CN102040582A - Preparation method of cyclohexanone 1,2-propanediol ketal - Google Patents

Preparation method of cyclohexanone 1,2-propanediol ketal Download PDF

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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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pimelinketone
propylene glycol
mesoporous material
preparation
catalyzer
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CN102040582B (en
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亢宇
谢伦嘉
黄文氢
王彦强
赵思源
田宇
孙竹芳
冯再兴
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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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

The preparation method of a kind of pimelinketone-1,2 propylene glycol ketal
Technical field
The present invention relates to the catalytic synthetic techniques field, be specifically related to the application of mesoporous material in synthesizing cyclohexanone-1,2 propylene glycol ketal of aromatic hydrocarbons sulfo group-cupric ion.
Background technology
Pimelinketone 1,2-propylene glycol ketal belongs to ketal compounds, characteristic with ketal compound, stable chemical performance, the fragrance that is better than parent ketone can be used as the fixative of fruit flavour type and banksia rose type daily essence, can play blender (He Jian in bouquet type composition, Sun Baoguo. flavor chemistry and technology-natural, synthetic, mediation spices [M]. Beijing: Chemical Industry Press, 1995:259-260).Studies show that some solid acids are (as H 3PW 12O 40, TiSiW 12O 40/ TiO 2, H 3PW 12O 40/ PAn etc.) to synthetic acetal (ketone) reaction have good katalysis (Luo Yumei, Yang Shuijin. ketal [J] is synthesized in phosphotungstic acid catalyst catalysis. rare metal, 2004,28 (4): 787-789).Advantages such as that though the solid acid as catalyst has is cheap and easy to get, acidity reaches the catalytic activity height by force, temperature of reaction is low, have that consumption is big, Separation and Recovery and regeneration difficulty, side reaction are many, poor selectivity, aftertreatment complexity, environmental pollution seriously, problems such as etching apparatus, production technique be discontinuous.Therefore, as select for use the better heterogeneous catalyst of catalytic effect to replace solid acid, not only can avoid above-mentioned defective, also can make the homogeneous catalysis heterogenize.
The present invention utilizes single stage method directly to synthesize ethylphenyl sulfonic group-mesoporous material earlier, and (expression formula is SBA-Ar-SO 3H), again with copper trifluoromethanesulfcomposite (Cu (OTf) 2) (expression formula is SBA-Ar-(SO to carry out ion-exchange 3) 2Cu), make the synthetic catalyzer both have the catalytic characteristics of ethylphenyl sulfonic group-mesoporous material, the feature that has the metallic copper catalyzer again, become a kind of bifunctional catalyzer, with this method synthetic mesoporous material is novel super-strong acid catalytic material, has shown excellent catalytic performance in catalyzed reaction, and it is used for catalysis of pimelinketone 1,2-propylene glycol ketal also obtains pimelinketone important in the industry 1, the reaction process of 2-propylene glycol ketal product.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, the preparation method of a kind of pimelinketone-1,2 propylene glycol ketal is provided.Utilization contains the mesoporous material of ethylphenyl sulfonic acid copper as catalyst pimelinketone and 1,2 propylene glycol obtain pimelinketone-1,2 propylene glycol ketals, in catalyzed reaction, has higher transformation efficiency, not only can reduce side reaction, improve product purity, and still keep high conversion and highly selective after using repeatedly, environmental pollution is less.
The preparation method of the present invention's a kind of pimelinketone-1,2 propylene glycol ketal may further comprise the steps:
(1) in reactor, add pimelinketone and 1,2 propylene glycol, and add contain ethylphenyl sulfonic acid copper mesoporous material as catalyzer, by the quality feed ratio, pimelinketone: 1,2 propylene glycol: catalyzer=1: 1～10: 0.01～0.3,
(2) divided under the condition of water stirring reaction 0.1～72 hour in reflux, be cooled to room temperature after, centrifugal solid-liquid separates;
(3), obtain product pimelinketone-1,2 propylene glycol ketal with the liquid product rectifying separation that obtains.Rectifying separation adopts conventional known technology.
To the solid product that the 2nd step centrifugation obtains, vacuum-drying is 1 hour～24 hours under 25 ℃～200 ℃ temperature, the catalyzer that obtains reclaiming.
The present invention adopts the mesoporous material that contains ethylphenyl sulfonic acid copper as catalyzer, and the described mesoporous material that contains ethylphenyl sulfonic acid copper is at the outside surface of SBA-15 mesoporous material and/or inner hole wall grafting ethylphenyl sulfonic acid copper.
This moment, described mesoporous material expression formula was
Figure B2009102355549D0000031
Wherein,
Figure B2009102355549D0000032
Representative is selected from aforesaid-Ar-SO 3Aromatic hydrocarbons sulfonate group a kind of, i.e. ethylphenyl sulfonate group.
For copper ions not, only, be designated as at the outside surface of SBA-15 mesoporous material and/or the mesoporous material of inner hole wall grafting ethylphenyl sulfonic acid group
Contain the preparation method of the mesoporous material of ethylphenyl sulfonic acid copper, may further comprise the steps:
(1) triblock copolymer polyoxyethylene-polyoxytrimethylene-polyoxyethylene (is called for short: PEO-PPO-PEO), join in the aqueous hydrochloric acid, by the mole feed ratio, triblock copolymer polyoxyethylene-polyoxytrimethylene-polyoxyethylene: water: hydrogenchloride=1: 9000～15000: 100～500
Under 25～60 ℃ of temperature, be stirred to dissolving, the material that the preferred U.S. chemical abstract registration number of described triblock copolymer polyoxyethylene-polyoxytrimethylene-polyoxyethylene is 9003-11-6, its average molecular mass Mn=5800.
(2) in previous step gained solution, add tetraethoxy, under 25～60 ℃ of temperature, stir more than 25 minutes; Add 2-(4-chlorine sulfonyl-phenyl) ethyl trimethoxy silane again, under 25～60 ℃ of temperature, stir more than 10 hours; By the mole feed ratio, triblock copolymer polyoxyethylene-polyoxytrimethylene-polyoxyethylene: tetraethoxy: 2-(4-chlorine sulfonyl-phenyl) ethyl trimethoxy silane=1: 20～100: 2～10.
(3) will go up step gained solution and place closed reaction vessel, crystallization is 10～40 hours under 90～150 ℃ of temperature.
(4) with the filtration of crystallization after product, washing, drying, obtain mesoporous material raw powder.
(5) the gained mesoporous material raw powder was washed 10～40 hours under 90～120 ℃ of temperature with ethanol, remove the masterplate agent, obtain containing the sulfonic mesoporous material of ethylphenyl.
(6) will go up the step gained contain the sulfonic mesoporous material of ethylphenyl and acetone, copper trifluoromethanesulfcomposite are put into closed reaction vessel jointly, by the quality feed ratio, contain the sulfonic mesoporous material of ethylphenyl: acetone: copper trifluoromethanesulfcomposite=1: 1～12: 0.1～16, under 25～150 ℃ of conditions, stirred 1～72 hour; Preferably with (5) mesoporous material that obtains of step 25 ℃～150 ℃ following vacuum-dryings 1 hour～24 hours, be cooled to room temperature after, carry out the reaction of (6) step again.
(7) product is cooled to room temperature, after the employing centrifugation,, obtains containing the mesoporous material solid product of ethylphenyl sulfonic acid copper 25～200 ℃ of following vacuum-dryings 1～24 hour.
Catalyst S BA (the Ar-SO that utilizes the present invention to prepare 3) 2Cu is to pimelinketone and 1,2 propylene glycol have carried out catalyzed reaction, content according to the gas chromatographic analysis pimelinketone is 3.9%, pimelinketone-1,2 propylene glycol ketal content are 96.2%, and the content of pimelinketone is 6.87% after the recycling, pimelinketone-1,2 propylene glycol ketal content are 34.1%, quadric catalysis post catalyst reaction SBA-Ar-(SO 3) 2Cu still keeps the distinctive orderly hexagonal hole road structure (seeing Fig. 1 and Fig. 2) of mesoporous material SBA-15.Under similarity condition, do not add and utilize gas chromatographic analysis reaction product liquid composition after any catalyzer reacts, do not see to measure other products.
The invention has the beneficial effects as follows:
The present invention will have the novel mesoporous material that sulfonic characteristic has the characteristic of metal ion again and be applied to pimelinketone important in the compound probability-1,2 propylene glycol ketal reactions, transformation efficiency height, selectivity height in catalyzed reaction, not only can reduce side reaction, improve product purity, and still keep high conversion and highly selective after using repeatedly, environmental pollution is less.
Description of drawings
Fig. 1 is
Figure B2009102355549D0000051
With of the present invention
Figure B2009102355549D0000052
Structure comparison diagram before and after the quadric catalysis reaction.
Fig. 2 is
Figure B2009102355549D0000053
With of the present invention
Figure B2009102355549D0000054
Pore structure synoptic diagram before and after the quadric catalysis reaction.
Fig. 3 be SBA-15,
Figure B2009102355549D0000055
With of the present invention
Figure B2009102355549D0000056
29Si CP/MAS NMR spectrogram.
Fig. 4 is
Figure B2009102355549D0000057
With of the present invention
Figure B2009102355549D0000058
Microscopic appearance figure before and after the quadric catalysis reaction.
Fig. 5 is
Figure B2009102355549D0000059
With of the present invention X ray energy spectrum analytical results figure.
Embodiment
Transformation efficiency in the following example is to calculate according to the result that gas chromatography-mass spectrography is analyzed to get.
Embodiment 1 preparation contains the mesoporous material of ethylphenyl sulfonic acid copper
(1) 4.0 gram P123 (registration number at U.S. chemical abstract is the material of 9003-11-6, its average molecular mass Mn=5800) is joined in the solution of 120ml 2N hydrochloric acid and 6ml water, be stirred to P123 at 40 ℃ and dissolve fully;
(2) again the 8.2ml tetraethoxy is joined in the above-mentioned solution, stirred 45 minutes, add 1.3 gram 2-(4-chlorine sulfonyl-phenyl) ethyl trimethoxy silanes again, stirred 24 hours at 40 ℃ at 40 ℃;
(3) gained solution is transferred in the teflon-lined reactor, 100 ℃ of crystallization 24 hours;
(4) through obtaining former powder mesoporous material after filtration, washing, the drying;
(5) former powder mesoporous material was under refluxad washed 24 hours with ethanol, remove the masterplate agent, obtain containing in the skeleton the sulfonic mesoporous material of ethylphenyl;
(6) with the above-mentioned sulfonic mesoporous material of ethylphenyl that contains of 1g 150 ℃ of following vacuum-dryings 6 hours, after being cooled to room temperature, again 15ml acetone and 1g copper trifluoromethanesulfcomposite are put into 100ml teflon-lined reactor together, the capping still stirred 24 hours under 55 ℃ of conditions;
(7) be cooled to room temperature after, obtain solid product behind the centrifugation filter liquide, with its 150 ℃ of vacuum-dryings 4 hours to remove impurity.Obtain product
Figure B2009102355549D0000061
Figure (1) a is XRD spectra, figure (1) b be
Figure B2009102355549D0000063
XRD spectra, figure (1) c be that quadric catalysis is reacted
Figure B2009102355549D0000064
XRD spectra.By above-mentioned three spectrograms as can be known,
Figure B2009102355549D0000065
And
Figure B2009102355549D0000066
Hexagonal hole road structure with the peculiar sequential 2 D of mesoporous material SBA-15, and after carrying out twice catalyzed reaction
Figure B2009102355549D0000067
Order mesoporous structure still remain unchanged.
Embodiment 2 preparation pimelinketone-1,2 propylene glycol ketals
Take by weighing 1.2 gram mesoporous materials
Figure B2009102355549D0000068
Take by weighing 12 grams 1 again, 2 propylene glycol, 10 gram pimelinketone are put into 100ml teflon-lined reactor successively, under refluxad stirred 1 hour, after being cooled to room temperature, centrifugation utilizes gas chromatographic analysis reaction product liquid composition, the content of pimelinketone is 3.9%, pimelinketone-1,2 propylene glycol ketal content is 96.2%, the solid catalyst mesoporous material
Figure B2009102355549D0000071
150 ℃ of following vacuum-dryings 6 hours, be cooled to room temperature after, utilize again after the recovery.
Preparation of Catalyst pimelinketone-1, the 2 propylene glycol ketal that embodiment 3 usefulness reclaim
1.2 gram mesoporous materials with embodiment 2 recyclings
Figure B2009102355549D0000072
Take by weighing 12 grams 1 again, 2 propylene glycol, 10 gram pimelinketone are put into 100ml teflon-lined reactor successively, under refluxad stirred 1 hour, after being cooled to room temperature, centrifugation utilizes gas chromatographic analysis reaction product liquid composition, and the content of pimelinketone is 6.87%, pimelinketone-1,2 propylene glycol ketal content is 34.1%.Comparative Examples 1
Take by weighing 12 the gram 1,2 propylene glycol, 10 the gram pimelinketone put into 100ml teflon-lined reactor successively, under refluxad stirred 1 hour, be cooled to room temperature after, centrifugation utilizes gas chromatographic analysis reaction product liquid composition, does not see to measure product.
Fig. 1 is
Figure B2009102355549D0000073
With of the present invention
Figure B2009102355549D0000074
Structure comparison diagram before and after the quadric catalysis reaction.Wherein figure (1) a is
Figure B2009102355549D0000075
XRD spectra, figure (1) b be
Figure B2009102355549D0000076
XRD spectra, figure (1) c be that quadric catalysis is reacted
Figure B2009102355549D0000077
XRD spectra.Compose the peak as can be known by the Small angle that XRD spectra occurs,
Figure B2009102355549D0000078
And before and after the quadric catalysis reaction The hexagonal hole road structure that still keeps the peculiar sequential 2 D of mesoporous material SBA-15.
Fig. 2 is With of the present invention
Figure B2009102355549D00000711
Quadric catalysis reaction front and rear gaps structural representation.Wherein figure (2) a is
Figure B2009102355549D0000081
The pore structure synoptic diagram, figure (2) b be
Figure B2009102355549D0000082
The pore structure synoptic diagram, figure (2) c be
Figure B2009102355549D0000083
The reacted pore structure synoptic diagram of quadric catalysis.As seen from the figure,
Figure B2009102355549D0000084
The front and back of quadric catalysis reaction still keep the hexagonal hole road structure of the peculiar sequential 2 D of mesoporous material SBA-15, and this result is consistent with the result of XRD.
Fig. 3 be SBA-15,
Figure B2009102355549D0000085
With of the present invention
Figure B2009102355549D0000086
29Si CP/MAS NMR spectrogram.Wherein figure (3) a is SBA-15's 29Si CP/MAS NMR spectrogram, figure (3) b is
Figure B2009102355549D0000087
29Si CP/MASNMR spectrogram, figure (3) c is 29Si CP/MAS NMR spectrogram.By spectrogram as can be seen,
Figure B2009102355549D0000089
29In the SiCP/MAS NMR spectrogram, (SiO) 2Si (OH) 2(Q 2The position), (SiO) 3Si (OH) (Q 3The position) and (SiO) 4Si (Q 4The position) three kinds connect skeleton Si go out the identical of peak position and SBA-15.Compare with SBA-15, except above-mentioned three peaks,
Figure B2009102355549D00000810
And
Figure B2009102355549D00000811
29Si CP/MAS NMR spectrogram new peak all occurs at 55ppm and 60ppm place respectively, and these two emerging spectrum peaks can belong to T m(T m=RSi (OSi) m(OH) 3-m, m=1-3; T 2At δ=-55 and T 3δ=-60ppm).These two emerging spectrum peaks show
Figure B2009102355549D00000812
Group successfully is grafted on the skeleton of SBA-15, and after carrying out ion exchange reaction
Figure B2009102355549D00000813
Skeleton structure still remains unchanged.
Fig. 4 is
Figure B2009102355549D00000814
With of the present invention Microscopic appearance figure before and after the quadric catalysis reaction.Wherein figure (4) a is
Figure B2009102355549D00000816
Microscopic appearance figure, figure (4) b be
Figure B2009102355549D00000817
Microscopic appearance figure, figure (4) c be
Figure B2009102355549D0000091
The reacted microscopic appearance figure of quadric catalysis.As seen from the figure,
Figure B2009102355549D0000092
Microscopic appearance is consistent with the result of bibliographical information before and after the quadric catalysis reaction.
Fig. 5 a is
Figure B2009102355549D0000093
X ray energy spectrum analytical results figure, Fig. 5 b is of the present invention X ray energy spectrum analytical results figure.The analysis of x ray energy spectrum shows
Figure B2009102355549D0000095
After carrying out ion exchange reaction, contained cupric ion in the skeleton.
Table 1 is x fluorometric analysis result, and the result shows SBA-Ar-SO 3H contains metal ion copper really in carrying out the ion exchange reaction back skeleton, this result also is consistent with x ray energy spectrum analytical results.
Table 1x fluorometric analysis result
Sample Sample Cu mass content (%)
a 0
b 3.7

Claims (2)

1. the preparation method of pimelinketone-1,2 a propylene glycol ketal is characterized in that, adopts the mesoporous material that contains ethylphenyl sulfonic acid copper as catalyzer, is raw material with pimelinketone and 1,2 propylene glycol, and preparation pimelinketone-1,2 propylene glycol ketal comprises the steps:
(1) in reactor, add pimelinketone and 1,2 propylene glycol, and add contain ethylphenyl sulfonic acid copper mesoporous material as catalyzer, by the quality feed ratio, pimelinketone: 1,2 propylene glycol: catalyzer=1: 1～10: 0.01～0.3,
(2) stirring reaction 0.1～72 hour under the condition of reflux, be cooled to room temperature after, centrifugal solid-liquid separates;
(3), obtain product pimelinketone-1,2 propylene glycol ketal with the liquid product rectifying separation that obtains.
2. the preparation method of pimelinketone-1,2 propylene glycol ketal according to claim 1 is characterized in that, to the solid product that the 2nd step centrifugation obtains, vacuum-drying is 1 hour～24 hours under 25 ℃～200 ℃ temperature, the catalyzer that obtains reclaiming.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JUAN A. MELERO ET AL.: "Acidic Mesoporous Silica for the Acetylation of Glycerol: Synthesis of Bioadditives to Petrol Fuel", 《ENERGY & FUELS》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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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