CN102070758B - Resorcinol formaldehyde resin base solid acid and preparation method and application thereof - Google Patents
Resorcinol formaldehyde resin base solid acid and preparation method and application thereof Download PDFInfo
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- CN102070758B CN102070758B CN201010583316A CN201010583316A CN102070758B CN 102070758 B CN102070758 B CN 102070758B CN 201010583316 A CN201010583316 A CN 201010583316A CN 201010583316 A CN201010583316 A CN 201010583316A CN 102070758 B CN102070758 B CN 102070758B
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Abstract
The invention discloses a resorcinol formaldehyde resin base solid acid and a preparation method and application thereof, belonging to the technical field of chemical synthesis. The invention is characterized in that the preparation method comprises the following steps: by using resorcinol as a raw material, a formaldehyde solution (the mol ratio of the raw material to the formaldehyde solution is (1:1)-(1:3)) as a crosslinking agent and hydroxy-ethyl sulfonic acid (the mol ratio of the raw material to the hydroxy-ethyl sulfonic acid is (1:0.1)-(1:1)) as an active molecule, adding water (the mass ratio of the resorcinol to the water is 1:5-1:20) to prepare a solution; carrying out condensation reaction at 65-95 DEG C for 60-120 hours, and drying by rotary evaporation to obtain the RF (resorcinol formaldehyde) resin; then, carrying out carbonization condensation reaction at 180-300 DEG C for 2-32 hours; and after the reaction, washing with hot water at the temperature higher than 80 DEG C, filtering to remove free acidic materials, and drying the product in a baking oven at 120 DEG C to obtain the resorcinol formaldehyde resin base solid acid. The resorcinol formaldehyde resin base solid acid disclosed by the invention has the advantages of high thermal stability, high acid value, favorable catalysis effect and the like, and can be repeatedly used.
Description
Technical field:
After the present invention relates to Resorcinol, formaldehyde and hydroxyethylsulfonic acid be condensed into resin earlier, under the high temperature nitrogen condition, carry out carbonization again and the resorcinol formaldehyde resin based solid acid that is insoluble to polar solvent that obtains and above-mentioned solid acid as the purposes of solid acid catalyst.
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 order to break this present situation, hope to appear at performance and the solid acid catalyst of cost aspect above liquid acid.
In addition, in inorganic system, with zirconium white (ZrO
2) use vitriolization; The sulfuric acid trace that obtains (sulfuric acid trace) zirconium white is for having the most highly acid solid acid catalyst; But the sulfuric acid trace on surface is few, and sour point (acid point) number of per unit weight lacks a lot than liquid acid, therefore also far can not satisfy above-mentioned requirements.
Have based on this, the applicant makes the present invention.
Summary of the invention:
First aspect purpose of the present invention is to provide a kind of eco-friendly, economic resorcinol formaldehyde resin based solid acid catalyst.
The technical scheme that the present invention takes is following, and a kind of resorcinol formaldehyde resin based solid acid is characterized in that: be raw material with the Resorcinol; With material molar ratio be that 1: 1～1: 3 formaldehyde solution is linking agent, with material molar ratio be 1: 0.1～1: the hydroxyethylsulfonic acid of 1mol is a bioactive molecule, and adding with the Resorcinol mass ratio is 1: 5～1: 20 water wiring solution-forming; Behind condensation reaction 60～120h under 65～95 ℃ of conditions, revolve and steam to doing, get the RF resin; Place then and carry out carbonization condensation reaction 2～32h under 180～300 ℃; After reaction finished, the hot water that adds more than 80 ℃ washed, and filtered; Remove the free acidic substance, product is drying to obtain the resorcinol formaldehyde resin based solid acid in 120 ℃ baking oven.
Resorcinol formaldehyde resin based solid acid of the present invention; Be a kind of solid acid catalyst with wide range of industrial applications prospect; It is matrix that the present invention's employing has large-area resorcinol formaldehyde resin sill, and this material has the stable basic framework of physical actions such as heat, is conceived to use hydroxyethylsulfonic acid to be bioactive molecule; As the earlier synthetic resorcinol formaldehyde resin sill of catalyzer; Wherein comprise more hydroxyethylsulfonic acid, then at high temperature carry out carbonization and condensation, make the functional group reactions such as hydroxyl and phenolic hydroxyl group of hydroxyethylsulfonic acid and be attached on the resin-based materials.In order to prevent the excessive carbonization of material; Selecting hydroxyethylsulfonic acid is gentle acid catalyst; For the more sulfonic group of introducing, select the hydroxy functional group of hydroxyethylsulfonic acid and the hydroxyl of Resorcinol to carry out condensation, thereby obtain the functionalized solid-acid material of sulfonic group.
The resorcinol formaldehyde resin based solid acid of the present invention preparation can be widely used in reactions such as catalytic esterification, condensation, alkylation, etherificate, through check, has the acid number height, good stability, and catalytic efficiency (is high, and is synthetic easy, advantage such as can repeat repeatedly to use.
Second aspect purpose of the present invention provides a kind of preparation method of above-mentioned resorcinol formaldehyde resin based solid acid, it is characterized in that, may further comprise the steps:
(1), the building-up reactions of carbon-based solid acid: in Erlenmeyer flask, add Resorcinol; With material molar ratio be 1: 0.1～1: the hydroxyethylsulfonic acid of 1mol is a bioactive molecule, and adding with the Resorcinol mass ratio is 1: 5～1: 20 water wiring solution-forming, under agitation condition, drips and the Resorcinol mol ratio is 1: 1～1: 3 a formaldehyde solution; Be placed at condensation reaction 60～120h in 65～95 ℃ of baking ovens; Obtain red solid, revolve and steam, get the RF resin to doing; The above-mentioned resin of synthetic is placed silica tube, under condition of nitrogen gas, under 180～300 ℃, carry out carbonization condensation reaction 2～32h, get black solid;
(2), washing suction filtration and oven dry: behind the black solid cool to room temperature with step 1 preparation; The hot water that adds more than 80 ℃ washs; And filter, till the filtrating clarification does not have acidity, place 120 ℃ baking oven to dry catalyzer again and got product in 1～2 day.
Third aspect of the invention purpose provides a kind of above-mentioned resorcinol formaldehyde resin based solid acid and is used for reactions such as catalytic esterification, condensation, alkylation, etherificate as solid acid catalyst, and the present invention is as solid acid catalyst, during reaction such as catalyzer esterification, condensation, alkylation, etherificate; Reaction yield reaches more than 90%; And after reaction finished, catalyzer carried out filtered and recycled, and with washing; After drying again; Directly be used for reacting, through detecting, its catalyst activity still remains unchanged basically next time.
The present invention compares with background technology, has following beneficial effect:
(1) the synthesis of solid acid heat stability is high, and heat decomposition temperature is more than 150 ℃;
(2) the solid acid acid number is high, and general acid number is at 1～4mmol/g;
(3) compound method green non-pollution;
(4) synthesis of solid acid has bigger specific surface area;
(5) excellent catalytic effect, to general acid catalyzed reaction as: esterification, condensation, alkylation, etherificate etc. all 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:
Embodiment 1: the preparation of resorcinol formaldehyde resin based solid acid
(1), the building-up reactions of carbon-based solid acid:
In Erlenmeyer flask, add Resorcinol 0.01mol, hydroxyethylsulfonic acid 0.001mol, water 15g; Mix, become clear solution, under agitation condition, drip the formaldehyde solution of 0.02mol; After placing 85 ℃ of baking oven condensation 72h immediately after dripping fully; Obtain red solid, revolve and steam, must contain the hydroxyethylsulfonic acid resin to doing.The synthetic resin is placed silica tube, under condition of nitrogen gas, under 250 ℃, carry out carbonization condensation reaction 10h, get black solid;
(2), washing suction filtration and oven dry:
After treating the black solid cool to room temperature of above-mentioned preparation, the hot water that adds more than 80 ℃ washs, and filters; Until the filtrating clarification, and till the acidity, place 120 ℃ baking oven to dry 1 day solid again; The acid number that obtains catalyzer is 2.3mmol/g, and heat decomposition temperature is 180 ℃.
Embodiment 2-4:
The preparation method is with embodiment 1, and difference is: it is as shown in table 1 to change the carbonization condensation reaction time.
Table 1: catalyst performance contrast under the different carbonization condensation reaction times
| Embodiment | Reaction times/h | Acid number/mmol/g | Heat decomposition temperature/℃ |
| 2 | 16 | 2.4 | 180 |
| 3 | 24 | 2.5 | 200 |
| 4 | 32 | 2.6 | 190 |
Embodiment 5-7:
The preparation method is with embodiment 1, and difference is: the consumption that changes hydroxyethylsulfonic acid is as shown in table 2.
Table 2: catalyst performance contrast under the consumption of different hydroxyethylsulfonic acids
Embodiment 8-10
The preparation method is with embodiment 1, and difference is: it is as shown in table 3 to change the carbonization setting-up point.
Table 3: catalyst performance contrast under the different carbonization setting-up point
| Embodiment | Temperature of reaction/℃ | Acid number/mmol/g | Heat decomposition temperature/℃ |
| 8 | 200 | 2.4 | 190 |
| 9 | 220 | 3.0 | 200 |
| 10 | 300 | 2.5 | 210 |
Embodiment 11: the resorcinol formaldehyde resin based solid acid is in the application of catalytic esterification
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 of 0.5g then; Carrying out reflux stirs; The water that reaction is produced is told from water trap, reaction 4h, and calculated yield is 98.8%.
Embodiment 12-16:
Except that following difference, all the other and embodiment 11, after reaction finished, catalyzer carried out filtered and recycled, behind washing with acetone, place 100 ℃ of baking oven dryings after, continue reaction, the result sees table 4.
Table 4: the catalytic effect contrast under the different catalysts reuse number of times
| Embodiment | Catalyzer reuse number of times | Productive rate/% |
| 12 | 0 | 98.8 |
| 13 | 1 | 98.3 |
| 14 | 2 | 97.9 |
| 15 | 3 | 97.4 |
| 16 | 4 | 97.0 |
Embodiment 17: the resorcinol formaldehyde resin based solid acid is in the application of catalyzing and condensing reaction
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, about reaction 2h; Yield is that 99%. catalyzer are reused 5 times, and catalytic activity does not change.
Embodiment 18: the resorcinol formaldehyde resin based solid acid is in the application of catalytic alkylation reaction
Catalytic alkylation reaction: having induction stirring; Reflux condensing tube; Add 0.1mol pyrocatechol, the 0.15mol trimethyl carbinol and 0.1g catalyzer in the 100mL three-necked bottle of water trap, carry out reflux and stir, about reaction 4h; Yield is that 93%. catalyzer are reused 5 times, and catalytic activity does not change.
Embodiment 19: the resorcinol formaldehyde resin based solid acid is in the application of catalyst etherifying reaction
The 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; About reaction 6h, yield is that 88%. catalyzer are reused 5 times, and catalytic activity does not change.
Claims (4)
1. resorcinol formaldehyde resin based solid acid is characterized in that: be raw material with the Resorcinol, with material molar ratio be that 1: 1～1: 3 formaldehyde solution is linking agent; With material molar ratio be that 1: 0.1～1: 1 hydroxyethylsulfonic acid is a bioactive molecule, adding with the Resorcinol mass ratio is 1: 5～1: 20 water wiring solution-forming, behind condensation reaction 60～120h under 65～95 ℃ of conditions; Revolve and steam to doing; Get the RF resin, place then and carry out carbonization condensation reaction 2～32h under 180～300 ℃, after reaction finishes; The hot water that adds more than 80 ℃ washs; Filter, remove the free acidic substance, product is drying to obtain the resorcinol formaldehyde resin based solid acid in 120 ℃ baking oven.
2. the preparation method of the said resorcinol formaldehyde resin based solid acid of claim 1 is characterized in that, may further comprise the steps:
(1), the building-up reactions of carbon-based solid acid: in Erlenmeyer flask, add Resorcinol; With material molar ratio be that 1: 0.1～1: 1 hydroxyethylsulfonic acid is a bioactive molecule, adding with the Resorcinol mass ratio is 1: 5～1: 20 water wiring solution-forming, under agitation condition, drips and the Resorcinol mol ratio is 1: 1～1: 3 a formaldehyde solution; Be placed at condensation reaction 60～120h in 65～95 ℃ of baking ovens; Obtain red solid, revolve and steam, get the RF resin to doing; The above-mentioned resin of synthetic is placed silica tube, under condition of nitrogen gas, under 180～300 ℃, carry out carbonization condensation reaction 2～32h, get black solid;
(2), washing suction filtration and oven dry: behind the black solid cool to room temperature with step 1 preparation; The hot water that adds more than 80 ℃ washs; And filter; Till the filtrating clarification does not have acidity, place 120 ℃ baking oven to dry the resorcinol formaldehyde resin based solid acid that obtains again and got product in 1～2 day.
3. the application of the said resorcinol formaldehyde resin based solid acid of claim 1 in the catalyzing and condensing reaction.
4. the application of resorcinol formaldehyde resin based solid acid in the catalyzing and condensing reaction of the said method preparation of claim 2.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102627748B (en) * | 2012-03-27 | 2013-07-03 | 绍兴文理学院 | Preparation method of acidic ionic liquid resorcinol formaldehyde resin copolymer material |
| CN102618392A (en) * | 2012-03-27 | 2012-08-01 | 绍兴文理学院 | Method for synthetizing biodiesel from resin solid acid catalyzed waste oil |
| CN102659592A (en) * | 2012-05-11 | 2012-09-12 | 绍兴文理学院 | Method for synthesizing tributyl citrate by using resorcinol formaldehyde resin based solid acid as catalyst |
| CN104492482A (en) * | 2014-11-26 | 2015-04-08 | 绍兴文理学院 | Polymerized ionic liquid-silicon dioxide composite solid acid and preparation method thereof |
| CN112973589B (en) * | 2021-02-05 | 2022-04-29 | 中国工程物理研究院激光聚变研究中心 | Preparation method of sulfonated RF aerogel microspheres |
| CN114797898A (en) * | 2022-04-29 | 2022-07-29 | 合肥工业大学 | Solid carbon sulfonic acid catalyst, preparation method and application thereof |
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| CN101550223A (en) * | 2009-04-27 | 2009-10-07 | 西北师范大学 | Sulfonated phenolic resin and preparation and application as catalyst thereof |
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| CN101550223A (en) * | 2009-04-27 | 2009-10-07 | 西北师范大学 | Sulfonated phenolic resin and preparation and application as catalyst thereof |
Non-Patent Citations (3)
| Title |
|---|
| Kazuaki Ishihara，et al."Polystyrene-Bound Tetrafluorophenylbis(triflyl)methane as an Organic-Solvent-Swellable and Strong Brø |
| Kazuaki Ishihara,et al."Polystyrene-Bound Tetrafluorophenylbis(triflyl)methane as an Organic-Solvent-Swellable and Strong Brø * |
| nsted Acid Catalyst".《Angewandte Chemie》.2001,第113卷(第21期),4201-4203. |
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