CN108043455A - For synthesizing solid acid catalyst of seven ring of dioxy and preparation method thereof and the method using solid acid catalyst synthesis seven ring of dioxy - Google Patents
For synthesizing solid acid catalyst of seven ring of dioxy and preparation method thereof and the method using solid acid catalyst synthesis seven ring of dioxy Download PDFInfo
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- CN108043455A CN108043455A CN201711272780.5A CN201711272780A CN108043455A CN 108043455 A CN108043455 A CN 108043455A CN 201711272780 A CN201711272780 A CN 201711272780A CN 108043455 A CN108043455 A CN 108043455A
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/12—Oxidising
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D321/00—Heterocyclic compounds containing rings having two oxygen atoms as the only ring hetero atoms, not provided for by groups C07D317/00 - C07D319/00
- C07D321/02—Seven-membered rings
- C07D321/04—Seven-membered rings not condensed with other rings
- C07D321/06—1,3-Dioxepines; Hydrogenated 1,3-dioxepines
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Abstract
The invention discloses a kind of for synthesizing the solid acid catalyst of seven ring of dioxy, sulfonic acid group is grafted on carrier silicas surface, production method is：It will contain mercaptoorganosilicon coupling agent using rear Graft Method to be grafted on nonloaded silica carrier material, solid acid catalyst then is made through processes such as peroxidating, acidifyings.Method using above-mentioned solid acid catalyst synthesis seven ring of dioxy includes：Solid acid catalyst and Isosorbide-5-Nitrae butylene glycol, n-butanal and water entrainer are reacted, heating divides water to be back to anhydrous generation, filtering, vacuum distillation sub-argument, collect under vacuum degree 0.098MPa, 100 120 DEG C of boiling point when fraction, obtain seven ring of product dioxy.Solid acid catalyst provided by the invention have many advantages, such as not etching apparatus, non-wastewater discharge, at low cost, product yield is high and catalyst is easily recycled recycling.
Description
Technical field
The present invention relates to vitamin production technical fields, and in particular to is related to synthesize vitamin B6 intermediate dioxy seven
Solid acid catalyst of ring and preparation method thereof and the method using solid acid catalyst synthesis seven ring of dioxy.
Background technology
The technique of domestic production vitamin is mainly to be carried out using the azepine conjugated diene structure of azoles ring with dienophile
Diels-Alder reactions synthesize to synthesize, i.e. oxazole method.Important intermediate wherein as dienophile is exactly 2- alkyl -4,
7- dihydros -1,3- English in bis- heptan (seven ring of abbreviation dioxy), is obtained by n-butanal or isobutylaldehyde etc. and butylene glycol condensation reaction
Acetal compound, currently used acid catalyst are that hydrochloric acid, sulfuric acid, p-methyl benzenesulfonic acid, sulfamic acid, citric acid etc. are easy
The liquid acid of organic solvent is dissolved in, because it is acid too strong after reaction, to consersion unit seriously corroded, wastewater discharge is big, and produces
Raw viscous shape residue, makes troubles to post processing in production, seriously affects the yield and quality of product.
Therefore, in view of the above-mentioned problems, it is necessary to propose further solution.
The content of the invention
The present invention seeks to：There is provided it is a kind of have environmental-friendly, at low cost, high income, it is easy to operate, be easily recycled, can
The seven ring catalyst for synthesizing of dioxy of recycling, to solve the above problems.
The technical scheme is that：
For synthesizing the solid acid catalyst of seven ring of dioxy, carrier silicas is grafted with sulfonic acid group on surface.
The preparation method of above-mentioned solid acid catalyst includes rear Graft Method and copolymerization method.
Graft Method includes the following steps after wherein：
(1) processing of carrier：When processing 4-12 is small under the conditions of silica supports are placed in 100 DEG C -500 DEG C；
(2) take 10 grams of silica supports add in 50 milliliters nonpolar or polar organic solvent in, the organic solvent
In have the 0.5-2 grams of organo-silicon coupling agent containing sulfonic acid group presoma, be heated to reflux, obtain the first suspension；
(3) first suspension is filtered, leaves and takes solid portion, fully washed with organic solvent, then 100
It is dry under DEG C -200 DEG C of temperature conditionss, obtain the first solid；
(4) first solid is added in 50 milliliters of aqueous hydrogen peroxide solutions, wherein content of hydrogen peroxide is described organic
1-5 times of silicone couplet mole when return stirring 2-6 is small at 100 DEG C, obtains the second suspension；
(5) by second suspension filter, leave and take solid portion, fully washed with deionized water, then in 100 DEG C-
It is dry under 200 DEG C of temperature conditionss, obtain the second solid；
(6) second solid is immersed in 1wt% sulfuric acid solutions, it is small that 4 is stirred under the temperature conditionss less than 100 DEG C
When, obtain the 3rd suspension；
(7) the 3rd suspension is filtered, leaves and takes solid portion, fully washed to filtrate and be in neutrality with deionized water,
Then dried under 100 DEG C -200 DEG C of temperature conditionss to get to the silica solid acid catalyst of sulfonic acid funtionalized.
Further, silica supports described in step (1) are aerosil, microsphere silica gel and mesoporous dioxy
Any one or more in silicon nitride material.
Further, the earth silicon material specific surface is more than 200m2/g。
Further, organic solvent described in step (2) and step (3) is any one in dry toluene or ethyl alcohol
Kind.
Further, organo-silicon coupling agent described in step (2) is the organo-silicon coupling agent containing sulfydryl or sulfonic acid chloride group.
Further, first solid is added in 50 milliliters of aqueous hydrogen peroxide solutions in step (4), wherein hydrogen peroxide
Content is 3.5 times of the organo-silicon coupling agent mole, when return stirring 4 is small at 100 DEG C.
The method of seven ring of dioxy is made using above-mentioned solid acid catalyst to be included：By solid acid catalyst and 1,4- butylene two
Alcohol, aldehyde and water entrainer are reacted, and the molar ratio of the Isosorbide-5-Nitrae-butylene glycol and aldehyde is 1：1.2, the solid acid catalyst
Dosage is the 5wt% of Isosorbide-5-Nitrae-butylene glycol, and the molar ratio of the water entrainer and the Isosorbide-5-Nitrae-butylene glycol is 1.5:1, heating point
Water is back to anhydrous generation, filtering, vacuum distillation sub-argument, collect under vacuum degree -0.098MPa, 100-120 DEG C of boiling point when evaporate
Point, obtain seven ring of product dioxy.
Further, the aldehyde is any one in propionic aldehyde, n-butanal or isobutylaldehyde, and the water entrainer is benzene, hexamethylene
Any one in alkane, petroleum ether.
Solid acid catalyst provided by the invention have not etching apparatus, non-wastewater discharge, at low cost, product yield it is high with
And catalyst is easily recycled the advantages that recycling.
Specific embodiment
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, With reference to embodiment
The present invention is described in further detail.
The structure of solid acid catalyst is：(anchoring) is grafted on carrier silicas surface sulfonic acid group, except possessing
Outside the advantages of solid acid, have the advantages that be swollen in organic solvent compared with resinae solid acid catalyst.It is led
Production method is wanted to have：Graft Method and copolymerization method afterwards, the rear Graft Method are first synthetic vectors silica then sulfonic group work(
Energy group or its growth precursor are grafted to the surface of carrier silicas, and the copolymerization method is exactly the mistake in synthetic vectors silica
The silane coupling agent combined polymerization with sulfonic acid group or its presoma is formed in journey.
It will contain mercaptoorganosilicon coupling agent using rear Graft Method in the present invention to be grafted on nonloaded silica carrier material,
Then solid acid catalyst is made through processes such as peroxidating, acidifyings.It specifically includes following rapid：
Step 1：The processing of carrier；
The step specific as follows can perform：It is small that 4-12 is handled under the conditions of silica supports are placed in 100 DEG C -500 DEG C
When, to remove physical absorption water.The specific surface is more than 200m2The silica supports of/g are aerosil, microballoon silicon
Any one or more in glue and Metaporous silicon dioxide material.
Step 2：Obtain the first suspension；
The step specific as follows can perform：Take 10 grams of silica supports add in 50 milliliters it is nonpolar or polarity is organic
In solvent, there is the 0.5-2 grams of organo-silicon coupling agent containing sulfonic acid group presoma in the organic solvent, be heated to reflux, obtain
First suspension.Wherein, the organo-silicon coupling agent containing sulfonic acid group presoma can be selected containing sulfydryl or sulfonic acid chloride group
Organo-silicon coupling agent, such as (3- mercaptos propyl) trimethoxy silane or 2- (4- chlorine sulfonyl-phenyl) ethyl trimethoxy silane；Have
Dry toluene, dichloromethane, methanol or ethyl alcohol etc. may be selected in solvent.
Step 3：Make the first solid；
The step specific as follows can perform：First suspension is filtered, solid portion is left and taken, using corresponding
Organic solvent fully wash, it is then dry under 100 DEG C -200 DEG C of temperature conditionss, obtain the first solid.
Step 4：Make the second suspension；
The step specific as follows can perform：First solid is added in 50 milliliters of aqueous hydrogen peroxide solutions, wherein mistake
1-5 times that hydrogen content is the organo-silicon coupling agent mole is aoxidized, when return stirring 2-6 is small at 100 DEG C, it is outstanding to obtain second
Supernatant liquid.
Step 5：Make the second solid；
The step specific as follows can perform：Second suspension is filtered, solid portion is left and taken, is filled with deionized water
Divide washing, it is then dry under 100 DEG C -200 DEG C of temperature conditionss, obtain the second solid.
Step 6：Make the 3rd suspension；
The step specific as follows can perform：Second solid is immersed in 1wt% sulfuric acid solutions, in less than 100 DEG C
Temperature conditionss under stirring 4 it is small when, obtain the 3rd suspension.
Step 7：Obtain the silica solid acid catalyst of sulfonic acid funtionalized.
The step specific as follows can perform：3rd suspension is filtered, solid portion is left and taken, is filled with deionized water
Point washing is in neutrality to filtrate, is then dried under 100 DEG C -200 DEG C of temperature conditionss to get to the titanium dioxide of sulfonic acid funtionalized
Silicon solid acid catalyst.
After above-mentioned seven steps, solid acid catalyst is completed the production.After this seven steps, dioxy seven can also be made
Ring.
Step 8：Seven ring of dioxy is synthesized using above-mentioned solid acid catalyst.
The step specific as follows can perform：Solid acid catalyst and 1,4- butylene glycols, aldehyde and water entrainer are carried out anti-
Should, the molar ratio of the water entrainer, Isosorbide-5-Nitrae-butylene glycol and aldehyde is 1.5：1：1.2, the dosage of the solid acid catalyst is 1,
The 5wt% of 4- butylene glycols, the aldehyde are any one in propionic aldehyde, n-butanal or isobutylaldehyde, and the water entrainer is benzene, hexamethylene
Any one in alkane, petroleum ether, heating divide water to be back to anhydrous generation, and filtering, vacuum distillation sub-argument collect corresponding fraction,
Obtain seven ring of product dioxy.
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, it is further with reference to embodiment
Illustrate technical scheme.But the invention is not restricted to listed embodiment, should also it be included in of the presently claimed invention
Other any well known changes in interest field.
First, " one embodiment " or " embodiment " referred to herein refers to may be included at least one realization side of the present invention
A particular feature, structure, or characteristic in formula." in one embodiment " that different places occur in the present specification not refers both to
Same embodiment, nor the individual or selective embodiment mutually exclusive with other embodiment.
Embodiment 1
The implementation case shows that solid acid catalyst makes seven ring of dioxy as follows：
By 10 grams of specific surface 350m2The SiO 2 powder carrier of/g be placed in 150 DEG C of baking oven dry 12 it is small when；After
Be added into 50 milliliters of anhydrous toluene solutions containing 1 gram of (3- mercaptos propyl) front three oxosilane, be heated to reflux 4 it is small when, cooling,
Filtering, is washed 3 times or more with toluene, will obtain solid when 120 DEG C of dryings 6 are small；Above-mentioned drying solid is placed in containing 0.6 gram
H2O250 milliliters of aqueous solutions in, be heated to reflux 4 it is small when, filtering, deionized water wash 3 times or more, in 120 degree dry 6 it is small when,
And be placed in the sulfuric acid solution of 50 milliliters of 1wt%, when stirring acidifying 4 is small at 90 DEG C, filtering, deionized water is washed to filtrate
Be in neutrality, at 150 DEG C it is dry 6 it is small when more than, obtained solid catalyst is closed to be saved backup.
Above-mentioned prepared solid acid catalyst is generated into seven ring of dioxy for the acetal of 1,4- butylene glycols and n-butanal
Reaction.The 1,4- butylene glycols of addition and the molar ratio of n-butanal are 1：1.2；Catalyst amount is the 5% of Isosorbide-5-Nitrae-butylene glycol,
The molar ratio of 1,4- butylene glycol of the cyclohexane with adding in is 1.5:1.Heating divides water to be back to anhydrous generation, filter,
Be evaporated under reduced pressure sub-argument, collect under vacuum degree -0.098MPa, 100-120 DEG C of boiling point when fraction, obtain seven ring of product dioxy, produce
Rate reaches 93.0%.After catalyst reuses 8 times, the yield of seven ring of dioxy is 91.3%.
Embodiment 2
The implementation case shows that solid acid catalyst makes seven ring of dioxy as follows：
Except (3- mercaptos propyl) three ethoxy silane is used to replace (3- mercaptos propyl) front three oxosilane in embodiment 1, catalysis
Agent preparation condition and reaction condition are identical in embodiment 1, obtain seven ring of product dioxy, and yield reaches 92.5%.Catalysis
After agent reuses 8 times, the yield of seven ring of dioxy is 90.7%.
Embodiment 3
The implementation case shows that solid acid catalyst makes seven ring of dioxy as follows：
It is 721m except using 10 grams of specific surface areas2The mesoporous SBA-15 earth silicon material of/g replaces comparing in embodiment 1
Surface 350m2Outside the SiO 2 powder carrier of/g, catalyst preparation conditions and reaction condition are identical in embodiment 1,
Seven ring of product dioxy is obtained, yield reaches 96.5%.After catalyst reuses 8 times, the yield of seven ring of dioxy is 92.6%.
Compared with prior art, the beneficial effects of the invention are as follows：The present invention solid acid catalyst have it is environmental-friendly, into
This is low, high income, it is easy to operate, be easily recycled, repeat the characteristics of utilizing.
It should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although with reference to preferable
The present invention is described in detail in embodiment, it will be understood by those of ordinary skill in the art that, it can be to the technology of the present invention
Scheme is modified or replaced equivalently, and without departing from the spirit and scope of technical solution of the present invention, should all be covered in this hair
Among bright right.
Claims (10)
1. for synthesizing the solid acid catalyst of seven ring of dioxy, it is characterised in that：Carrier silicas is grafted with sulfonic acid on surface
Group.
2. for synthesizing the preparation method of the solid acid catalyst of seven ring of dioxy, it is characterised in that：This method includes rear Graft Method
And copolymerization method.
3. the preparation method of solid acid catalyst according to claim 2, which is characterized in that Graft Method is included such as after described
Lower step：
(1) processing of carrier：When processing 4-12 is small under the conditions of silica supports are placed in 100 DEG C -500 DEG C；
(2) take 10 grams of silica supports add in 50 milliliters nonpolar or polar organic solvent in, have in the organic solvent
The 0.5-2 grams of organo-silicon coupling agent containing sulfonic acid group presoma, is heated to reflux, and obtains the first suspension；
(3) first suspension is filtered, leaves and takes solid portion, fully washed with organic solvent, then 100 DEG C-
It is dry under 200 DEG C of temperature conditionss, obtain the first solid；
(4) first solid is added in 50 milliliters of aqueous hydrogen peroxide solutions, wherein content of hydrogen peroxide is even for the organosilicon
Join 1-5 times of agent mole, when return stirring 2-6 is small at 100 DEG C, obtain the second suspension；
(5) second suspension is filtered, leaves and takes solid portion, fully washed with deionized water, then in 100 DEG C -200 DEG C
Temperature conditionss under it is dry, obtain the second solid；
(6) second solid is immersed in 1wt% sulfuric acid solutions, when stirring 4 is small under the temperature conditionss less than 100 DEG C, obtained
To the 3rd suspension；
(7) the 3rd suspension is filtered, leaves and takes solid portion, fully washed to filtrate and be in neutrality with deionized water, then
It is dried under 100 DEG C -200 DEG C of temperature conditionss to get to the silica solid acid catalyst of sulfonic acid funtionalized.
4. the preparation method of solid acid catalyst according to claim 3, it is characterised in that：Dioxy described in step (1)
SiClx carrier is any one or more in aerosil, microsphere silica gel and Metaporous silicon dioxide material.
5. the preparation method of solid acid catalyst according to claim 4, it is characterised in that：The earth silicon material ratio
Surface is more than 200m2/g。
6. the preparation method of solid acid catalyst according to claim 3, it is characterised in that：In step (2) and step (3)
The organic solvent is any one in dry toluene or ethyl alcohol.
7. the preparation method of solid acid catalyst according to claim 3, it is characterised in that：It is organic described in step (2)
Silicone couplet is the organo-silicon coupling agent containing sulfydryl or sulfonic acid chloride group.
8. the preparation method of solid acid catalyst according to claim 3, it is characterised in that：By described the in step (4)
One solid is added in 50 milliliters of aqueous hydrogen peroxide solutions, and wherein content of hydrogen peroxide is the 3.5 of the organo-silicon coupling agent mole
Times, when return stirring 4 is small at 100 DEG C.
A kind of 9. method using solid acid catalyst synthesis seven ring of dioxy, it is characterised in that：By claim 2-8 any one
The solid acid catalyst obtained is reacted with Isosorbide-5-Nitrae-butylene glycol, aldehyde and water entrainer, the Isosorbide-5-Nitrae-butylene glycol and aldehyde
Molar ratio is 1：1.2, the dosage of the solid acid catalyst is the 5wt% of Isosorbide-5-Nitrae-butylene glycol, the water entrainer and described 1,
The molar ratio of 4- butylene glycols is 1.5:1, heating divides water to be back to anhydrous generation, and filtering, vacuum distillation sub-argument collect vacuum
Under degree -0.098MPa, 100-120 DEG C of boiling point when fraction, obtain seven ring of product dioxy.
10. the method according to claim 9 using solid acid catalyst synthesis seven ring of dioxy, it is characterised in that：It is described
Aldehyde is any one in propionic aldehyde, n-butanal or isobutylaldehyde, and the water entrainer is any one in hexamethylene, petroleum ether.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711272780.5A CN108043455A (en) | 2017-12-06 | 2017-12-06 | For synthesizing solid acid catalyst of seven ring of dioxy and preparation method thereof and the method using solid acid catalyst synthesis seven ring of dioxy |
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|---|---|---|---|
| CN201711272780.5A CN108043455A (en) | 2017-12-06 | 2017-12-06 | For synthesizing solid acid catalyst of seven ring of dioxy and preparation method thereof and the method using solid acid catalyst synthesis seven ring of dioxy |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114931972A (en) * | 2022-04-26 | 2022-08-23 | 榆林学院 | High-dispersity Ni/Mo cluster-loaded mesoporous Beta catalyst, and preparation method and application thereof |
-
2017
- 2017-12-06 CN CN201711272780.5A patent/CN108043455A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114931972A (en) * | 2022-04-26 | 2022-08-23 | 榆林学院 | High-dispersity Ni/Mo cluster-loaded mesoporous Beta catalyst, and preparation method and application thereof |
| CN114931972B (en) * | 2022-04-26 | 2023-10-24 | 榆林学院 | High-dispersity Ni/Mo cluster supported mesoporous Beta catalyst, preparation method and application |
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