CN102040582A - Preparation method of cyclohexanone 1,2-propanediol ketal - Google Patents
Preparation method of cyclohexanone 1,2-propanediol ketal Download PDFInfo
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- CN102040582A CN102040582A CN2009102355549A CN200910235554A CN102040582A CN 102040582 A CN102040582 A CN 102040582A CN 2009102355549 A CN2009102355549 A CN 2009102355549A CN 200910235554 A CN200910235554 A CN 200910235554A CN 102040582 A CN102040582 A CN 102040582A
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- cyclohexanone
- propylene glycol
- mesoporous material
- catalyst
- ketal
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- PEURWGJLPWOZNR-UHFFFAOYSA-N CC(O)CO.O=C1CCCCC1 Chemical compound CC(O)CO.O=C1CCCCC1 PEURWGJLPWOZNR-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000013335 mesoporous material Substances 0.000 claims abstract description 37
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims description 11
- 229960004063 propylene glycol Drugs 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- UXSMLYKRRCTZOK-UHFFFAOYSA-N CC[Cu]c1ccccc1 Chemical compound CC[Cu]c1ccccc1 UXSMLYKRRCTZOK-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 25
- 239000010949 copper Substances 0.000 abstract description 8
- 238000007086 side reaction Methods 0.000 abstract description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052802 copper Inorganic materials 0.000 abstract description 3
- 235000013772 propylene glycol Nutrition 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 description 19
- -1 ethyl phenyl Chemical group 0.000 description 14
- 238000001228 spectrum Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- UGHLEPMKNSFGCE-UHFFFAOYSA-N 2-ethylbenzenesulfonic acid Chemical group CCC1=CC=CC=C1S(O)(=O)=O UGHLEPMKNSFGCE-UHFFFAOYSA-N 0.000 description 5
- 238000004400 29Si cross polarisation magic angle spinning Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229920000428 triblock copolymer Polymers 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- SBTSVTLGWRLWOD-UHFFFAOYSA-L copper(ii) triflate Chemical compound [Cu+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F SBTSVTLGWRLWOD-UHFFFAOYSA-L 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000010183 spectrum analysis Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- NYIDSUMRGUILGR-UHFFFAOYSA-N 4-(2-trimethoxysilylethyl)benzenesulfonyl chloride Chemical compound CO[Si](OC)(OC)CCC1=CC=C(S(Cl)(=O)=O)C=C1 NYIDSUMRGUILGR-UHFFFAOYSA-N 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000011973 solid acid Substances 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 241000764238 Isis Species 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000007036 catalytic synthesis reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000012921 fluorescence analysis Methods 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VMHGXUATEGUEAJ-UHFFFAOYSA-N OS([Cu])(=O)=O Chemical compound OS([Cu])(=O)=O VMHGXUATEGUEAJ-UHFFFAOYSA-N 0.000 description 1
- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- 238000000441 X-ray spectroscopy Methods 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000001160 cross-polarisation magic angle spinning nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- XDRMBCMMABGNMM-UHFFFAOYSA-N ethyl benzenesulfonate Chemical group CCOS(=O)(=O)C1=CC=CC=C1 XDRMBCMMABGNMM-UHFFFAOYSA-N 0.000 description 1
- 239000000834 fixative Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 239000008369 fruit flavor Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000000449 magic angle spinning nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Classifications
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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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of the application of a catalyst, in particular to a reaction technology which applies a mesoporous material containing copper arene-sulfonate in the preparation of cyclohexanone 1,2-propanediol ketal, wherein in the preparation method, cyclohexanone and 1,2-propanediol is used. The invention has the following advantages: the conversion rate is high, the side reactions are reduced, the product purity is increased, high conversion rate can be maintained when the mesoporous material is used repeatedly and the pollution to the environment is less.
Description
Technical Field
The invention relates to the technical field of catalytic synthesis, in particular to application of an arene sulfo-copper ion mesoporous material in synthesizing cyclohexanone-1, 2 propylene glycol ketal.
Background
Cyclohexanone 1, 2-propylene glycol ketal is ketal compound, has characteristics of ketal compound, stable chemical performance, fragrance superior to parent ketone, can be used as fragrance fixative for fruit-flavor type and radix aucklandiae type daily essence, and can play a role of coordinator in flower-flavor type essence (what hardness, Sun Bao. perfume chemistry and technology-natural, synthetic, and harmonized perfume [ M]Beijing: chemical industry publishers, 1995: 259-260). Studies have shown that some solid acids (e.g., H)3PW12O40、TiSiW12O40/TiO2、H3PW12O40PAn, etc.) has good catalytic action on the reaction of synthesizing acetal (ketone) (Royumei, poplar gold, phosphotungstic acid catalyst catalytic synthesis of ketal [ J]Rare metal, 2004, 28 (4): 787-789). The solid acid as catalyst has the advantages of low cost, easy obtaining, strong acidity, high catalytic activity, low reaction temperature, etc., but has large dosage and low costDifficult separation recovery and regeneration, more side reactions, poor selectivity, complex post-treatment, serious environmental pollution, corrosion of equipment, discontinuous production process and the like. Therefore, if a heterogeneous catalyst with better catalytic effect is selected to replace the solid acid, the defects can be avoided, and the homogeneous catalysis can be heterogenized.
The invention firstly utilizes a one-step method to directly synthesize the ethyl phenyl sulfonic group-mesoporous material (the expression is SBA-Ar-SO)3H) And further with copper trifluoromethanesulfonate (Cu (OTf)2) Ion exchange is carried out (expression is SBA-Ar- (SO)3)2Cu) so that the synthesized catalyst has the catalytic characteristics of an ethyl phenyl sulfonic acid group-mesoporous material and the characteristics of a metal copper catalyst, and becomes a dual-function catalyst, the mesoporous material synthesized by the method is a novel super-strong acid catalytic material, shows excellent catalytic performance in catalytic reaction, and is used for catalyzing cyclohexanone 1, 2-propylene glycol ketal and obtaining the reaction process of the cyclohexanone 1, 2-propylene glycol ketal product which is important in industry.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of cyclohexanone-1, 2 propylene glycol ketal. The mesoporous material containing the copper ethylphenylsulfonate is used as a catalyst to catalyze cyclohexanone and 1, 2-propanediol to obtain cyclohexanone-1, 2-propanediol ketal, and the catalyst has high conversion rate in catalytic reaction, so that side reaction can be reduced, the product purity is improved, high conversion rate and high selectivity can be maintained after repeated use, and the environmental pollution is less.
The invention relates to a preparation method of cyclohexanone-1, 2 propylene glycol ketal, which comprises the following steps:
(1) adding cyclohexanone and 1, 2-propylene glycol into a reactor, adding a mesoporous material containing ethyl phenyl copper sulfonate as a catalyst, wherein the mass ratio of the cyclohexanone to the 1, the 2-propylene glycol to the catalyst is 1: 1-10: 0.01-0.3,
(2) stirring and reacting for 0.1-72 hours under the condition of heating reflux and water separation, cooling to room temperature, and centrifuging for solid-liquid separation;
(3) and rectifying and separating the obtained liquid phase product to obtain the product cyclohexanone-1, 2 propylene glycol ketal. The rectification separation adopts the conventional well-known technology.
And (3) carrying out vacuum drying on the solid-phase product obtained by the centrifugal separation in the step 2 at the temperature of between 25 and 200 ℃ for 1 to 24 hours to obtain the recovered catalyst.
The mesoporous material containing the copper ethylphenyl sulfonate is used as a catalyst, and the mesoporous material containing the copper ethylphenyl sulfonate is grafted on the outer surface and/or the inner hole wall of the SBA-15 mesoporous material.
At the moment, the expression of the mesoporous material is shown as
Wherein,
represents-Ar-SO selected from the group mentioned before3One of the arenesulfonate groups is an ethylphenylsulfonate group.
For the mesoporous material without copper ions and grafted with ethyl phenyl sulfonic acid groups only on the outer surface and/or the inner hole wall of the SBA-15 mesoporous material, the mark is
The preparation method of the mesoporous material containing the copper ethylphenylsulfonate comprises the following steps:
(1) adding triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene (PEO-PPO-PEO for short) into hydrochloric acid aqueous solution, wherein the ratio of the triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene to the water to the hydrogen chloride is 1: 9000-15000: 100-500 by mol,
stirring the mixture at a temperature of between 25 and 60 ℃ until the mixture is dissolved, wherein the triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene is preferably a substance with the American chemical abstracts registration number of 9003-11-6, and the average molecular weight Mn of the triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene is 5800.
(2) Adding tetraethoxysilane into the solution obtained in the last step, and stirring for more than 25 minutes at the temperature of 25-60 ℃; then adding 2- (4-chlorosulfonyl phenyl) ethyl trimethoxy silane, and stirring at 25-60 ℃ for more than 10 hours; the feed ratio of the triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene, tetraethoxysilane and 2- (4-chlorosulfonyl phenyl) ethyl trimethoxy silane is 1: 20-100: 2-10 in terms of mole.
(3) And (3) placing the solution obtained in the previous step into a closed reaction container, and crystallizing for 10-40 hours at the temperature of 90-150 ℃.
(4) And filtering, washing and drying the crystallized product to obtain the mesoporous material raw powder.
(5) Washing the obtained mesoporous material raw powder with ethanol at the temperature of 90-120 ℃ for 10-40 hours, and removing the template agent to obtain the mesoporous material containing ethyl phenyl sulfonic acid group.
(6) Putting the mesoporous material containing the ethyl phenyl sulfonic group, acetone and copper trifluoromethanesulfonate into a closed reaction container together, wherein the mesoporous material containing the ethyl phenyl sulfonic group comprises the following components in mass ratio: acetone and copper trifluoromethanesulfonate in the ratio of 1 to 1-12 to 0.1-16, and stirring at 25-150 deg.c for 1-72 hr; preferably, the mesoporous material obtained in the step (5) is dried in vacuum at 25-150 ℃ for 1-24 hours, cooled to room temperature, and then subjected to the reaction in the step (6).
(7) And cooling the product to room temperature, performing centrifugal separation, and performing vacuum drying at 25-200 ℃ for 1-24 hours to obtain a mesoporous material solid product containing copper ethylphenylsulfonate.
The catalyst SBA (-Ar-SO) prepared by the invention3)2Cu catalyzed reaction of cyclohexanone and 1, 2-propanediol, analysis of cyclohexane by gas chromatographyThe content of ketone is 3.9 percent, the content of cyclohexanone-1, 2 propylene glycol ketal is 96.2 percent, the content of cyclohexanone after recycling is 6.87 percent, the content of cyclohexanone-1, 2 propylene glycol ketal is 34.1 percent, and the catalyst SBA-Ar- (SO) after secondary catalytic reaction3)2The Cu still maintains the ordered hexagonal channel structure characteristic of the mesoporous material SBA-15 (see fig. 1 and 2). After the reaction was carried out under the same conditions without adding any catalyst, the liquid components of the reaction product were analyzed by gas chromatography, and no other product was detected.
The invention has the beneficial effects that:
the invention applies the novel mesoporous material with the characteristics of sulfonic group and metal ion to the cyclohexanone-1, 2 propylene glycol ketal reaction which is important in the synthesis industry, has high conversion rate and high selectivity in the catalytic reaction, can reduce side reaction and improve the product purity, and keeps high conversion rate and high selectivity after repeated use, and has less environmental pollution.
Drawings
FIG. 1 is
In accordance with the invention
Structural comparison before and after the secondary catalytic reaction.
FIG. 2 is
In accordance with the invention
Schematic pore structure before and after secondary catalytic reaction.
FIG. 3 shows SBA-15,
In accordance with the invention
Is/are as follows29Si CP/MAS NMR spectra.
FIG. 4 is
In accordance with the invention
And (4) microscopic morphology graphs before and after the secondary catalytic reaction.
FIG. 5 is
In accordance with the inventionThe result of the x-ray energy spectrum analysis is shown.
Detailed Description
The conversion in the following examples was calculated from the results of gas chromatography-mass spectrometry.
Example 1 preparation of mesoporous Material containing copper ethylphenylsulfonate
(1) 4.0 g of P123 (substance having a mean molecular weight Mn of 5800, registered under the American chemical Abstract, 9003-11-6) are added to a solution of 120ml of 2N hydrochloric acid and 6ml of water and stirred at 40 ℃ until the P123 is completely dissolved;
(2) adding 8.2ml of ethyl orthosilicate into the solution, stirring for 45 minutes at 40 ℃, adding 1.3 g of 2- (4-chlorosulfonylphenyl) ethyltrimethoxysilane, and stirring for 24 hours at 40 ℃;
(3) transferring the obtained solution into a reaction kettle with a polytetrafluoroethylene lining, and crystallizing for 24 hours at 100 ℃;
(4) filtering, washing and drying to obtain a raw powder mesoporous material;
(5) washing the original powder mesoporous material with ethanol under a reflux condition for 24 hours, and removing a template agent to obtain a mesoporous material containing ethyl phenyl sulfonic acid group in a framework;
(6) vacuum drying 1g of the mesoporous material containing ethyl phenyl sulfonic acid group at 150 ℃ for 6 hours, cooling to room temperature, then putting 15ml of acetone and 1g of copper trifluoromethanesulfonate into a reaction kettle with a 100ml of polytetrafluoroethylene lining, sealing the reaction kettle, and stirring at 55 ℃ for 24 hours;
(7) after cooling to room temperature, the liquid was filtered by centrifugation to give a solid product, which was dried under vacuum at 150 ℃ for 4 hours to remove impurities. Obtaining the product
FIG. 1 a isXRD spectrum of (1), b is
XRD spectrum of (1), and (c) is after the secondary catalytic reaction
XRD spectrum of (1). As can be seen from the above three spectra,
and
has a two-dimensional ordered hexagonal pore channel structure which is peculiar to the mesoporous material SBA-15, and after two catalytic reactions
Ordered mesoporous structure of (a)Still remaining unchanged.
EXAMPLE 2 preparation of Cyclohexanone-1, 2 propanediol ketal
Weighing 1.2 g of mesoporous material
Then weighing 12 g of 1, 2-propylene glycol and 10 g of cyclohexanone, sequentially putting the materials into a reaction kettle with a 100ml polytetrafluoroethylene lining, stirring the materials for 1 hour under the reflux condition, cooling the materials to room temperature, performing centrifugal separation, analyzing liquid phase components of a reaction product by using gas chromatography, wherein the content of the cyclohexanone is 3.9 percent, the content of the cyclohexanone-1, 2-propylene glycol ketal is 96.2 percent, and the content of the solid catalyst mesoporous material is
Vacuum drying at 150 deg.C for 6 hr, cooling to room temperature, and recovering for reuse.
EXAMPLE 3 Cyclohexanone-1, 2 propanediol ketal preparation with recovered catalyst
1.2 g of the mesoporous material recycled in example 2
Then 12 g of 1, 2-propylene glycol and 10 g of cyclohexanone are weighed and put into a reaction kettle with a 100ml polytetrafluoroethylene lining in sequence, stirred for 1 hour under the reflux condition, cooled to room temperature, centrifugally separated, and analyzed by gas chromatography to obtain a liquid phase component of a reaction product, wherein the content of the cyclohexanone is 6.87%, and the content of the cyclohexanone-1, 2-propylene glycol ketal is 34.1%. Comparative example 1
Weighing 12 g of 1, 2-propylene glycol and 10 g of cyclohexanone, sequentially putting into a reaction kettle with a 100ml polytetrafluoroethylene lining, stirring for 1 hour under the reflux condition, cooling to room temperature, performing centrifugal separation, and analyzing liquid phase components of a reaction product by using gas chromatography, wherein no product is detected.
FIG. 1 is
In connection with the present inventionIs/are as follows
Structural comparison before and after the secondary catalytic reaction. Wherein in figure (1) a is
XRD spectrum of (1), b is
XRD spectrum of (1), and (c) is after the secondary catalytic reaction
XRD spectrum of (1). The small-angle spectral peak appeared in the XRD spectrogram can be known,
and before and after the second catalytic reactionThe specific two-dimensional ordered hexagonal pore structure of the mesoporous material SBA-15 is still maintained.
FIG. 2 isIn accordance with the invention
Schematic pore structure before and after the secondary catalytic reaction. Wherein (2) a is
The hole structure of (2) b is
The hole structure of (2) c is
Schematic diagram of pore structure after secondary catalytic reaction. As can be seen from the figures, the,
the specific two-dimensional ordered hexagonal pore structure of the mesoporous material SBA-15 is still maintained before and after the secondary catalytic reaction, and the result is consistent with the result of XRD.
FIG. 3 shows SBA-15,
In accordance with the invention
Is/are as follows29Si CP/MAS NMR spectra. Wherein FIG. 3 a is SBA-1529Si CP/MAS NMR spectrum, FIG. 3 b is
Is/are as follows29Si CP/MASNMR spectrum, FIG. 3 c isIs/are as follows29Si CP/MAS NMR spectra. As can be seen from the spectrum,
is/are as follows29SiCP/MAS NMR Spectrum (SiO)2Si(OH)2(Q2Position), (SiO)3Si(OH)(Q3Position) and (SiO)4Si(Q4Position) the peak positions of the three connecting frameworks Si are matched with SBA-15. Compared with SBA-15, in addition to the three peaks described above,
and
is/are as follows29The Si CP/MAS NMR spectrum showed new peaks at 55ppm and 60ppm, respectively, which are attributable to Tm(Tm＝RSi(OSi)m(OH)3-m，m＝1-3；T2At delta-55 and T3At delta-60ppm). These two newly appearing peaks indicate
The group is successfully grafted on the SBA-15 skeleton and subjected to ion exchange reaction
The skeleton structure remains unchanged.
FIG. 4 is
In accordance with the inventionAnd (4) microscopic morphology graphs before and after the secondary catalytic reaction. Wherein a in FIG. 4 is
The microscopic topography of (4) b is
The microscopic topography of (4) c is
And (4) a micro-topography after the secondary catalytic reaction. As can be seen from the figures, the,
the micro-morphology before and after the secondary catalytic reaction is consistent with the results reported in the literature.
FIG. 5a is
FIG. 5b is a graph showing the results of the x-ray spectroscopy analysis of the present inventionThe result of the x-ray energy spectrum analysis is shown. x-ray energy spectrum analysis display
After the ion exchange reaction, the framework already contains copper ions.
Table 1 shows the results of x-fluorescence analysis, which shows that SBA-Ar-SO3The framework of H does contain metal ion copper after the ion exchange reaction, and the result is also consistent with the result of the X-ray energy spectrum analysis.
TABLE 1 results of fluorescence analysis
| Sample (I) | Sample Cu mass content (%) |
| a | 0 |
| b | 3.7 |
Claims (2)
1. A preparation method of cyclohexanone-1, 2 propylene glycol ketal is characterized in that mesoporous materials containing ethyl phenyl copper sulfonate are used as catalysts, cyclohexanone and 1, 2 propylene glycol are used as raw materials, and the preparation method of cyclohexanone-1, 2 propylene glycol ketal comprises the following steps:
(1) adding cyclohexanone and 1, 2-propylene glycol into a reactor, adding a mesoporous material containing ethyl phenyl copper sulfonate as a catalyst, wherein the mass ratio of the cyclohexanone to the 1, the 2-propylene glycol to the catalyst is 1: 1-10: 0.01-0.3,
(2) stirring and reacting for 0.1-72 hours under the condition of heating reflux, cooling to room temperature, and centrifuging for solid-liquid separation;
(3) and rectifying and separating the obtained liquid phase product to obtain the product cyclohexanone-1, 2 propylene glycol ketal.
2. The method for preparing cyclohexanone-1, 2-propanediol ketal according to claim 1, wherein the solid phase product obtained by the centrifugal separation in the step 2 is dried under vacuum at a temperature of 25 ℃ to 200 ℃ for 1 hour to 24 hours to obtain the recovered catalyst.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102355549A CN102040582B (en) | 2009-10-16 | 2009-10-16 | Preparation method of cyclohexanone 1,2-propanediol ketal |
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| CN115160110A (en) * | 2022-07-22 | 2022-10-11 | 中国科学院成都有机化学有限公司 | Method for synthesizing bisphenol Z |
| CN115160110B (en) * | 2022-07-22 | 2024-02-20 | 中国科学院成都有机化学有限公司 | Method for synthesizing bisphenol Z |
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