CN102617774A - Preparation method of solid acid material with carboxylic acid group and sulfonic acid group - Google Patents
Preparation method of solid acid material with carboxylic acid group and sulfonic acid group Download PDFInfo
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- CN102617774A CN102617774A CN2012100830376A CN201210083037A CN102617774A CN 102617774 A CN102617774 A CN 102617774A CN 2012100830376 A CN2012100830376 A CN 2012100830376A CN 201210083037 A CN201210083037 A CN 201210083037A CN 102617774 A CN102617774 A CN 102617774A
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Abstract
The invention discloses a preparation method of a solid acid material with carboxylic acid group and sulfonic acid group and belongs to the technical field of organic chemosynthesis. The preparation method is characterized in that a hydroxy sulfonate compound reacts with maleic anhydride to obtain a monoester compound containing olefinic link, sulfonic acid group and carboxyl group; the monoester compound is self-polymerized to form an oligomer; and then the oligomer is co-polymerized with divinyl benzene to form the solid acid material with the carboxylic acid group and the sulfonic acid group. The solid acid material with the carboxylic acid group and the sulfonic acid group, prepared by the invention has the advantages that the thermal stability is high, the catalysis effect is good, and accelerant can be used repeatedly.
Description
Technical field:
The present invention relates to the organic chemistry synthesis technical field, particularly a kind of carboxylic acid group and sulfonic solid-acid material preparation method of having concurrently.
Background technology:
Crisis occurs now in energy problem, environmental problem, do not produce unnecessary by product with a spot of energy and only generate the target that the purpose product becomes the modern chemical industry pursuit effectively.Acid catalyst is absolutely necessary in the chemical in modern times industry, is widely used in the manufacturing of variety of products such as medicine, petrochemical industry product, macromolecule product, but the most liquid acid catalyst as hydrochloric acid, sulfuric acid and so on that uses at present.The liquid catalyst that uses in process of production need be neutralized by alkali, through removing the operations such as salt that generated by neutralization, from product, separates, reclaims.But removing of above-mentioned neutralization and salt consumes quite a few energy in the operation.In addition, the salt excess supply that on market, reclaims, it is the little by product of operability mostly, therefore is difficult to usually handle.
With respect to above-mentioned situation; Because solid acid catalyst can not generate unnecessary by product in the operation of removing of separating, do not need when reclaiming above-mentioned neutralization or salt, and energy-conservation ground manufacturing purpose product; Therefore the research of this respect has received scientific worker's concern (Ishihara, K; Hasegawa, A; Yamamoto, H. Angew.Chem.Int.Ed.2001,40,4077.).Aspect the research and development of solid acid catalyst, solid acid catalysts such as zeolite, silica-alumina, moisture niobium have become the huge achievement of chemical industry, bring very big contribution to society.In addition,, can think that the material that the PS sulfonation is obtained is a solid acid, in the past always as having the tart Zeo-karb as the strong acid polymkeric substance.In addition, the known Nafion (registered trademark of E.I.Du Pont Company) that in the tetrafluoroethylene skeleton, has sulfo group also is the extremely strong solid acid (solid super-strong acid) of possess hydrophilic property, and the super acids that known their conducts have greater than the strength of acid of liquid acid works.But, the problem of selling at exorbitant prices when using is arranged in pair thermally labile, the industry.According to above-mentioned situation, consider that from aspects such as performance and costs use solid acid catalyst than using aforesaid liquid acid and more be difficult to design favourable industrial processes, nearly all now chemical industry all depends on liquid acid catalyst.In the classical acid catalyzer, generally only have an acid site, and differential responses also can be different to the acidity requirement of catalyzer, therefore, the polyacid center just becomes an important demand of solid acid catalyst.
For addressing the above problem, the present invention considers to prepare a kind of carboxylic acid group of having concurrently and sulfonic solid-acid material, makes material have multiple acid site, improves its catalytic efficiency (.
Summary of the invention:
The object of the present invention is to provide a kind of carboxylic acid group of having concurrently and sulfonic solid-acid material preparation method, the solid acid of this method preparation is recycled easy; Thermostability is high; Stable to water; The acid kind is many; Excellent catalytic effect.
The technical scheme that the present invention takes is following:
A kind of carboxylic acid group and sulfonic solid-acid material preparation method of having concurrently; It is characterized in that: with hydroxyl sulfoacid compound and maleic anhydride reaction; Obtain containing the monoester compound of ethylene linkage, sulfonic group and carboxyl; Monoester compound is carried out autohemagglutination, form oligopolymer, form carrying out copolymerization with Vinylstyrene again and have carboxylic acid group and sulfonic solid-acid material concurrently.
Further be provided with and be:
Described hydroxyl sulfoacid compound is any one of hydroxyethylsulfonic acid, hydroxypropyl sulfonic acid, p-hydroxybenzenyl sulfonate.
The mol ratio of described hydroxyl sulfoacid compound and maleic anhydride is 1:1.
A kind of carboxylic acid group and sulfonic solid-acid material preparation method of having concurrently is that raw material is dissolved in the ETHYLE ACETATE with the hydroxyl sulfoacid compound, drip be the ethyl acetate solution of maleic anhydride of 1:1 with hydroxyl sulfoacid compound mol ratio after; ETHYLE ACETATE is removed in distillation after stirring 4～12 hours under the room temperature condition; Obtain containing the monoester compound of ethylene linkage, sulfonic group and carboxyl, monoester compound is dissolved in ethanol after, add the azo isobutyronitrile initiator; Initiator amount is 0.5% of a monomer mass; Form oligopolymer after 4 hours carrying out the heated and stirred polymerization under 70 ℃, add again with the monoester compound mol ratio be the Vinylstyrene of 1:0.5～1:1.5, add the azo isobutyronitrile initiator simultaneously; Proceeding the heated and stirred polymerization under 70 ℃ after 2 hours; Be warming up to 80 ℃ and leave standstill after 24 hours and obtain white solid, behind the solid natural drying at room temperature, in 80 ℃ of baking ovens, promptly got in dry 12 hours again and have carboxylic acid group and sulfonic solid-acid material concurrently.
A kind of carboxylic acid group and sulfonic solid-acid material preparation method of having concurrently is characterized in that, may further comprise the steps:
The preparation of the 1st step, monoester compound:
Taking by weighing the hydroxyl sulfoacid compound is dissolved in the ETHYLE ACETATE; The ETHYLE ACETATE consumption is 20～50 times of hydroxyl sulfoacid compound quality; With the maleic anhydride massfraction is that 10% ethyl acetate solution is added drop-wise in the above-mentioned solution; Maleic anhydride is 1: 1 with the ratio of the amount of substance of hydroxyl sulfoacid compound, and ETHYLE ACETATE is removed in distillation after stirring 4～12 hours under the room temperature condition, obtains containing the monoester compound of ethylene linkage, sulfonic group and carboxyl;
The 2nd goes on foot, has concurrently the synthetic of carboxylic acid group and sulfonic solid-acid material:
The monoester compound of step 1 preparation is dissolved in ethanol; Amount of ethanol is 10～30 times of monoester compound quality, adds the azo isobutyronitrile initiator, and consumption is 0.5% of a monoesters quality; Form oligopolymer after 4 hours carrying out the heated and stirred polymerization under 70 ℃; Adding is the Vinylstyrene of 1:0.5～1:1.5 with the monoesters mol ratio again, adds the azo isobutyronitrile initiator simultaneously, and initiator amount is 0.5% of a monoesters quality; Proceeding the heated and stirred polymerization under 70 ℃ after 2 hours; Be warming up to 80 ℃ and leave standstill after 24 hours and obtain white solid, behind the solid natural drying at room temperature, in 80 ℃ of baking ovens, promptly got in dry 12 hours again and have carboxylic acid group and sulfonic solid-acid material concurrently.
The present invention compared with prior art has following beneficial effect:
(1) thermally-stabilised qualitative height, heat decomposition temperature is more than 190 ℃.
(2) sour kind is many, has carboxylic acid center and sulfonic acid center concurrently.
(3) recovery is easy, can separate through simple filtration.
(4) has bigger mesoporous hydrophobic surface.
(5) excellent catalytic effect, to general acid catalyzed reaction as: esterification, condensation, alkylation, etherificate etc. have very high catalytic activity.
(6) catalyzer can repeat repeatedly to use.
Below will do further elaboration to the present invention through concrete embodiment:
Embodiment:
One, preparation embodiment.
Embodiment 1:
The preparation of the 1st step, monoester compound:
Taking by weighing the hydroxyl sulfoacid compound is dissolved in the ETHYLE ACETATE; The ETHYLE ACETATE consumption is 30 times of hydroxyl sulfoacid compound quality; With the maleic anhydride massfraction is that 10% ethyl acetate solution is added drop-wise in the above-mentioned solution; Maleic anhydride is 1: 1 with the ratio of the amount of substance of hydroxyl sulfoacid compound, and ETHYLE ACETATE is removed in distillation after stirring 8 hours under the room temperature condition, obtains containing the monoester compound of ethylene linkage, sulfonic group and carboxyl;
The 2nd goes on foot, has concurrently the synthetic of carboxylic acid group and sulfonic solid-acid material:
The monoester compound of step 1 preparation is dissolved in ethanol, and amount of ethanol is 20 times of monoester compound quality, adds the azo isobutyronitrile initiator; Initiator amount is 0.5% of a monoesters quality, forms oligopolymer after 4 hours carrying out the heated and stirred polymerization under 70 ℃, add again with the monoester compound mol ratio be the Vinylstyrene of 1:1; And azo isobutyronitrile initiator; Initiator amount is 0.5% of a monoesters quality, is proceeding the heated and stirred polymerization under 70 ℃ after 2 hours, is warming up to 80 ℃ and leaves standstill after 24 hours and obtain white solid; Behind the solid natural drying at room temperature; Drying promptly got and has carboxylic acid group and sulfonic solid-acid material concurrently in 12 hours in 80 ℃ of baking ovens again, and the material acid number is 2.6mmol/g, 200 ℃ of thermotolerances.
Embodiment 2-4:
The preparation method is with embodiment 1, the ratio that difference is to regulate monoesters and Vinylstyrene, preparation have the carboxylic acid group concurrently and sulfonic solid-acid material is as shown in table 1.
Table 1: the preparation of the ratio of different monoesters and Vinylstyrene have carboxylic acid group and the contrast of sulfonic solid-acid material performance concurrently.
| Embodiment | N (monoesters)/n (Vinylstyrene) | Acid number/mmol/g | Heat decomposition temperature/℃ |
| 2 | 1:0.8 | 3.2 | 203 |
| 3 | 1:1.2 | 2.4 | 190 |
| 4 | 1:1.8 | 2.1 | 208 |
。
Two, application implementation example.
With embodiment 1 preparation have carboxylic acid group and sulfonic solid-acid material concurrently, be respectively applied for catalytic esterification, condensation reaction, alkylated reaction, etherification reaction, following embodiment.
Embodiment 5, catalytic esterification:
Having induction stirring, TM, reflux condensing tube; Adding 0.1mol Hydrocerol A, 0.45mol propyl carbinol carry out heated and stirred in the 100mL three-necked bottle of water trap, treat that Hydrocerol A dissolves back sampling and measuring acidity entirely, adds the catalyzer 0.25g of embodiment 1 preparation then; Carrying out reflux stirs; The water that reaction is produced is told from water trap, reacts 4 hours, and calculated yield is 98.6%.
Embodiment 6-10:
Except that following difference, all the other are with embodiment 5: after reaction finished, catalyzer carried out filtered and recycled, behind washing with acetone, place 100 ℃ of baking oven dryings after, continue on for catalyzed reaction, catalyzer reuse number of times and productive rate results of comparison are seen table 2.
Table 2, catalyzer reuse number of times and productive rate synopsis.
| Embodiment | Catalyzer reuse number of times | Productive rate/% |
| 6 | 0 | 98.6 |
| 7 | 1 | 98.3 |
| 8 | 2 | 97.9 |
| 9 | 3 | 97.4 |
| 10 | 4 | 97.0 |
。
Embodiment 11: the catalyzing and condensing reaction:
Having induction stirring; Reflux condensing tube; Add 0.1mol pimelinketone, 0.15mol terepthaloyl moietie, 10ml hexanaphthene and 0.1g catalyzer in the 100mL three-necked bottle of water trap, carry out the reflux stirring water and the entrainer azeotropic of reaction generation are steamed, reacted about 1.5 hours; Yield is reused 5 times for the 99.5%. catalyzer, and catalytic activity does not change.
Embodiment 12, catalytic alkylation reaction:
Having induction stirring, reflux condensing tube adds 0.1mol pyrocatechol, the 0.15mol trimethyl carbinol and 0.1g catalyzer in the 100mL three-necked bottle of water trap; Carrying out reflux stirs; Reacted about 4 hours, yield is that 88%. catalyzer are reused 5 times, and catalytic activity does not change.
Embodiment 13, catalyst etherifying reaction:
Having induction stirring, reflux condensing tube adds 0.1mol2-naphthols, 0.15mol methyl alcohol and 0.1g catalyzer in the 100mL three-necked bottle of water trap; Carrying out reflux stirs; Reacted about 6 hours, yield is that 82%. catalyzer are reused 5 times, and catalytic activity does not change.
Claims (5)
1. one kind has carboxylic acid group and sulfonic solid-acid material preparation method concurrently; It is characterized in that: with hydroxyl sulfoacid compound and maleic anhydride reaction; Obtain containing the monoester compound of ethylene linkage, sulfonic group and carboxyl; Monoester compound is carried out autohemagglutination, form oligopolymer, carry out copolymerization with Vinylstyrene again and form and have carboxylic acid group and sulfonic solid-acid material concurrently.
2. a kind of carboxylic acid group and sulfonic solid-acid material preparation method of having concurrently according to claim 1 is characterized in that: described hydroxyl sulfoacid compound is any one of hydroxyethylsulfonic acid, hydroxypropyl sulfonic acid, p-hydroxybenzenyl sulfonate.
3. a kind of carboxylic acid group and sulfonic solid-acid material preparation method of having concurrently according to claim 1, it is characterized in that: the mol ratio of described hydroxyl sulfoacid compound and maleic anhydride is 1:1.
4. a kind of carboxylic acid group and sulfonic solid-acid material preparation method of having concurrently according to claim 1 is characterized in that: with the hydroxyl sulfoacid compound is that raw material is dissolved in the ETHYLE ACETATE, drip be the ethyl acetate solution of maleic anhydride of 1:1 with hydroxyl sulfoacid compound mol ratio after; ETHYLE ACETATE is removed in distillation after stirring 4～12 hours under the room temperature condition; Obtain containing the monoester compound of ethylene linkage, sulfonic group and carboxyl, monoester compound is dissolved in ethanol after, add the azo isobutyronitrile initiator; Initiator amount is 0.5% of a monomer mass; Form oligopolymer after 4 hours carrying out the heated and stirred polymerization under 70 ℃, add again with the monoester compound mol ratio be the Vinylstyrene of 1:0.5～1:1.5, add the azo isobutyronitrile initiator simultaneously; Proceeding the heated and stirred polymerization under 70 ℃ after 2 hours; Be warming up to 80 ℃ and leave standstill after 24 hours and obtain white solid, behind the solid natural drying at room temperature, in 80 ℃ of baking ovens, promptly got in dry 12 hours again and have carboxylic acid group and sulfonic solid-acid material concurrently.
5. a kind of carboxylic acid group and sulfonic solid-acid material preparation method of having concurrently according to claim 1 is characterized in that, may further comprise the steps:
The preparation of the 1st step, monoester compound:
Taking by weighing the hydroxyl sulfoacid compound is dissolved in the ETHYLE ACETATE; The ETHYLE ACETATE consumption is 20～50 times of hydroxyl sulfoacid compound quality; With the maleic anhydride massfraction is that 10% ethyl acetate solution is added drop-wise in the above-mentioned solution; Maleic anhydride is 1: 1 with the ratio of the amount of substance of hydroxyl sulfoacid compound, and ETHYLE ACETATE is removed in distillation after stirring 4～12 hours under the room temperature condition, obtains containing the monoester compound of ethylene linkage, sulfonic group and carboxyl;
The 2nd goes on foot, has concurrently the synthetic of carboxylic acid group and sulfonic solid-acid material:
The monoester compound of step 1 preparation is dissolved in ethanol; Amount of ethanol is 10～30 times of monoester compound quality, adds the azo isobutyronitrile initiator, and consumption is 0.5% of a monoesters quality; Form oligopolymer after 4 hours carrying out the heated and stirred polymerization under 70 ℃; Adding is the Vinylstyrene of 1:0.5～1:1.5 with the monoesters mol ratio again, adds the azo isobutyronitrile initiator simultaneously, and initiator amount is 0.5% of a monoesters quality; Proceeding the heated and stirred polymerization under 70 ℃ after 2 hours; Be warming up to 80 ℃ and leave standstill after 24 hours and obtain white solid, behind the solid natural drying at room temperature, in 80 ℃ of baking ovens, promptly got in dry 12 hours again and have carboxylic acid group and sulfonic solid-acid material concurrently.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113333036A (en) * | 2021-05-26 | 2021-09-03 | 华东理工大学 | Preparation method and application of niobium modified hydrophobic acidic cation exchange resin |
| CN115477759A (en) * | 2021-05-31 | 2022-12-16 | 中国石油化工股份有限公司 | Metal organic framework material with sulfonyl ketene structure, preparation method and application thereof, and carboxylic acid esterification method |
-
2012
- 2012-03-27 CN CN2012100830376A patent/CN102617774A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| 潘祖仁: "《高分子化学（第二版）》", 30 June 1997, 化学工业出版社 * |
| 贺英等: "《涂料树脂化学》", 31 August 2007, 化学工业出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113333036A (en) * | 2021-05-26 | 2021-09-03 | 华东理工大学 | Preparation method and application of niobium modified hydrophobic acidic cation exchange resin |
| CN115477759A (en) * | 2021-05-31 | 2022-12-16 | 中国石油化工股份有限公司 | Metal organic framework material with sulfonyl ketene structure, preparation method and application thereof, and carboxylic acid esterification method |
| CN115477759B (en) * | 2021-05-31 | 2023-10-10 | 中国石油化工股份有限公司 | Metal organic framework material with sulfonyl ketene structure, preparation method and application thereof, and carboxylic acid esterification method |
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Application publication date: 20120801 |