CN106674017B - A kind of synthetic method and its application of asymmetry bi-quaternary ammonium salt - Google Patents
A kind of synthetic method and its application of asymmetry bi-quaternary ammonium salt Download PDFInfo
- Publication number
- CN106674017B CN106674017B CN201510750137.3A CN201510750137A CN106674017B CN 106674017 B CN106674017 B CN 106674017B CN 201510750137 A CN201510750137 A CN 201510750137A CN 106674017 B CN106674017 B CN 106674017B
- Authority
- CN
- China
- Prior art keywords
- quaternary ammonium
- ammonium salt
- solvent
- asymmetric
- halogenated alkane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The present invention provides a kind of preparation methods of asymmetric bi-quaternary ammonium salt, the following steps are included: (i) long-chain halogenated alkane, two tertiary amines and auxiliary agent are added in the first solvent, heating is reacted, to be separated by solid-liquid separation after reaction, optionally washing and drying solid, obtain asymmetric bi-quaternary ammonium salt intermediate；(ii) intermediate, the short chain halogenated alkane obtained step (i) is added in the second solvent, and heating is reacted, and to be separated by solid-liquid separation after reaction, optionally washs simultaneously drying solid, obtains asymmetric bi-quaternary ammonium salt.The present invention also provides application of the asymmetric bi-quaternary ammonium salt being prepared according to the method in Zeolite synthesis.The present invention can synthesize a series of asymmetric bi-quaternary ammonium salt, method is simple, and raw material is easy to get by the continuous quaternization reaction of two steps, reaction process is steady, easy to operate, with control, product purity and yield are higher, and solvent and unconverted raw material recoverable, basic up to no pollution.
Description
Technical field
The present invention relates to Minute Organic Synthesis fields, and in particular to a kind of synthetic method of asymmetry bi-quaternary ammonium salt also relates to
And the asymmetric bi-quaternary ammonium salt is in the application in Zeolite synthesis field.
Background technique
Currently, because Jie's mesoporous-microporous composite molecular sieve had not only had strong acidic site and weak acid position, but also there is good diffusion, by
The common concern of people.Synthesis Jie's mesoporous-microporous composite molecular sieve usually requires the common work by mesoporous template and micropore template agent
With step is various, and process is complicated.Therefore, it finds a kind of while there is the guiding role of micropore and the mould of mesoporous guiding role
Plate agent, and simplify synthesis process, become the research hotspot of synthesis Jie's mesoporous-microporous composite molecular sieve.
Studies have shown that asymmetric bi-quaternary ammonium salt had not only had the function of micropore guiding, but also have the function of mesoporous guiding, may be used also
Mesoporous size is controlled with the size by adjusting substituent group group.US 20130184147A1,EP 2592049A2,
Nature 416 (2009) 246-249 is reported using asymmetric bi-quaternary ammonium salt synthesis nano flake MFI structure molecular sieve
Method.The thickness of synthesized nano flake MFI structure molecular sieve can be down to the size of single structure cell, greatly improve molecule
The diffusion of sieve, and the material has good (water) thermal stability and adjustable acidity, and there is stronger catalysis to answer
Use prospect.
Above-mentioned patent and the document template used in synthesis nano flake MFI structure molecular sieve technique are asymmetric double
Quaternary ammonium salt template, molecular formula are as follows:
Wherein, R1Selected from C1-C6One of alkyl, R2Selected from C10-C22One of alkyl, X Br.
The synthesis process of asymmetric bi-quaternary ammonium salt is continuous quaternization reaction, is generally completed in two steps, i.e. intermediate and production
Two steps of synthesis of object.In the first step in the synthesis of mesosome, the degree for controlling reaction is the key that reaction and difficult point, and Br is former
The reactivity of son cannot be too strong, should guarantee the yield of mono-quaternaries, reduces the generation of side reaction again.Second step product
Synthesis then on the contrary, to improve the reactivity of Br atom, shortening reaction time as far as possible.
CN 102784584A discloses a kind of asymmetric Cationic Gemini Surfactant and preparation method thereof.The party
Method first reacts tetramethylethylenediamine with short chain brominated alkanes, then obtained product is reacted with long-chain brominated alkanes, and ethyl alcohol is
Solvent has synthesized C6-2-18And C8-2-16Two kinds of product.
CN 200910060443.9 discloses a kind of asymmetrical type cationic surfactant and preparation method thereof.The party
For method using dimethyl tertiary amine and dihalo hydrocarbon as raw material, acetonitrile is solvent, has synthesized the asymmetrical type cation form of Cn-s-m type
Face activating agent.
CN 201110226291.2 discloses a kind of cation Gemini surfactant and preparation method thereof.This method with
4-methyl hexamethylene diamine and bromo-octadecane are raw material, and acetonitrile is solvent, has synthesized C6-6-18Cationic surfactant.
In the prior art, there is long step, expensive raw material price and easily cause ring in the synthesis of asymmetric bi-quaternary ammonium salt
The problems such as border is polluted.Therefore, optimum synthesis technique reduces production cost, and it will be from now on or even very one section long for reducing environmental pollution
Research emphasis in time.
Summary of the invention
In view of the above the deficiencies in the prior art, the purpose of the present invention is to provide a kind of synthesis sides of asymmetric bi-quaternary ammonium salt
Method, unilateral including long-chain halogenated alkane and two tertiary amines reacts and unilateral reaction product and short chain halogenated alkane react.It should
Method has the advantages that synthesis technology is simple and production cost is controllable.
The present invention also provides the asymmetry bi-quaternary ammonium salts according to made from the method to have nano flake structure in synthesis
MFI structure molecular sieve in application.It is described asymmetry bi-quaternary ammonium salt can be improved the molecular sieve catalysis reaction in
Diffusion control, to improve its catalytic activity.
The present invention provides a kind of preparation methods of asymmetric bi-quaternary ammonium salt, comprising the following steps:
(i) long-chain halogenated alkane, two tertiary amines and auxiliary agent are added in the first solvent, heating is reacted, to the end of reacting
After be separated by solid-liquid separation, optionally washing and drying solid, obtain asymmetric bi-quaternary ammonium salt intermediate；
(ii) intermediate, the short chain halogenated alkane obtained step (i) is added in the second solvent, and heating is reacted, to
It is separated by solid-liquid separation after reaction, optionally washing and drying solid, obtains asymmetric bi-quaternary ammonium salt.
It should be understood that the long-chain halogenated alkane and short chain halogenated alkane are that in contrast, long-chain halogenated alkane is than short chain halogen
There is longer carbochain for alkane.
The auxiliary agent that the present invention uses effectively changes the Cloud Distribution of carbon-halogen bond in halogenated alkane, is increasing carbon atom just
Electrically, be conducive to the nucleophilic substitution of tertiary amine, to accelerate reaction speed, and help to obtain higher total yield of products.
According to the present invention, the long-chain halogenated alkane is preferably selected from C10-C22Chlorine or bromine is for one of alkane, more preferably
Selected from C14-C18One of brominated alkanes.The short chain halogenated alkane is preferably selected from C1-C6Chlorine or bromine for one of alkane,
It is more preferably selected from C2-C4One of brominated alkanes.In the present invention, first two tertiary amines and long-chain halogenated alkane are carried out unilateral anti-
It answers, then unilateral reaction product is reacted with short chain halogenated alkane.The long-chain halogenated alkane and short chain halogenated alkane are at this
In the range of invention limits, the reaction speed of step (ii) can be accelerated, and improve product yield.
In certain specific embodiments of the invention, the long-chain halogenated alkane can be bromodecane, chloro 12
One of alkane, chloro-tetradecane, bromohexadecane, bromo-octadecane, bromo eicosane and bromo docosane.The short chain
Halogenated alkane can be one of bromomethane, chloric ethane, chloro-propane, butyl bromide, bromo pentane and bromo hexane.
Two tertiary amine is preferably selected from C4-C16One of two tertiary amines, more preferable C6-C12One of two tertiary amines, it is optimal
Select N, N, N ', N ' -4-methyl hexamethylene diamine.
The auxiliary agent preferably includes C2-C10Alcohols and C2-C10At least one of amide more preferably includes C2-C5Alcohols and
C2-C6At least one of at least one of amide, also preferably ethyl alcohol, normal propyl alcohol and dimethylformamide, most preferably diformazan
Base formamide.
First solvent preferably includes C3-C6One of ketone, more preferable acetone.
In a preferred embodiment of the invention, the molar ratio of two tertiary amine and long-chain halogenated alkane is (0.5-16):
1, more preferable (1-10): 1, most preferably 2:1.The molar ratio of first solvent and two tertiary amines is (2-20): 1, more preferable (5-
15): 1, most preferably 10:1.The molar ratio of the auxiliary agent and the first solvent is (0.1-3): 1, more preferable (0.1-1): 1, most preferably
(0.125-0.5):1。
The temperature of the heating is preferably 30-100 DEG C, more preferable 40-80 DEG C, most preferably 60 DEG C.The time of the reaction
Preferably 5-20h, more preferable 8-15h, most preferably 12h.
In the specific embodiment of the present invention, step (i) includes by the long-chain halogenated alkane, two tertiary amines and helping
Agent is added in the first solvent and is uniformly mixed, and stirring is heated and reacted under condensing reflux.When reaction solution is in viscous pasty state
Reaction was completed, is cooled to room temperature, filtering, by remaining dope organic solvent preferred acetone extract 3-4 times, at 40-60 DEG C
Vacuum drying is to get to asymmetric quaternary ammonium salt intermediate.
According to the present invention, in step (ii), second solvent preferably includes C3-C6At least one of alcohols, it is more excellent
Choosing includes at least one of ethyl alcohol, normal propyl alcohol and isopropanol, most preferably normal propyl alcohol.
In a preferred embodiment of the invention, mole of the short chain halogenated alkane and asymmetric bi-quaternary ammonium salt intermediate
Than for (1-8): 1, more preferable (1-5): 1, most preferably 3:1.The molar ratio of second solvent and intermediate is (20-150): 1,
More preferably (50-100): 1, most preferably 80:1.
The temperature of the heating is preferably 50-120 DEG C, more preferable 85-95 DEG C, most preferably 90 DEG C.The time of the reaction
Preferably 40-120h, more preferable 60-90h, most preferably 72h.
In the specific embodiment of the present invention, step (ii) includes that the short chain halogenated alkane and asymmetry is double
Quaternary ammonium salt intermediate is added in the second solvent and is uniformly mixed, and stirring is heated and reacted under condensing reflux.After reaction
It is cooled to room temperature, solvent under reduced pressure is steamed into 60-90wt%, the preferred acetone washing of organic solvent is added to there is white precipitate precipitation,
Filtering, the vacuum drying at 40-60 DEG C, obtained white solid are asymmetric bi-quaternary ammonium salt.
In the present invention, the organic solvent used when step (i) and step (ii) are washed is preferably ketones solvent
The lower organic solvent of isopolarity or nonpolar solvent.Within this range, the present invention can obtain higher intermediate yield and
Product yield.
In the preparation process of asymmetric bi-quaternary ammonium salt provided by the invention, halogenated alkane is reacted with di-tertiary amine, is first generated
Mono-quaternaries containing tertiary amine, further reaction generates bi-quaternary ammonium salt, and control asymmetric bi-quaternary ammonium salt intermediate synthesis is
The key and difficult point of this reaction.It uses ketone for solvent in the synthetic system of the first step of the present invention, adds amide or alcohols is to help
Agent.By the polarity of modulation solvent, achievees the purpose that control first step reaction speed, to improve the yield of intermediate, and mention
The efficiency and total recovery of this high reaction.In addition, solvent is used as usually using acetonitrile and toluene mixing in the prior art, to environment dirt
Dye is serious.Ketones and alcohols are used only as solvent in the present invention, and environmental pollution is small, remain to reach under the reaction condition of optimization
Higher yield.
According to the present invention, the yield of the asymmetric bi-quaternary ammonium salt intermediate of step (i) can reach 85% or more, and step (ii) is no
The yield of symmetrical bi-quaternary ammonium salt can reach 95% or more.The yield of asymmetry bi-quaternary ammonium salt preparation method provided by the invention is reachable
To 80% or more.
In a preferred embodiment of the invention, two tertiary amine is N, N, N ', N ' -4-methyl hexamethylene diamine synthesizes at this time
The preparation-obtained molecular sieve of asymmetric bi-quaternary ammonium salt have higher activity.The structural formula of the asymmetry bi-quaternary ammonium salt is such as
(a) shown in, synthesis process is such as shown in (b):
Wherein, R1It is preferably selected from C1-C6One of alkyl is more preferably selected from C2-C4One of alkyl；R2It is preferably selected from
C10-C22One of alkyl is more preferably selected from C14-C18One of alkyl；X is Cl or Br, more preferable Br.
The present invention synthesizes asymmetric bi-quaternary ammonium salt using two tertiary amines and halogenated alkane as raw material, through two step substitution reactions.Pass through
The actual conditions for optimizing substitution reaction rationally control reaction time and the reaction condition of halogenated alkane substitution, further increase
The yield of reaction, and the purifying difficulty of finished product is reduced, it can be obtained the higher finished product of purity without purification.Into one
Step ground, the asymmetry Bis-quaternary Ammonium Salt Surfactant can be used for the list of synthesizing new structure as special structure directing agent
Structure cell nanometer layer MFI catalyst has the application of extensive market.
The beneficial effect of the present invention compared with prior art is:
1. industrial chemicals needed for preparation is the raw material of industry, cheap, raw material need not carry out any removal of impurities processing；
2. synthesis device is simple, only need popular response container equipped with heating, stirring condenses facility；
3. total recovery is high, general up to 80% or more, there is outstanding economic benefit；
4. preparation process meets environmental requirement, solvent and unconverted raw material recoverable, no pollution is basically reached.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
It can be with conventional products that are commercially available.
Embodiment 1
The preparation of asymmetric bi-quaternary ammonium salt intermediate: 45mL N', N', N' being added into the three-necked flask with thermometer,
N- 4-methyl hexamethylene diamine, α mL acetone and β mL dimethylformamide (specific value of α and β are shown in Table 1), are slowly stirred, are warming up to
60 DEG C, it is slowly added to 36mL 1- bromo docosane with dropping funel, after being added dropwise to complete, back flow reaction 12h, reaction solution at this time
It in thick, is cooled to room temperature, filters, with acetone washing, 50 DEG C of drying.Obtain midbody product C22H45Br-N(CH3)2-
(CH2)6--N(CH3)2.The midbody product yield that the acetone and dimethylformamide of different ratio obtain is shown in Table 1.
Table 1
| α | β | Acetone and dimethylformamide molar ratio | Theoretical yield/g | Actual production/g | Yield |
| 150 | 15 | 10:1 | 50.34 | 31.57 | 62.71% |
| 150 | 18 | 8:1 | 50.34 | 36.39 | 72.29% |
| 150 | 30 | 5:1 | 50.34 | 40.82 | 81.09% |
| 150 | 75 | 2:1 | 50.34 | 38.92 | 77.31% |
| 150 | 150 | 1:1 | 50.34 | 29.46 | 58.52% |
Embodiment 2
The preparation of asymmetric bi-quaternary ammonium salt intermediate: 45mL N', N', N' being added into the three-necked flask with thermometer,
N- 4-methyl hexamethylene diamine, α mL acetone and β mL ethyl alcohol (specific value of α and β are shown in Table 2), are slowly stirred, are warming up to 60 DEG C, with drop
Liquid funnel is slowly added to 36mL 1- bromo docosane, and after being added dropwise to complete, back flow reaction 12h, reaction solution is in thick at this time,
It is cooled to room temperature, filters, with acetone washing, 50 DEG C of drying.Obtain midbody product C22H45Br-N(CH3)2-(CH2)6-N
(CH3)2.The midbody product yield that the acetone and ethyl alcohol of different ratio obtain is shown in Table 2.
Table 2
| α | β | Acetone and ethyl alcohol molar ratio | Theoretical yield/g | Actual production/g | Yield |
| 150 | 12.5 | 10:1 | 50.34 | 23.81 | 47.30% |
| 150 | 15 | 8:1 | 50.34 | 27.35 | 54.33% |
| 150 | 25 | 5:1 | 50.34 | 30.59 | 60.77% |
| 150 | 62.5 | 2:1 | 50.34 | 28.37 | 56.36% |
| 150 | 125 | 1:1 | 50.34 | 27.63 | 54.89% |
Embodiment 3
The preparation of asymmetric bi-quaternary ammonium salt intermediate: 45mL N', N', N', N- are added in the three-necked flask with thermometer
4-methyl hexamethylene diamine, α mL acetone and β mL normal propyl alcohol (specific value of α and β are shown in Table 3), are slowly stirred, are warming up to 60 DEG C, with drop
Liquid funnel is slowly added to 36mL 1- bromo docosane, and after being added dropwise to complete, back flow reaction 12h, reaction solution is in thick at this time,
It is cooled to room temperature, filters, with acetone washing, 50 DEG C of drying.Obtain midbody product C22H45Br-N(CH3)2-(CH2)6-N
(CH3)2.The midbody product yield that the acetone and normal propyl alcohol of different ratio obtain is shown in Table 3.
Table 3
| α | β | Acetone and normal propyl alcohol molar ratio | Theoretical yield/g | Actual production/g | Yield |
| 150 | 15 | 10:1 | 50.34 | 29.90 | 59.40% |
| 150 | 30 | 5:1 | 50.34 | 38.42 | 76.32% |
| 150 | 75 | 2:1 | 50.34 | 35.63 | 70.78% |
| 150 | 150 | 1:1 | 50.34 | 34.70 | 68.93% |
Embodiment 4
The preparation of asymmetric bi-quaternary ammonium salt intermediate: 40mL N', N', N' being added into the three-necked flask with thermometer,
N- tetramethylethylenediamine, α mL butanone and β mL acetamide (specific value of α and β are shown in Table 4), are slowly stirred, and are warming up to 80 DEG C, use
Dropping funel is slowly added to 32mL 1- chloro-hexadecane, and after being added dropwise to complete, back flow reaction 10h, reaction solution is in thick at this time,
It is cooled to room temperature, filters, with acetone washing, 50 DEG C of drying.Obtain midbody product C16H33Cl-N(CH3)2-(CH2)2-N
(CH3)2.The midbody product yield that the acetone and acetamide of different ratio obtain is shown in Table 4.
Table 4
| α | β | Butanone and acetamide molar ratio | Theoretical yield/g | Actual production/g | Yield |
| 120 | 16 | 5:1 | 37.52 | 25.73 | 68.58% |
| 120 | 2540 | 2:1 | X37.52 | 23.69 | 63.14% |
Embodiment 5
The preparation of asymmetric bi-quaternary ammonium salt: the product of 20g embodiment 1 is added in the three-necked flask with thermometer
C22H45Br-N(CH3)2-(CH2)6-N(CH3)2, 15mL bromo hexane and 150mL normal propyl alcohol, be slowly stirred, be warming up to 80 DEG C, return
72h is flowed, reaction solution is in brown color at this time, is cooled to room temperature, and is filtered, with acetone washing, 50 DEG C of drying.Obtain asymmetric double quaternary ammoniums
Salt C22H45Br-N(CH3)2-(CH2)6-N(CH3)2-C6H13Br, yield 84%.
Embodiment 6
The preparation of asymmetric bi-quaternary ammonium salt: the product of 20g embodiment 1 is added in the three-necked flask with thermometer
C22H45Br-N(CH3)2-(CH2)6-N(CH3)2, 15mL bromo hexane and 150mL normal propyl alcohol, be slowly stirred, be warming up to 90 DEG C, return
72h is flowed, reaction solution is in brown color at this time, is cooled to room temperature, and is filtered, with acetone washing, 50 DEG C of drying.Obtain asymmetric double quaternary ammoniums
Salt C22H45Br-N(CH3)2-(CH2)6-N(CH3)2-C6H13Br, yield 94%.
Embodiment 7
The preparation of asymmetric bi-quaternary ammonium salt: the product of 20g embodiment 1 is added in the three-necked flask with thermometer
C22H45Br-N(CH3)2-(CH2)6-N(CH3)2, 30mL bromo hexane and 150mL normal propyl alcohol, be slowly stirred, be warming up to 80 DEG C, return
72h is flowed, reaction solution is in brown color at this time, is cooled to room temperature, and is filtered, with acetone washing, 50 DEG C of drying.Obtain asymmetric double quaternary ammoniums
Salt C22H45Br-N(CH3)2-(CH2)6-N(CH3)2-C6H13Br, yield 94%.
Embodiment 8
The preparation of asymmetric bi-quaternary ammonium salt: the product of 20g embodiment 4 is added in the three-necked flask with thermometer
C16H33Cl-N(CH3)2-(CH2)2-N(CH3)2, 27mL chloro-propane and 150mL ethyl alcohol, be slowly stirred, be warming up to 80 DEG C, reflux
72h, reaction solution is in brown color at this time, is cooled to room temperature, and is filtered, with acetone washing, 50 DEG C of drying.Obtain asymmetric bi-quaternary ammonium salt
C16H33Cl-N(CH3)2-(CH2)2-N(CH3)2-C2H5Cl, yield 86%.
Embodiment 9
The preparation of asymmetric bi-quaternary ammonium salt: with embodiment 8 the difference is that, chloric ethane 50mL, reaction temperature
It is 90 DEG C.Obtain asymmetric bi-quaternary ammonium salt C16H33Cl-N(CH3)2-(CH2)2-N(CH3)2-C2H5Cl, yield 93%.
Comparative example 1
Difference from example 1 is that dimethylformamide is not added, back flow reaction 12h.Obtain intermediate product
C22H45Br-N(CH3)2-(CH2)6-N(CH3)2, yield 38%.
Comparative example 2
Difference from example 1 is that acetone is not added, 150mL dimethylformamide, back flow reaction 10h is added.
Obtain intermediate product C22H45Br-N(CH3)2-(CH2)6-N(CH3)2, yield 46%.
Comparative example 3
Difference from example 1 is that acetone and dimethylformamide are not added, acetonitrile 150mL is added.In obtaining
Between product C22H45Br-N(CH3)2-(CH2)6-N(CH3)2, yield 45%.
Comparative example 4
The difference is that, normal propyl alcohol is not added with embodiment 6, acetonitrile 150mL is added.Obtain asymmetric bi-quaternary ammonium salt
C22H45Br-N(CH3)2-(CH2)6-N(CH3)2-C6H13Br, yield 92%.
Existed by the synthetic method that above embodiments and comparative example can be seen that asymmetric bi-quaternary ammonium salt provided by the invention
Under the synergistic effect of the solvent and auxiliary agent, higher yield can be obtained.Such as the yield highest of the intermediate product of comparative example 1-3
No more than 50%；And in embodiment 1-4, under the synergy by solvent and auxiliary agent, yield is significantly improved.Especially in reality
It applies in example 1, when the molar ratio of auxiliary agent dimethylformamide and acetone is 1:5, yield can reach 81%.Comparative example 4 uses
Acetonitrile is only 92% as solvent, the product yield of acquisition；And embodiment 6 uses normal propyl alcohol that can obtain 94% as solvent
Yield.It can be seen that the preparation method provided through the invention can obtain, yield is higher and cost is lower asymmetric double
Quaternary ammonium salt, and it is smaller to the pollution of environment, it is with a wide range of applications.
It should be noted that embodiment described above for explaining only the invention, is not constituted to of the invention any
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (15)
1. a kind of preparation method of asymmetry bi-quaternary ammonium salt, comprising the following steps:
(i) by long-chain halogenated alkane, two tertiary amines and auxiliary agent be added the first solvent in, heating reacted, to after reaction into
Row is separated by solid-liquid separation, optionally washing and drying solid, obtains asymmetric bi-quaternary ammonium salt intermediate；
(ii) intermediate, the short chain halogenated alkane obtained step (i) is added in the second solvent, and heating is reacted, wait react
After be separated by solid-liquid separation, optionally washing and drying solid, obtain asymmetric bi-quaternary ammonium salt；
Wherein, the long-chain halogenated alkane is selected from C10-C22Chlorine or bromine is for one of alkane；And/or
The short chain halogenated alkane is selected from C1-C6Chlorine or bromine is for one of alkane；And
Wherein, in step (ii), the molar ratio of second solvent and intermediate is (20-150): 1；
In step (i), the auxiliary agent is at least one of ethyl alcohol, normal propyl alcohol and dimethylformamide；And/or
First solvent is acetone；
Two tertiary amine is N, N, N ', N ' -4-methyl hexamethylene diamine；
Second solvent includes at least one of normal propyl alcohol and isopropanol.
2. the method according to claim 1, wherein in step (i), mole of the auxiliary agent and the first solvent
Than for (0.1-3): 1.
3. according to the method described in claim 2, it is characterized in that, in step (i), mole of the auxiliary agent and the first solvent
Than for (0.1-1): 1.
4. the method according to claim 1, wherein the long-chain halogenated alkane is selected from C14-C18In brominated alkanes
One kind；And/or
The short chain halogenated alkane is selected from C2-C4One of brominated alkanes.
5. the method according to claim 1, wherein in step (i), two tertiary amine and long-chain halogenated alkane
Molar ratio be (0.5-16): 1；And/or
The molar ratio of first solvent and two tertiary amines is (2-20): 1.
6. according to the method described in claim 5, it is characterized in that, in step (i), two tertiary amine and long-chain halogenated alkane
Molar ratio be (1-10): 1；And/or
The molar ratio of first solvent and two tertiary amines is (5-15): 1.
7. the method according to claim 1, wherein the temperature of the heating is 30-100 in step (i)
℃；The time of the reaction is 5-20h.
8. the method according to the description of claim 7 is characterized in that the temperature of the heating is 40-80 DEG C in step (i)；
The time of the reaction is 8-15h.
9. the method according to claim 1, wherein in step (ii), second solvent and intermediate
Molar ratio is (50-100): 1.
10. the method according to claim 1, wherein second solvent is normal propyl alcohol.
11. the method according to claim 1, wherein in step (ii), the short chain halogenated alkane with it is not right
The molar ratio of bi-quaternary ammonium salt intermediate is referred to as (1-8): 1.
12. according to the method for claim 11, which is characterized in that in step (ii), the short chain halogenated alkane with not
The molar ratio of symmetric double quaternary ammonium salt intermediate is (1-5): 1.
13. the method according to claim 1, wherein the temperature of the heating is 50-120 in step (ii)
℃；And/or
The time of the reaction is 40-120h.
14. according to the method for claim 13, which is characterized in that in step (ii), the temperature of the heating is 85-95
℃；And/or
The time of the reaction is 60-90h.
15. a kind of application of asymmetry bi-quaternary ammonium salt in Zeolite synthesis；It include: to utilize any one of claim 1-14
The method prepares asymmetric bi-quaternary ammonium salt, and the asymmetric bi-quaternary ammonium salt is then used for Zeolite synthesis.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510750137.3A CN106674017B (en) | 2015-11-06 | 2015-11-06 | A kind of synthetic method and its application of asymmetry bi-quaternary ammonium salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510750137.3A CN106674017B (en) | 2015-11-06 | 2015-11-06 | A kind of synthetic method and its application of asymmetry bi-quaternary ammonium salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106674017A CN106674017A (en) | 2017-05-17 |
| CN106674017B true CN106674017B (en) | 2018-12-28 |
Family
ID=58858440
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510750137.3A Active CN106674017B (en) | 2015-11-06 | 2015-11-06 | A kind of synthetic method and its application of asymmetry bi-quaternary ammonium salt |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106674017B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107321262A (en) * | 2017-07-14 | 2017-11-07 | 太原理工大学 | A kind of preparation method of asymmetric gemini quaternary ammonium salt cationic surfactant |
| CN110746308B (en) * | 2019-11-06 | 2022-04-08 | 山东泰和水处理科技股份有限公司 | Continuous production method of biquaternary ammonium salt |
| CN113526518B (en) * | 2020-04-17 | 2022-10-21 | 中国石油化工股份有限公司 | All-silicon molecular sieve with ITH structure and synthesis method thereof |
| CN112536067B (en) * | 2020-04-20 | 2022-12-23 | 青岛理工大学 | Preparation method and application of hierarchical pore SAPO-11 molecular sieve and long paraffin isomerization catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102701998A (en) * | 2012-06-11 | 2012-10-03 | 福州大学 | Method for preparing quaternary ammonium salt foaming agent |
| CN104311857A (en) * | 2014-10-17 | 2015-01-28 | 中国科学技术大学 | Preparation method for double quaternary ammonium side long chain anion-exchange membrane |
| WO2015069760A1 (en) * | 2013-11-05 | 2015-05-14 | Temple University Of The Commonwealth System Of Higher Education | Biscationic and triscationic amphiles as antimicrobial agents |
-
2015
- 2015-11-06 CN CN201510750137.3A patent/CN106674017B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102701998A (en) * | 2012-06-11 | 2012-10-03 | 福州大学 | Method for preparing quaternary ammonium salt foaming agent |
| WO2015069760A1 (en) * | 2013-11-05 | 2015-05-14 | Temple University Of The Commonwealth System Of Higher Education | Biscationic and triscationic amphiles as antimicrobial agents |
| CN104311857A (en) * | 2014-10-17 | 2015-01-28 | 中国科学技术大学 | Preparation method for double quaternary ammonium side long chain anion-exchange membrane |
Non-Patent Citations (1)
| Title |
|---|
| One-pot synthesis of hierarchical mordenite and its performance in the benzylation of benzene with benzyl alcohol;Yuping Li etal;《J Mater Sci》;20150429;第50卷;第5060页实验部分 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106674017A (en) | 2017-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106674017B (en) | A kind of synthetic method and its application of asymmetry bi-quaternary ammonium salt | |
| CN104084230A (en) | Preparation method of solid catalyst for Knoevenagel reaction | |
| CN108203384B (en) | Method for preparing o-nitrobenzyl bromide | |
| CN102786499B (en) | Method for preparing cyclohexene oxide | |
| CN109046452A (en) | A kind of supported heteropolyacid catalyst and its preparation method and application | |
| CN105772080B (en) | Tripolite loading palladium catalyst, preparation method and applications | |
| CN104402731A (en) | Method utilizing catalytic hydrogenation synthesis of nitrobenzene compounds to prepare aniline compounds | |
| CN107235891B (en) | Preparation method of 4-bromocarbazole | |
| CN101863847A (en) | Preparation method of sulfonanilide compound | |
| CN107552093B (en) | Supported iridium catalyst for bisphenol F and esterification reaction and preparation method thereof | |
| CN105732439A (en) | Multi-sulfonic-acid-group acidic functionalized ionic liquid and preparation method thereof | |
| CN105294570B (en) | A kind of synthetic method of 3,4 dihydropyrimidinonesands/thioketone | |
| CN108623468B (en) | Method for preparing benzylamine by adopting microchannel reaction device | |
| CN103464192A (en) | Mesoporous nickel-molybdenum oxide catalyst, and preparation method and application thereof | |
| CN104475058B (en) | A kind of sewage-treating agent | |
| CN107903182B (en) | Synthesis method of 2-amino-4-acetamino anisole | |
| CN102633682B (en) | Continuous production process of cyanoacetate | |
| CN104557785A (en) | Method for jointly preparing styrene oxide and benzaldehyde by heterogeneous catalytic epoxidized styrene | |
| CN106674018B (en) | A kind of method and its application synthesizing asymmetric bi-quaternary ammonium salt | |
| CN107694610A (en) | A kind of phase transfer catalyst for cyclohexanol synthesizing cyclohexanone and preparation method thereof | |
| CN109422663A (en) | A kind of method of continuous flow synthesis quaternary ammonium salt | |
| CN109438402B (en) | Benzofuranone derivatives and synthesis method thereof | |
| CN106083632A (en) | A kind of synthetic method of dye composition fast red KD base | |
| CN104310504B (en) | The treatment process of organic pollutant in a kind of dyeing waste water | |
| CN107915694A (en) | 1 [2 (2,4 3,5-dimethylphenyl sulfydryl) phenyl] piperazine hydrochloride and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |