CN106588705A - Technology for synthesizing glycol dibenzenesulfonate from nano-solid alkali catalyst - Google Patents
Technology for synthesizing glycol dibenzenesulfonate from nano-solid alkali catalyst Download PDFInfo
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- CN106588705A CN106588705A CN201611134991.8A CN201611134991A CN106588705A CN 106588705 A CN106588705 A CN 106588705A CN 201611134991 A CN201611134991 A CN 201611134991A CN 106588705 A CN106588705 A CN 106588705A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
- C07C303/28—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids by reaction of hydroxy compounds with sulfonic acids or derivatives thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali metals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a technology for synthesizing glycol dibenzenesulfonate from a nano-solid alkali catalyst. Glycol dibenzenesulfonate is prepared from raw materials including glycol, pyridine, benzene sulfonyl chloride, the home-made caesium modified nano-scale Ti/Al composite solid alkali catalyst and the like through operating means including ice-water bath, reduced-pressure distillation, magnetic stirring and the like.
Description
Technical field
The present invention relates to a kind of technique by nano solid base catalyst synthesizing glycol DAADBSA ester, belongs to organic
Synthesis field.
Background technology
Since first crown compound being found from Pedersen in 1967, the research and development to cyclic polyether
Fast development.Further investigation of the people to its specific structure and complex performance, not only organic chemistry started " Crownether Chemistry ",
" host-guest chemistry ", " supramolecular chemistry " frontier, and in a large number the crown ether and its functional deriv of Various Functions is synthesized out
Come.One of the most frequently used intermediate of crown ether is multiethylene-glycol DAADBSA ester.Synthesize the process route of glycol DAADBSA ester at present
More complicated, yield is also bad.I have invented a kind of modified nanoscale Ti/Al complex solids base catalyst of homemade caesium to close
Into the technique of Glycol dibenzenesulfonate, the technological operation is simple, and raw material sources are convenient, and product purity yield is good.
The content of the invention
For the problem that above-mentioned prior art is present, the present invention provides a kind of by nano solid base catalyst synthesis second two
The technique of alcohol DAADBSA ester.
To achieve these goals, the technical solution used in the present invention is：A kind of nanoscale Ti/ being modified with homemade caesium
The technique of Al complex solid base catalyst synthesizing glycol DAADBSA esters.Comprise the following steps：
Step 1, glycol and pyridine are mixed evenly in a reservoir, 2 DEG C are cooled to ice-water bath under magnetic agitation；
Step 2, by homemade caesium be modified nanoscale Ti/Al complex solid base catalysts, in being added to container, then
Benzene sulfonyl chloride is added in beaker with chloroform, and then magnetic agitation 2h mix homogeneously, is then added drop-wise in container with per minute 90
Drop speed Deca, the magnetic agitation in Deca, control temperature continues magnetic agitation 5h at 3-5 DEG C, after completion of dropwise addition；
Step 3 and then mixture is poured in 500mL frozen water, abundant magnetic agitation, separates organic layer, reclaimed homemade
The modified nanoscale Ti/Al complex solid base catalysts of caesium, it is 7.0 to be washed with deionized number to pH value；
Step 4 and then in vacuum distillation, by moisture, solvent is evaporated, and obtains crude product；
Step 5 and then dehydrated alcohol recrystallization is used crude product, finally give Glycol dibenzenesulfonate.
The modified nanoscale Ti/Al complex solid base catalysts of caesium, preparation technology is as follows：
Step 1, by aluminium oxide, titanium dioxide first processes 2h under ultrasound wave；
Step 2 and then carry out calcination processing：First in air, 500 DEG C, 4h, then in nitrogen, 600 are calcined under 0.2kpa
DEG C, calcine 3h under 0.4kpa；
Step 3, calcining carry out helium-atmosphere and enclose lower purging 3h after terminating；
Step 4 and then cesium element is introduced using infusion process：By 10g aluminium oxidies, 5g titanium dioxide in mass ratio 2:1 mixes
Close, be then immersed in 12h in the Cs2CO3 solution of 0.5mol/L；
Step 5 and then hot alkali treatment is adopted, 2h is processed under 180 DEG C of hot-airs, be then immersed in 5% sodium hydroxide
5h is processed in solution, in being then transferred into beaker；
Step 6, carry out coupling processing：0.05mol coupling agent kh500 are added drop-wise in the mixture after hot alkali treatment, side
Deca side magnetic agitation；
Step 7,0.05mol surfactant diglycollic amides are added drop-wise in the mixture after coupling processing, side Deca
Side magnetic agitation, is then carrying out microwave treatment；
After step 8, microwave treatment terminate, 110 DEG C in thermostatic drying chamber of elder generation is dried 12h, is then calcined in tube furnace
Process：First in nitrogen and ammonia 1:3,650 DEG C, 4h is calcined under 0.3kpa, then in nitrogen, 700 DEG C, calcined under 0.6kpa
5h, finally gives the modified nanoscale Ti/Al complex solid base catalysts of caesium.
Beneficial effect:The nanoscale Ti/Al complex solids base catalyst synthesis second that a kind of homemade caesium of the present invention is modified
The technique of glycol DAADBSA ester, the technological operation is simple, and raw material is relatively easily obtained, by receiving of adding homemade caesium modified
Meter level Ti/Al complex solid base catalysts, effectively raise reaction rate, the generation of side reaction are reduced, in building-up process
In processed by magnetic agitation etc., activation can be played to reactant enables reaction to be more smoothed out, and makes reaction towards pre-
The direction of phase is carried out, and the yield for making target product is improved.By ice-water bath, vacuum distillation can obtain purer ethylene glycol
DAADBSA ester.Wherein embodiment 1 produces glycol, and benzene sulfonyl chloride, the modified nanoscale Ti/Al complex solid alkali of homemade caesium is urged
Agent mass ratio 18:105:0.6 sample.Glycol 18g, benzene sulfonyl chloride 105g, the modified nanoscale Ti/Al composite solids of homemade caesium
Body base catalyst 0.6g.Pyridine 1.2mol, chloroform 150ml.And embodiment 2 produces glycol, benzene sulfonyl chloride, homemade caesium is modified
Nanoscale Ti/Al complex solid base catalysts mass ratio 26:100:0.5 sample.Glycol 26g, benzene sulfonyl chloride 100g, it is homemade
The modified nanoscale Ti/Al complex solid base catalyst 0.5g of caesium.Pyridine 1.1mol, chloroform 160ml.Obtained ethylene glycol hexichol
Sulphonic acid ester purity and yield is best.
Specific embodiment
Embodiment 1
The modified nanoscale Ti/Al complex solid base catalysts of caesium, preparation technology is as follows：
Step 1, by aluminium oxide, titanium dioxide first processes 2h under ultrasound wave；
Step 2 and then carry out calcination processing：First in air, 500 DEG C, 4h, then in nitrogen, 600 are calcined under 0.2kpa
DEG C, calcine 3h under 0.4kpa；
Step 3, calcining carry out helium-atmosphere and enclose lower purging 3h after terminating；
Step 4 and then cesium element is introduced using infusion process：By 10g aluminium oxidies, 5g titanium dioxide in mass ratio 2:1 mixes
Close, be then immersed in 12h in the Cs2CO3 solution of 0.5mol/L；
Step 5 and then hot alkali treatment is adopted, 2h is processed under 180 DEG C of hot-airs, be then immersed in 5% sodium hydroxide
5h is processed in solution, in being then transferred into beaker；
Step 6, carry out coupling processing：0.05mol coupling agent kh500 are added drop-wise in the mixture after hot alkali treatment, side
Deca side magnetic agitation；
Step 7,0.05mol surfactant diglycollic amides are added drop-wise in the mixture after coupling processing, side Deca
Side magnetic agitation, is then carrying out microwave treatment；
After step 8, microwave treatment terminate, 110 DEG C in thermostatic drying chamber of elder generation is dried 12h, is then calcined in tube furnace
Process：It is 1 first in nitrogen and ammonia volume ratio:3 mixing, calcine 4h by 650 DEG C under 0.3kpa, then in nitrogen, 700 DEG C,
5h is calcined under 0.6kpa, the modified nanoscale Ti/Al complex solid base catalysts of caesium are finally given.
The preparation of Glycol dibenzenesulfonate：
Produce glycol, benzene sulfonyl chloride, the modified nanoscale Ti/Al complex solid base catalysts mass ratio 18 of homemade caesium:
105:0.6 sample.Glycol 18g, benzene sulfonyl chloride 105g, the modified nanoscale Ti/Al complex solid base catalysts of homemade caesium
0.6g.Pyridine 1.2mol, chloroform 150ml.
Step 1,18g glycol and 1.2mol pyridines are mixed evenly in a reservoir, 2 are cooled to ice-water bath under magnetic agitation
℃；
Step 2, the nanoscale Ti/Al complex solid base catalysts that the homemade caesiums of 0.6g are modified, in being added to container, so
105g benzene sulfonyl chlorides and 150ml chloroforms are added in beaker afterwards, then magnetic agitation 2h mix homogeneously, is then added drop-wise to container
In with per minute 90 drop speed Deca, the magnetic agitation in Deca, control temperature at 3-5 DEG C, after completion of dropwise addition continue magnetic force stir
Mix 5h；
Step 3 and then mixture is poured in 500mL frozen water, abundant magnetic agitation, separates organic layer, reclaimed homemade
The modified nanoscale Ti/Al complex solid base catalysts of caesium, it is 7.0 to be washed with deionized number to pH value；
Step 4 and then in vacuum distillation, by moisture, solvent is evaporated, and obtains crude product；
Step 5 and then dehydrated alcohol recrystallization is used crude product, finally give Glycol dibenzenesulfonate.
Embodiment 2 produces glycol, benzene sulfonyl chloride, the modified nanoscale Ti/Al complex solid base catalyst matter of homemade caesium
Amount compares 26:100:0.5 sample.Glycol 26g, benzene sulfonyl chloride 100g, the modified nanoscale Ti/Al complex solid alkali of homemade caesium is urged
Agent 0.5g.Pyridine 1.1mol, chloroform 160ml.Operating procedure is as embodiment 1.
Embodiment 3 produces glycol, benzene sulfonyl chloride, the modified nanoscale Ti/Al complex solid base catalyst matter of homemade caesium
Amount compares 18:105:0.5 sample.Glycol 18g, benzene sulfonyl chloride 105g, the modified nanoscale Ti/Al complex solid alkali of homemade caesium is urged
Agent 0.5g.Other raw materials, operating procedure is as embodiment 1.
Embodiment 4 produces glycol, benzene sulfonyl chloride, the modified nanoscale Ti/Al complex solid base catalyst matter of homemade caesium
Amount compares 18:105:0.4 sample.Glycol 18g, benzene sulfonyl chloride 105g, the modified nanoscale Ti/Al complex solid alkali of homemade caesium is urged
Agent 0.4g.Other raw materials, operating procedure is as embodiment 1.
Embodiment 5 produces glycol, benzene sulfonyl chloride, the modified nanoscale Ti/Al complex solid base catalyst matter of homemade caesium
Amount compares 18:105:0.3 sample.Glycol 18g, benzene sulfonyl chloride 105g, the modified nanoscale Ti/Al complex solid alkali of homemade caesium is urged
Agent 0.3g.Other raw materials, operating procedure is as embodiment 1.
Embodiment 6 produces glycol, benzene sulfonyl chloride, the modified nanoscale Ti/Al complex solid base catalyst matter of homemade caesium
Amount compares 18:105:0.2 sample.Glycol 18g, benzene sulfonyl chloride 105g, the modified nanoscale Ti/Al complex solid alkali of homemade caesium is urged
Agent 0.2g.Other raw materials, operating procedure is as embodiment 1.
Embodiment 7 produces glycol, benzene sulfonyl chloride, the modified nanoscale Ti/Al complex solid base catalyst matter of homemade caesium
Amount compares 18:105:0.1 sample.Glycol 18g, benzene sulfonyl chloride 105g, the modified nanoscale Ti/Al complex solid alkali of homemade caesium is urged
Agent 0.1g.Other raw materials, operating procedure is as embodiment 1.
Embodiment 8 produces glycol, benzene sulfonyl chloride, the modified nanoscale Ti/Al complex solid base catalyst matter of homemade caesium
Amount compares 18:105:0.7 sample.Glycol 18g, benzene sulfonyl chloride 105g, the modified nanoscale Ti/Al complex solid alkali of homemade caesium is urged
Agent 0.7g.Other raw materials, operating procedure is as embodiment 1.
Embodiment 9 produces glycol, benzene sulfonyl chloride, the modified nanoscale Ti/Al complex solid base catalyst matter of homemade caesium
Amount compares 18:105:0.8 sample.Glycol 18g, benzene sulfonyl chloride 105g, the modified nanoscale Ti/Al complex solid alkali of homemade caesium is urged
Agent 0.8g.Other raw materials, operating procedure is as embodiment 1.
Embodiment 10 produces glycol, benzene sulfonyl chloride, the modified nanoscale Ti/Al complex solid base catalyst matter of homemade caesium
Amount compares 18:105:0.9 sample.Glycol 18g, benzene sulfonyl chloride 105g, the modified nanoscale Ti/Al complex solid alkali of homemade caesium is urged
Agent 0.9g.Other raw materials, operating procedure is as embodiment 1.
Embodiment 11 produces glycol, benzene sulfonyl chloride, the modified nanoscale Ti/Al complex solid base catalyst matter of homemade caesium
Amount compares 18:105:1 sample.Glycol 18g, benzene sulfonyl chloride 105g, the modified nanoscale Ti/Al complex solid base catalysiss of homemade caesium
Agent 1g.Other raw materials, operating procedure is as embodiment 1.
Embodiment 12 produces glycol, benzene sulfonyl chloride, the modified nanoscale Ti/Al complex solid base catalyst matter of homemade caesium
Amount compares 18:105:1.1 sample.Glycol 18g, benzene sulfonyl chloride 105g, the modified nanoscale Ti/Al complex solid alkali of homemade caesium is urged
Agent 1.1g.Other raw materials, operating procedure is as embodiment 1.
Embodiment 13 produces glycol, benzene sulfonyl chloride, the modified nanoscale Ti/Al complex solid base catalyst matter of homemade caesium
Amount compares 18:105:1.2 sample.Glycol 18g, benzene sulfonyl chloride 105g, the modified nanoscale Ti/Al complex solid alkali of homemade caesium is urged
Agent 1.2g.Other raw materials, operating procedure is as embodiment 1.
Embodiment 14 produces glycol, benzene sulfonyl chloride, the modified nanoscale Ti/Al complex solid base catalyst matter of homemade caesium
Amount compares 18:105:1.3 sample.Glycol 18g, benzene sulfonyl chloride 105g, the modified nanoscale Ti/Al complex solid alkali of homemade caesium is urged
Agent 1.3g.Other raw materials, operating procedure is as embodiment 1.
Embodiment 15 produces glycol, benzene sulfonyl chloride, the modified nanoscale Ti/Al complex solid base catalyst matter of homemade caesium
Amount compares 18:105:1.4 sample.Glycol 18g, benzene sulfonyl chloride 105g, the modified nanoscale Ti/Al complex solid alkali of homemade caesium is urged
Agent 1.4g.Other raw materials, operating procedure is as embodiment 1.
Reference examples 1 produce glycol, benzene sulfonyl chloride, the modified nanoscale Ti/Al complex solid base catalyst matter of homemade caesium
Amount compares 18:105:0.6 sample.Glycol 18g, benzene sulfonyl chloride 105g, the modified nanoscale Ti/Al complex solid alkali of homemade caesium is urged
Agent 0.6g.Do not carry out magnetic agitation, but mechanical agitation, other raw materials, operating procedure is as embodiment 1.
Reference examples 2 produce glycol, benzene sulfonyl chloride, the modified nanoscale Ti/Al complex solid base catalyst matter of homemade caesium
Amount compares 18:105:0.6 sample.Glycol 18g, benzene sulfonyl chloride 105g, the modified nanoscale Ti/Al complex solid alkali of homemade caesium is urged
Agent 0.6g.Without ice-water bath controlling reaction temperature, but carry out at room temperature, other raw materials, operating procedure is with embodiment 1 one
Sample.
Reference examples 3 produce glycol, benzene sulfonyl chloride, the modified nanoscale Ti/Al complex solid base catalyst matter of homemade caesium
Amount compares 18:105:06 sample.Glycol 18g, benzene sulfonyl chloride 105g, the modified nanoscale Ti/Al complex solid alkali of homemade caesium is urged
Agent 0.6g.Deionized water wash terminate after not into neutrality, other raw materials, operating procedure is as embodiment 1.
Reference examples 4 produce glycol, benzene sulfonyl chloride, the modified nanoscale Ti/Al complex solid base catalyst matter of homemade caesium
Amount compares 18:105:0.6 sample.Glycol 18g, benzene sulfonyl chloride 105g, the modified nanoscale Ti/Al complex solid alkali of homemade caesium is urged
Agent 0.5g.Do not carry out recrystallization process, other raw materials, operating procedure is as embodiment 1.
Reference examples 5 are added without the modified nanoscale Ti/Al complex solid base catalysts of homemade caesium, other raw material dosages,
Operating procedure is as embodiment 1.
The addition dodecylbenzene sodium sulfonate catalyst 0.5g of reference examples 6, other raw materials, operating procedure is as embodiment 1.
Reference examples 7, technique, proportioning raw materials are completely the same with embodiment 1, and difference is, the modified nanoscale of homemade caesium
The preparation of Ti/Al complex solid base catalysts, main difference is, after step 8, microwave treatment terminate, first in thermostatic drying chamber 110
DEG C 12h is dried, then carries out calcination processing in tube furnace：First in nitrogen and ammonia 1:1,650 DEG C, 4h is calcined under 0.3kpa,
Then in nitrogen, 700 DEG C, 5h is calcined under 0.6kpa, finally gives the modified nanoscale Ti/Al complex solid base catalysts of caesium.
Reference examples 8, technique, raw material, proportioning and embodiment 1 are completely the same, and difference is, the modified nanoscale of homemade caesium
The preparation of Ti/Al complex solid base catalysts, main difference is, after step 8, microwave treatment terminate, first in thermostatic drying chamber 110
DEG C 12h is dried, then carries out calcination processing in tube furnace：First in nitrogen and ammonia 3:1,650 DEG C, 4h is calcined under 0.3kpa,
Then in nitrogen, 700 DEG C, 5h is calcined under 0.6kpa, finally gives the modified nanoscale Ti/Al complex solid base catalysts of caesium.
Reference examples 9, technique, raw material, proportioning and embodiment 1 are completely the same, and difference is, the modified nanoscale of homemade caesium
The preparation of Ti/Al complex solid base catalysts, main difference is, after step 8, microwave treatment terminate, first in thermostatic drying chamber 110
DEG C 12h is dried, then carries out calcination processing in tube furnace：In nitrogen, 700 DEG C, 5h is calcined under 0.6kpa, finally give caesium and be modified
Nanoscale Ti/Al complex solid base catalysts.
Reference examples 10, technique, raw material, proportioning and embodiment 1 are completely the same, and difference is, the modified nanometer of homemade caesium
The preparation of level Ti/Al complex solid base catalysts, main difference is, after step 8, microwave treatment terminate, first in thermostatic drying chamber
110 DEG C are dried 12h, then carry out calcination processing in tube furnace：First under ammonia atmosphere, 650 DEG C, 4h is calcined under 0.3kpa,
Finally give the modified nanoscale Ti/Al complex solid base catalysts of caesium.
Reference examples 11, technique, raw material, proportioning and embodiment 1 are completely the same, and difference is that self-control nanoscale Ti/Al is combined
The preparation of solid base catalyst does not contain cesium element, and preparation technology is as follows：
Step 1, by aluminium oxide, titanium dioxide first processes 2h under ultrasound wave；
Step 2 and then carry out calcination processing：First in air, 500 DEG C, 4h, then in nitrogen, 600 are calcined under 0.2kpa
DEG C, calcine 3h under 0.4kpa；
Step 3, calcining carry out helium-atmosphere and enclose lower purging 3h after terminating；
Step 4, by 10g aluminium oxidies, 5g titanium dioxide in mass ratio 2:1 mixing；
Step 5 and then hot alkali treatment is adopted, 2h is processed under 180 DEG C of hot-airs, be then immersed in 5% sodium hydroxide
5h is processed in solution, in being then transferred into beaker；
Step 6, carry out coupling processing：0.05mol coupling agent kh500 are added drop-wise in the mixture after hot alkali treatment, side
Deca side magnetic agitation；
Step 7,0.05mol surfactant diglycollic amides are added drop-wise in the mixture after coupling processing, side Deca
Side magnetic agitation, is then carrying out microwave treatment；
After step 8, microwave treatment terminate, 110 DEG C in thermostatic drying chamber of elder generation is dried 12h, is then calcined in tube furnace
Process：It is 1 first in nitrogen and ammonia volume ratio:3 mixing, calcine 4h by 650 DEG C under 0.3kpa, then in nitrogen, 700 DEG C,
5h is calcined under 0.6kpa, nanoscale Ti/Al complex solid base catalysts are finally given.
The yield purity of experiment test product：
Liquid chromatograph：Agilent1200 high performance liquid chromatographs, chromatographic column:EclipseXDB-C18 chromatographic column (250mm
× 4.6mm, 5 μm)；Mobile phase is A:5mmol/L ammonium acetate solutions, B:Acetonitrile；Linear gradient elution program:0min (20%A+
80%B), 5min (5%A+95%B), 10min (100%), 20min (5%A+95%B), 22min (20%A+80%B)；Stream
Speed:0.5mL/min；Column temperature:30℃；Excitation wavelength:350nm；Launch wavelength:430nm..Detection product component, calculated purity,
Yield.
The purity of the Glycol dibenzenesulfonate of table one each product, yield result
Test result indicate that：It can be found that the Glycol dibenzenesulfonate product purity that the technique of embodiment 1,2 is obtained, yield
Preferably, proportioning of both techniques in raw material is illustrated, the production of the operation of technique most beneficial for target product.Make under other techniques
The product for obtaining is not especially desirable in purity, yield.Comparative example 1, and comparative example 1,2,3,4,5,6 can be found that.No
Carry out magnetic agitation, without ice-water bath controlling reaction temperature, but carry out at room temperature, deionized water wash terminate after not in
Property, recrystallization process is not carried out, the modified nanoscale Ti/Al complex solid base catalysts of homemade caesium are added without, using 12
The purity of Glycol dibenzenesulfonate obtained in alkyl benzene sulphonate sodium catalyst, yield is not high.
Matched group 7-10, it can be seen that the condition and environment of calcining is for the complex solid base catalyst for preparing
Apply in synthesis technique, for product purity, yield has tremendous influence.
Claims (4)
1. a kind of technique by nano solid base catalyst synthesizing glycol DAADBSA ester, it is characterised in that with glycol, pyrrole
The raw materials such as pyridine, benzene sulfonyl chloride, the modified nanoscale Ti/Al complex solid base catalysts of homemade caesium by ice-water bath, steam by decompression
Evaporate, the operational means such as magnetic agitation prepares Glycol dibenzenesulfonate.
2. a kind of technique by nano solid base catalyst synthesizing glycol DAADBSA ester, it is characterised in that including as follows
Step：
Step 1, glycol and pyridine are mixed evenly in a reservoir, stirring is lower cold with ice-water bath；
Step 2, will self-control complex solid base catalyst, in being added to container, then benzene sulfonyl chloride and chloroform are added to beaker
In, then it is uniformly mixed, then it is added drop-wise in container with per minute 90 drop speed Deca, stir in Deca, control temperature
Degree continues to stir at 3-5 DEG C, after completion of dropwise addition;
Step 3 and then mixture is poured in frozen water, is sufficiently stirred for, separate organic layer, reclaim homemade complex solid base catalysiss
Agent, it is 7.0 to be washed with deionized number to pH value；
Step 4 and then in vacuum distillation, by moisture, solvent is evaporated, and obtains crude product；
Step 5 and then dehydrated alcohol recrystallization is used crude product, finally give Glycol dibenzenesulfonate.
3. a kind of technique by nano solid base catalyst synthesizing glycol DAADBSA ester according to claim 2,
It is characterized in that：Described step 1,2,3 stirrings are magnetic agitation.
4. a kind of technique by nano solid base catalyst synthesizing glycol DAADBSA ester according to claim 1,
It is characterized in that：Described complex solid base catalyst is the nanoscale Ti/Al complex solid base catalysts that caesium is modified, concrete system
Standby technique is as follows：
Step 1, by aluminium oxide, titanium dioxide first processes 2h under ultrasound wave;
Step 2 and then carry out calcination processing：First in air, 500 DEG C, 4h is calcined under 0.2kpa, then in nitrogen, 600 DEG C,
3h is calcined under 0.4kpa;
Step 3, calcining carry out helium-atmosphere and enclose lower purging 3h after terminating;
Step 4 and then cesium element is introduced using infusion process：By 10g aluminium oxidies, 5g titanium dioxide in mass ratio 2:1 mixing, so
12h in the Cs2CO3 solution of 0.5mol/L is immersed in afterwards;
Step 5 and then hot alkali treatment is adopted, 2h is processed under 180 DEG C of hot-airs, be then immersed in 5% sodium hydroxide solution
5h is processed, in being then transferred into beaker；
Step 6, carry out coupling processing：0.05mol coupling agent kh500 are added drop-wise in the mixture after hot alkali treatment, side Deca
Side magnetic agitation；
Step 7,0.05mol surfactant diglycollic amides are added drop-wise in the mixture after coupling processing, the magnetic in Deca
Power is stirred, and is then carrying out microwave treatment；
After step 8, microwave treatment terminate, 110 DEG C in thermostatic drying chamber of elder generation is dried 12h, then carries out calcination processing in tube furnace：
Mix atmosphere, volume ratio 1 with ammonia in nitrogen first:3,650 DEG C, 4h is calcined under 0.3kpa, then in nitrogen atmosphere, 700 DEG C,
5h is calcined under 0.6kpa, the modified nanoscale Ti/Al complex solid base catalysts of caesium are finally given.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106588717A (en) * | 2016-12-13 | 2017-04-26 | 新沂市中诺新材料科技有限公司 | Technique for compounding glycol dibenzenesulfonate by nanometer solid alkali catalyst |
| CN107946643A (en) * | 2017-11-14 | 2018-04-20 | 石家庄圣泰化工有限公司 | A kind of high-performance lithium battery electrolyte |
| WO2019095636A1 (en) * | 2017-11-14 | 2019-05-23 | 石家庄圣泰化工有限公司 | Method for synthesizing benzenesulfonate derivative |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106588717A (en) * | 2016-12-13 | 2017-04-26 | 新沂市中诺新材料科技有限公司 | Technique for compounding glycol dibenzenesulfonate by nanometer solid alkali catalyst |
| CN107946643A (en) * | 2017-11-14 | 2018-04-20 | 石家庄圣泰化工有限公司 | A kind of high-performance lithium battery electrolyte |
| WO2019095636A1 (en) * | 2017-11-14 | 2019-05-23 | 石家庄圣泰化工有限公司 | Method for synthesizing benzenesulfonate derivative |
| CN107946643B (en) * | 2017-11-14 | 2019-12-10 | 石家庄圣泰化工有限公司 | High-performance lithium battery electrolyte |
| JP2021502950A (en) * | 2017-11-14 | 2021-02-04 | 石家庄▲聖▼泰化工有限公司 | Method for synthesizing benzenesulfonic acid ester derivative |
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| Publication number | Publication date |
|---|---|
| CN106588705B (en) | 2018-02-27 |
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