CN106674018B - A kind of method and its application synthesizing asymmetric bi-quaternary ammonium salt - Google Patents
A kind of method and its application synthesizing asymmetric bi-quaternary ammonium salt Download PDFInfo
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Abstract
The present invention provides a kind of methods for synthesizing asymmetric bi-quaternary ammonium salt, the following steps are included: (i) long-chain halogenated alkane, two tertiary amines 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；Wherein, the reaction in step (i) and/or step (ii) carries out under microwave heating.The present invention also provides application of the asymmetric bi-quaternary ammonium salt being prepared according to the method in Zeolite synthesis.Preparation method provided by the invention has step simple, and solvent usage is few, the advantage that reaction temperature is low and the reaction time is short.
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
Asymmetric bi-quaternary ammonium salt is the key that nano flake MFI Zeolite synthesis.The asymmetry bi-quaternary ammonium salt can use knot
Structure formula Cm-6-nIt indicates, wherein m value is corresponding with the asymmetric piece interlamellar spacing of quaternary ammonium salt, n value and nano flake MFI molecular sieve
Lamellar spacing is closely related.Synthesize the asymmetric bi-quaternary ammonium salt C with different m and n valuesm-6-nFor modulation nano flake MFI points
The texture property of son sieve is of great significance.
South Korea Ryoo professor seminar is with asymmetric bi-quaternary ammonium salt C within 200922H45N+(CH3)2C6H12N+(CH3)2C6H13
(Br-)2(abbreviation C22-6-6Br2) it is that template successfully synthesizes nano flake MFI structure molecular sieve.The nano flake MFI of synthesis is tied
Structure molecular sieve its in b axis direction straight channels length only unit cell dimensions, about 2nm or so, piece interlamellar spacing and asymmetric double quaternary ammoniums
The length of salt Long carbon chain is corresponding.The material effectively improves the diffusion of molecular sieve, and has good (water) heat steady
Qualitative and adjustable acidity, therefore there is stronger catalytic applications prospect.Around asymmetric bi-quaternary ammonium salt Cm-6-nBr2For template
Agent, molecular sieve, control molecular sieve lamellar spacing and the spacing of synthesis specific direction growth have received widespread attention.
The synthesis process of asymmetric bi-quaternary ammonium salt is a continuous quaternized reaction, is generally completed in two steps, i.e., intermediate
Two steps of body and Product formation.When the first step, the degree for controlling reaction is the key that reaction and difficult point, and the reaction of bromine atom is living
Property cannot be too strong, both guarantee the yield of mono-quaternaries, and reduce the generation of side reaction again；Second step synthesizes then on the contrary, to mention
The reactivity of high bromine atom, as far as possible shortening reaction time.The synthesis step of asymmetric bi-quaternary ammonium salt is long, expensive raw material price,
Limit its application as template synthesis Jie's mesoporous-microporous composite molecular sieve.
Patent CN 102784854A, 200910060443.9 CN disclose the preparation method of asymmetric bi-quaternary ammonium salt, with
Dimethyl tertiary amine and halogenated hydrocarbons are raw material, are synthesized in two steps, and generated time is long, and operating procedure is complicated.
However, such as requiring a large amount of solvent, reaction time since there are problems for the synthesis of asymmetric bi-quaternary ammonium salt
Long, yield is more low, limits it in the use of molecular sieve preparation field.
Summary of the invention
In order to overcome synthesis process complexity in the prior art, generated time grows the problem low with yield, the present invention provides
A method of rapidly and efficiently synthesizing asymmetric bi-quaternary ammonium salt, under microwave with long-chain halogenated alkane and two tertiary amines it is unilateral instead
Answer, unilateral reaction product is reacted with short chain halogenated alkane, the asymmetric bi-quaternary ammonium salt is prepared through two steps.The method contracting
Short asymmetric bi-quaternary ammonium salt Cn-6-mGenerated time, reduce solvent usage, improve yield, and effectively reduce and be produced into
This.
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 methods for synthesizing asymmetric bi-quaternary ammonium salt, comprising the following steps:
(i) long-chain halogenated alkane, two tertiary amines are added in the first solvent, heating is reacted, to carry out after reaction
It 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, to
It is separated by solid-liquid separation after reaction, optionally washing and drying solid, obtains asymmetric bi-quaternary ammonium salt；
Wherein, the reaction in step (i) and/or step (ii) carries out under microwave heating.
According to the present invention, the step (i) and step (ii) at least one step are reacted under microwave heating, excellent
Two steps are selected all to be reacted under microwave heating.
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.
Compared with conventional heating methods, the present invention changes the heating of material molecule by the simple operations of microwave heating
Mode can especially greatly improve reaction rate under relatively lower temp, and obtain higher product yield.
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.
According to the present invention, two tertiary amine is preferably selected from C4-C16One of two tertiary amines, more preferable C6-C12In two tertiary amines
One kind, most preferably N, N, N ', N ' -4-methyl hexamethylene diamine.
First solvent preferably includes C3-C5One of ketone, more preferable acetone.
In a preferred embodiment of the invention, the molar ratio of first solvent and long-chain halogenated alkane is (2-25):
1, more preferable (5-20): 1, most preferably (8-10): 1.The molar ratio of two tertiary amine and long-chain halogenated alkane is (1.5-14): 1,
More preferably (2-10): 1, most preferably (3-5): 1.Because reaction speed of the invention is comparatively fast easy to appear side reaction, as two uncle
The molar ratio of amine and long-chain halogenated alkane within this range, can preferably avoid two tertiary amines and long-chain after generating mono-quaternaries
The reaction was continued for halogenated alkane, generates symmetrical bi-quaternary ammonium salt, to obtain the intermediate of higher yields.
Preferably, the reaction in the step (i) carries out under microwave heating, and the heating temperature of microwave is 30-60 DEG C,
It is preferred that 40-48 DEG C.The power of the microwave is 100-600W, preferably 200-300W.The time of the reaction is preferably 1-
15min, more preferable 5-10min.
Compared with prior art, the present invention the quantity of solvent needed is decreased obviously, and the reaction time also greatly shortens.This
Outside, the temperature of microwave heating needed for the present invention is lower than the prior art, higher yield can be obtained at a lower temperature, in work
A large amount of energy consumptions can be saved in industry, and there is good economic benefit.
In the specific embodiment of the present invention, after step (i) reaction terminates to obtain product, remaining two are removed
Tertiary amine and the first solvent are to get to asymmetric bi-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, the asymmetric bi-quaternary ammonium salt intermediate and the molar ratio of the second solvent are
1:(1-25), more preferable 1:(1-20), most preferably 1:(1-5).The asymmetry bi-quaternary ammonium salt intermediate and short chain halogenated alkane
Molar ratio be 1:(1-16), more preferable 1:(1-10), most preferably 1:(2-5).In the present invention, when asymmetric double quaternary ammoniums
The molar ratio of salt intermediate and short chain halogenated alkane within this range, can increase the yield of the intermediate, to obtain more
High product yield, and control cost.
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.
Preferably, the reaction in the step (ii) carries out under microwave heating.The power of the microwave is 100-600W,
It is preferred that 200-300W.The heating temperature of the microwave is preferably 30-90 DEG C, and more preferable 60-80 DEG C.The time of the reaction is preferred
For 1-30min, more preferable 8-15min.
In the specific embodiment of the present invention, after step (ii) reaction terminates to obtain product, remove remnants'
Short chain halogenated alkane and the second solvent are to get to asymmetric bi-quaternary ammonium salt.
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 is efficient using microwave method, is quickly prepared for asymmetric bi-quaternary ammonium salt, and the total recovery of products therefrom can reach
To 60% or more.In addition, method provided by the invention highly shortened the reaction time for preparing asymmetric bi-quaternary ammonium salt, improve
Reaction rate；And the dosage of solvent is considerably reduced, raw material availability is high, and reaction condition is mild.
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.
The MARS 6 for the microwave reactor model U.S. CE M company that embodiment uses.
Embodiment 1
Asymmetric quaternary ammonium salt C22-6-6Br2Synthesis:
(1) asymmetric bi-quaternary ammonium salt intermediate C22-6The synthesis of Br
Take 45mL N, N, N ', N ' -4-methyl hexamethylene diamine and 40mL bromo docosane and 80mL acetone are added in beaker,
It stirs evenly, is placed in microwave reactor, carry out microwave reaction.The power for adjusting microwave is 350W, and heating temperature is 60 DEG C, instead
It is 12min between seasonable.Product is filtered after reaction, then with acetone washing remove unreacted 4-methyl hexamethylene diamine and
Asymmetric quaternary ammonium salt intermediate C can be obtained in bromo docosane22-6Br, yield 60%。
(2) synthesis of asymmetric bi-quaternary ammonium salt
Take the asymmetric quaternary ammonium salt intermediate C synthesized in 60g step (1)22-6Br, 45mL bromo hexane and 80mL normal propyl alcohol
It is added in beaker, stirs evenly, be placed in microwave reactor, carry out microwave reaction.The power for adjusting microwave is 400W, heating temperature
Degree is 80 DEG C, reaction time 15min.Acetone is added after reaction, is filtered after being sufficiently stirred, then with acetone washing
Obtain asymmetric quaternary ammonium salt C22-6-6Br2, yield 92%。
Embodiment 2
Asymmetric quaternary ammonium salt C18-6-5Br2Synthesis:
(1) asymmetric bi-quaternary ammonium salt intermediate C18-6The synthesis of Br
Take 45mL N, N, N ', N ' -4-methyl hexamethylene diamine and 35mL bromo-octadecane and 80mL acetone are added in beaker, stir
It mixes uniformly, is placed in microwave reactor, carry out microwave reaction.The power for adjusting microwave is 300W, and heating temperature is 55 DEG C, reaction
Time is 10min.Product is filtered after reaction, then removes unreacted 4-methyl hexamethylene diamine and bromine with acetone washing
For octadecane, asymmetric quaternary ammonium salt intermediate C can be obtained18-6Br, yield 62%。
(2) asymmetric bi-quaternary ammonium salt C18-6-5Br2Synthesis
Take the asymmetric quaternary ammonium salt intermediate C synthesized in 50g step (1)18-6Br, 30mL bromo pentane and 80mL isopropyl
Alcohol is added in beaker, stirs evenly, is placed in microwave reactor, carries out microwave reaction.The power for adjusting microwave is 400W, heating
Temperature is 80 DEG C, reaction time 12min.Acetone is added after reaction, is filtered after being sufficiently stirred, then with acetone washing, i.e.,
Asymmetric quaternary ammonium salt C can be obtained18-6-5Br2, yield 85%。
Embodiment 3
Asymmetric quaternary ammonium salt C16-6-4Br2Synthesis:
(1) asymmetric bi-quaternary ammonium salt intermediate C16-6The synthesis of Br
Take 45mLN, N, N ', N ' -4-methyl hexamethylene diamine and 30mL bromohexadecane and 80mL acetone are added in beaker, stirring
Uniformly, it is placed in microwave reactor, carries out microwave reaction.The power for adjusting microwave is 300W, and heating temperature is 50 DEG C, when reaction
Between be 10min.Product is filtered after reaction, then removes unreacted 4-methyl hexamethylene diamine and bromo with acetone washing
Asymmetric quaternary ammonium salt intermediate C can be obtained in hexadecane16-6Br, yield 58%。
(2) asymmetric bi-quaternary ammonium salt C16-6-4Br2Synthesis
The asymmetric quaternary ammonium salt intermediate synthesized in 45g step (1), 30mL bromination of n-butane and 80mL normal propyl alcohol is taken to be added
It in beaker, stirs evenly, is placed in microwave reactor, carry out microwave reaction.The power for adjusting microwave is 450W, and heating temperature is
70 DEG C, reaction time 20min.Acetone is added after reaction, is filtered after being sufficiently stirred, then with acetone washing, can be obtained
Asymmetric quaternary ammonium salt C16-6-4Br2, yield 90%.
Embodiment 4
With embodiment 3 the difference is that: in the synthesis process of intermediate, heating temperature be 40 DEG C.It obtains not
Asymmetric quaternary ammonium salt intermediate C16-6Br yield is 53%。
Embodiment 5
Asymmetric quaternary ammonium salt C12-2-3Cl2Synthesis:
(1) asymmetric bi-quaternary ammonium salt intermediate C12-2The synthesis of Cl
Take 45mL N, N, N ', N '-tetramethylethylenediamine and 20mL chlorinated dodecane and 50mL butanone are added in beaker, stir
It mixes uniformly, is placed in microwave reactor, carry out microwave reaction.The power for adjusting microwave is 300W, and heating temperature is 60 DEG C, reaction
Time is 15min.Product is filtered after reaction, then removes unreacted tetramethylethylenediamine and chlorine with acetone washing
For dodecane, asymmetric quaternary ammonium salt intermediate C can be obtained12-2Cl, yield 57%。
(2) asymmetric bi-quaternary ammonium salt C12-2-3Cl2Synthesis
Take the asymmetric quaternary ammonium salt intermediate C synthesized in 45g step (1)12-2Cl, 25mL chloro n-propane and 50mL ethyl alcohol
It is added in beaker, stirs evenly, be placed in microwave reactor, carry out microwave reaction.The power for adjusting microwave is 450W, heating temperature
Degree is 70 DEG C, reaction time 20min.Acetone is added after reaction, is filtered after being sufficiently stirred, then with acetone washing,.It obtains
Asymmetric quaternary ammonium salt C12-2-3Cl2Yield is 84%
Comparative example 1
Asymmetric quaternary ammonium salt C22-6-6Br2Synthesis:
(1) asymmetric bi-quaternary ammonium salt intermediate C22-6The synthesis of Br
45mL N', N', N', N- 4-methyl hexamethylene diamine and 150mL acetone are added into the three-necked flask with thermometer,
It is slowly stirred, using heating water bath, is warming up to 60 DEG C.40mL 1- bromo docosane is slowly added to dropping funel.It drips
Cheng Hou, back flow reaction 12h.When reaction solution is in thick, reaction was completed, is cooled to room temperature.It is washed after product is filtered with acetone
It washs, 50 DEG C of drying.Obtain midbody product C22-6Br, yield 38%.
(2) synthesis of asymmetric bi-quaternary ammonium salt
Take the product C of 50g step (1)22-6Br, 45mL bromo hexane and 150mL normal propyl alcohol, are placed in three equipped with thermometer
It in mouth flask, is slowly stirred, using heating water bath, is warming up to 80 DEG C, flow back 72h.When reaction solution is in brown color, reaction was completed,
It is cooled to room temperature.Acetone washing, 50 DEG C of drying are used after product is filtered.Obtained asymmetric bi-quaternary ammonium salt C22-6-6Br2Yield is
83%.
Comparative example 2
Asymmetric quaternary ammonium salt C18-6-3Br2Synthesis:
(1) asymmetric bi-quaternary ammonium salt intermediate C18-6The synthesis of Br
45mL N', N', N', N- 4-methyl hexamethylene diamine and 150mL acetone are added in three-necked flask with thermometer, delays
Slow stirring, using heating water bath, is warming up to 60 DEG C, is slowly added to 30mL 1- bromohexadecane with dropping funel, is added dropwise to complete
Afterwards, back flow reaction 12h, reaction solution is in thick at this time, is cooled to room temperature, and is filtered, with acetone washing, 50 DEG C of vacuum dryings.?
To midbody product C18-6Br, yield 35%.
(2) synthesis of asymmetric bi-quaternary ammonium salt
Take the product C of 50g above-mentioned steps (1)18-6Br, 30mL bromo propane and 150mL normal propyl alcohol are placed in thermometer
Three-necked flask in, be slowly stirred, using heating water bath, be warming up to 80 DEG C, flow back 72h, and reaction solution is in brown color at this time, cooling
To room temperature, filtering, with acetone washing, 50 DEG C of vacuum dryings.Obtained asymmetric bi-quaternary ammonium salt C18-6-3Br2Yield is 80%.
Comparative example 3
With comparative example 2 the difference is that: in the synthesis process of intermediate, be warming up to 40 DEG C.Obtained intermediate
Product C18-6Br yield is 22%.
By above embodiments and comparative example it is found that the microwave provided according to the present invention synthesizes the side of asymmetric bi-quaternary ammonium salt
Method can obtain higher yield under lower reaction temperature, and when can substantially reduce required quantity of solvent and shorten reaction
Between.If embodiment 4 is under lower reaction temperature, obtain with yield similar in embodiment 3, and be higher than comparative example 2 and 3.This
Outside, embodiment 4 is compared with comparative example 2 and 3, and solvent usage declines to a great extent from 150mL to 80mL, and the reaction time also shortens from 12h
Yield for 10min, and intermediate is greatly improved.It can be seen that industrially using provided by the invention micro-
The method that wave synthesizes asymmetric bi-quaternary ammonium salt, can be quickly obtained the product of higher yield while cost is reduced, and having can
The economic benefit of sight.
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 (20)
1. a kind of method for synthesizing asymmetric bi-quaternary ammonium salt, comprising the following steps:
(i) long-chain halogenated alkane, two tertiary amines are added in the first solvent, heating is reacted, to carry out solid-liquid after reaction
Separation, optionally washing and drying solid, obtain asymmetric bi-quaternary ammonium salt intermediate；Two tertiary amine is N, N, N ', N '-tetramethyl
Base hexamethylene diamine；
(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 reaction in step (i) and step (ii) carries out under microwave heating；
Wherein, the reaction in step (i) carries out under microwave heating, and the heating temperature of microwave is 30-60 DEG C, the power of microwave
It is 1-15min for the time of 100-600W and the reaction；
Reaction in step (ii) carries out under microwave heating, and the power of the microwave is 100-600W；The heating of the microwave
Temperature is 30-90 DEG C；The time of the reaction is 1-30min；
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.
2. the method according to claim 1, wherein the reaction in step (i) carries out under microwave heating, and micro-
The heating temperature of wave is 40-48 DEG C.
3. method according to claim 1 or 2, which is characterized in that the reaction in step (i) carries out under microwave heating,
And the power of microwave is 200-300W；With
The time of the reaction is 5-10min.
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. method according to claim 1 or 2, which is characterized in that in step (i), two tertiary amine and long-chain are halogenated
The molar ratio of alkane is (1.5-14): 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 (2-10): 1.
7. according to the method described in claim 6, it is characterized in that, in step (i), two tertiary amine and long-chain halogenated alkane
Molar ratio be (3-5): 1.
8. method according to claim 1 or 2, which is characterized in that in step (i), first solvent and long-chain halogen
Molar ratio for alkane is (2-25): 1.
9. according to the method described in claim 8, it is characterized in that, in step (i), first solvent and long-chain alkyl halide
The molar ratio of hydrocarbon is (5-20): 1.
10. according to the method described in claim 9, it is characterized in that, first solvent and long-chain are halogenated in step (i)
The molar ratio of alkane is (8-10): 1.
11. according to the method described in claim 8, it is characterized in that, in step (i), first solvent be include C3-C5
One of ketone.
12. according to the method for claim 11, which is characterized in that in step (i), first solvent is acetone.
13. method according to claim 1 or 2, which is characterized in that in step (ii), second solvent includes C3-
C6At least one of alcohols.
14. according to the method for claim 13, which is characterized in that in step (ii), second solvent include ethyl alcohol,
At least one of normal propyl alcohol and isopropanol.
15. according to the method for claim 14, which is characterized in that in step (ii), second solvent is normal propyl alcohol.
16. method according to claim 1 or 2, which is characterized in that in step (ii), the asymmetry bi-quaternary ammonium salt
The molar ratio of intermediate and short chain halogenated alkane is 1:(1-16)；And/or
The molar ratio of the asymmetry bi-quaternary ammonium salt intermediate and the second solvent is 1:(1-25).
17. according to the method for claim 16, which is characterized in that in step (ii), in the asymmetry bi-quaternary ammonium salt
The molar ratio of mesosome and short chain halogenated alkane is 1:(1-10)；And/or
The molar ratio of the asymmetry bi-quaternary ammonium salt intermediate and the second solvent is 1:(1-20).
18. according to the method for claim 17, which is characterized in that in step (ii), in the asymmetry bi-quaternary ammonium salt
The molar ratio of mesosome and short chain halogenated alkane is 1:(2-5)；And/or
The molar ratio of the asymmetry bi-quaternary ammonium salt intermediate and the second solvent is 1:(1-5).
19. the method according to claim 1, wherein the reaction in step (ii) carries out under microwave heating, institute
The power for stating microwave is 200-300W；And/or
The heating temperature of the microwave is 60-80 DEG C；And/or
The time of the reaction is 8-15min.
20. a kind of application of asymmetry bi-quaternary ammonium salt in Zeolite synthesis；Including first with any one in claim 1-19
Method described in prepares asymmetric bi-quaternary ammonium salt；Then the asymmetric quaternary ammonium salt is used for Zeolite synthesis.
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