1,5-bis-(crassitude) bromide through carbon-13 nmr spectra, but the yield of product is only the 12.0mol% of theoretical yield.Compared with method of the present invention, to illustrate that under room temperature and lower concentration speed of response is comparatively slow and yield is lower.
Comparative example 2
N-crassitude, pentamethylene bromide, acetone each 40mL, 30mL, 70.5mL are mixed in the there-necked flask of band reflux, make mixture high degree of agitation at room temperature 35 DEG C react 24 hours, form firm bulk solid product.This product can not normally take out from there-necked flask.There-necked flask is smashed, takes out product and be chopped into fritter.Successive method is identical with embodiment 1, last gained solid product, turns out to be pentane-1,5-bis-(crassitude) bromide through carbon-13 nmr spectra, and yield is the 35mol% of theoretical yield.Compared with method of the present invention, illustrate that at high temperature under high density, if do not apply ultrasonic disperse effect, speed of response is relatively slow, and easily generates bulk solid, is unfavorable for successor operation.
Claims (11)
1. a synthetic method for bi-quaternary ammonium salt, comprises the steps:
(1) at 35 ~ 50 DEG C, by 1, pentamethylene bromide, N-crassitude and organic solvent mix under constantly stirring, and then apply ultrasonic wave to this reaction system, are ultrasonic reaction 0.1 ~ 12.0 hour under the effect of 50 ~ 150KHZ in ultrasonic frequency; The volume of described N-crassitude and pentamethylene bromide and account for 50% ~ 65% of step (1) gained system cumulative volume;
(2) by the suspension liquid crystallization of step (1) gained, filter;
(3) step (2) obtain solid matter washing, recrystallization, filtration, repeat said process 0 ~ 5 time, obtain bi-quaternary ammonium salt pentane-1,5-bis-(crassitude) bromide.
2. in accordance with the method for claim 1, it is characterized in that described ultrasonic frequency is 50 ~ 100KHZ, the ultrasonic reaction time is 1.0 ~ 12.0 hours.
3. in accordance with the method for claim 1, it is characterized in that in step (1), mol ratio >=2.0 of N-crassitude/pentamethylene bromide.
4. in accordance with the method for claim 1, it is characterized in that in step (1), the mol ratio of N-crassitude/pentamethylene bromide is 2.0 ~ 2.5.
5. the organic solvent that in accordance with the method for claim 1, it is characterized in that described in step (1) is one or more in methyl alcohol, ethanol, acetone, ether.
6. in accordance with the method for claim 1, it is characterized in that the organic solvent described in step (1) is ethanol.
7. in accordance with the method for claim 1, it is characterized in that step (3) described washing organic solvent used is one or more in methyl alcohol, ethanol, acetone, ether.
8. in accordance with the method for claim 1, it is characterized in that step (3) described washing organic solvent used is one or more in acetone, ether.
9. in accordance with the method for claim 1, it is characterized in that the wash temperature of step (3) is the atmospheric boiling point temperature of 25 DEG C ~ organic solvent; The amount of organic solvent used should ensure that the solid matter of step (1) gained is dissolved in organic solvent completely.
10. in accordance with the method for claim 1, it is characterized in that described crystallization and recrystallization adopt cryogenic freezing crystallization, or make the method for organic solvent evaporation make product crystallization by heating.
11. in accordance with the method for claim 1, and it is characterized in that described crystallization and recrystallization adopt cryogenic freezing crystallization, freezing temp is-15 ~ 0 DEG C.
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| CN103708491B (en) * | 2012-09-28 | 2015-07-29 | 中国石油化工股份有限公司 | The method of synthesis IM-5 molecular sieve |
| CN106588816B (en) * | 2015-10-20 | 2018-11-20 | 中国石油化工股份有限公司 | Gemini quaternary ammonium salt or quaternary amine alkali cpd and preparation method |
| US9815705B2 (en) * | 2016-04-12 | 2017-11-14 | Chevron U.S.A. Inc. | Synthesis of molecular sieve SSZ-98 |
| CN113004149A (en) * | 2021-02-26 | 2021-06-22 | 大连理工大学 | Preparation method of double quaternary ammonium salt compound |
| WO2024179455A1 (en) * | 2023-02-28 | 2024-09-06 | Basf Corporation | Synthesis of cha zeolitic materials, cha zeolitic materials obtainable therefrom and scr catalysts comprising the same |
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| CN1671622A (en) * | 2002-05-23 | 2005-09-21 | 康斯乔最高科学研究公司 | Microporous crystalline zeolite material (zeolite ITQ-22), its synthesis method and its application as a catalyst |
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| CN1671622A (en) * | 2002-05-23 | 2005-09-21 | 康斯乔最高科学研究公司 | Microporous crystalline zeolite material (zeolite ITQ-22), its synthesis method and its application as a catalyst |
| WO2004002430A2 (en) * | 2002-06-28 | 2004-01-08 | Combinatorx Incorporated | Combinations for the treatment of fungal infections |
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