CN104326915A - Method for synthesizing ethyl p-hydroxybenzoate through catalysis of modified metal oxide type solid super acid - Google Patents
Method for synthesizing ethyl p-hydroxybenzoate through catalysis of modified metal oxide type solid super acid Download PDFInfo
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- CN104326915A CN104326915A CN201410523176.5A CN201410523176A CN104326915A CN 104326915 A CN104326915 A CN 104326915A CN 201410523176 A CN201410523176 A CN 201410523176A CN 104326915 A CN104326915 A CN 104326915A
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- solid super
- modified metal
- oxide type
- ethyl
- strong acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
Abstract
The present invention discloses a method for synthesizing ethyl p-hydroxybenzoate through catalysis of a modified metal oxide type solid super acid. The method comprises: (1) adopting a modified metal oxide type solid super acid as a catalyst, heating p-hydroxybenzoic acid and excess ethanol, carrying out an esterification reaction at a reflux temperature of 75-85 DEG C, and co-boiling part of the ethanol and the water produced by the reaction so as to take away the ethanol; and (2) after reacting for 3-4 h, filtering to separate and recover the solid super acid catalyst, wherein the filtrate presents the yellow oil state; and carrying out rotary evaporation to remove the excess ethanol to obtain the ethyl p-hydroxybenzoate. According to the present invention, the modified metal oxide type solid super acid is adopted as the catalyst for the ethyl p-hydroxybenzoate synthesis reaction, such that the catalysis effect is significant, the environment protection effect is provided, the solid super acid is easily recovered and regenerated, can maintain the high activity and can be reused.
Description
Technical field
The present invention relates to chemical synthesis process, be specifically related to a kind of method of modified metal-oxide type Synthesis of Ethyl-p-Hydroxyl-Benzoate with Solid Super Strong Acid as Catalyst.
Background technology
Nipagin esters and p-Hydroxybenzoate, the ester normally formed by P-hydroxybenzoic acid and C1-C7 lower aliphatic alcohols is the sanitas of a kind of safe, efficient, the wide spectrum adopted in the world at present.As the intermediate of organic synthesis, due to it, to have toxicity little, nonirritant and can be used for the advantages such as wider pH value scope and be widely used in food, makeup and medicine industry is one of product of the food preservativess such as the alternative Sodium Benzoate given priority to of China.In addition, the dyestuff intermediate in the intermediate of nipagin esters or new ester organic lcd and thermal recording material, therefore, researchs and develops this series products and has a extensive future.
In recent years, quite active to the research of nipagin esters synthetic method both at home and abroad, mainly concentrate on the selection of used catalyst when P-hydroxybenzoic acid and correspondent alcohol carry out esterification.Sulfuric acid catalysis synthesis is classical way and the traditional technology of nipagin esters synthesis, the shortcomings such as effect better and technical maturity, but exists that side reaction is many, etching apparatus and contaminate environment; All there is product postprocessing complexity in the synthesis of sulfonic acid, inorganic salt and heteropoly acid catalysis, catalyzer is difficult to deficiencies such as reclaiming and reuse.
Solid super-strong acid can overcome the shortcoming of liquid strong acid, is easily separated with liquid-phase reaction system as catalyzer, and aftertreatment is simple, recyclablely reuses.In heterogeneous catalytic reaction, metal oxide-loaded type solid super strong acid heat stability is obviously better than other catalyzer of the same type, and corrosion device, the advantage such as free from environmental pollution receive increasing concern because its catalytic activity is high, selectivity is good, active ingredient not easily runs off, not.Strength of acid due to metal oxide-loaded type solid super-strong acid can't adapt to some acid catalyzed reaction requirement, therefore passes through its modification to improve stability and the catalytic activity of catalyzer further.
The research of metal oxide-loaded type solid super-strong acid and modified metal-oxide type solid super-strong acid is just becoming recent domestic and is seeking one of focus of novel green effective catalyst; and be widely used in the aspects such as alkylation, acidylate, esterification and alkane isomerization, but but have no report with the research of modified metal-oxide type solid superacid as catalyst synthesis nipagin esters series product always.Therefore, modified metal-oxide type Synthesis of Ethyl-p-Hydroxyl-Benzoate with Solid Super Strong Acid as Catalyst is significant to " green chemical industry " future development for its suitability for industrialized production.
A kind of eco-friendly ethyl p-hydroxybenzoate green synthesis process with prospects for commercial application of current shortage.
Summary of the invention
The object of the invention is to propose a kind of method with the eco-friendly modified metal-oxide type Synthesis of Ethyl-p-Hydroxyl-Benzoate with Solid Super Strong Acid as Catalyst of prospects for commercial application.
Technical scheme of the present invention is as follows: a kind of method of modified metal-oxide type Synthesis of Ethyl-p-Hydroxyl-Benzoate with Solid Super Strong Acid as Catalyst, comprises the steps:
(1) with modified metal-oxide type solid super-strong acid for catalyzer, by P-hydroxybenzoic acid and excess ethyl alcohol heat temperature raising, under reflux conditions, carry out esterification, part ethanol and water generation reaction azeotropic are taken out of;
(2), after reaction terminates, filter with Separation and Recovery solid super acid catalyst, filtrate is yellow oily, through rotary evaporation removing excess ethyl alcohol, and obtained ethyl p-hydroxybenzoate.
Further, in step (1), described metal-oxide solid super-strong acid is tungstic oxide/zirconium dioxide WO
3/ ZrO
2; Described modified metal-oxide type solid super-strong acid is tungstic oxide/boron trioxide-zirconium dioxide WO
3/ B
2o
3-ZrO
2.
Further, in step (1), the molar ratio of described P-hydroxybenzoic acid and ethanol is 1: 5-9.
Further, in step (1), the mass ratio that feeds intake of described P-hydroxybenzoic acid and modified metal-oxide type solid super-strong acid is 6-10: 1.Reclaiming catalyst levels is identical with fresh catalyst dosage.
Beneficial effect: the solid super acid catalyst reclaimed in the present invention is through manipulation of regeneration and can be recycled after vacuum-drying, the present invention adopts the modified metal-oxide type solid super-strong acid of high catalytic activity to be used for catalyzing and synthesizing ethyl p-hydroxybenzoate as catalyzer, not only catalytic effect is remarkable, environmentally friendly, and solid super-strong acid reclaiming is easy, and high reactivity can be kept to reuse.Thus on the basis of Optimal reaction conditions, propose the green synthesis process of ethyl p-hydroxybenzoate, there is good prospects for commercial application, higher economic benefit and social benefit can be produced.
Embodiment
To be further described specifically the present invention by specific embodiment below, but can not be interpreted as it is limiting the scope of the present invention.
Embodiment 1
Prepare modified metal-oxide type solid super-strong acid:
By ZrOCl
28H
2o is dissolved in deionized water and is mixed with certain concentration solution, first add the boric acid of quantitative Analysis, stirring and dissolving, after add a certain proportion of ammonium metawolframate, stirring and dissolving, under agitation joined solution and 6mol/l ammoniacal liquor are dropwise added in the ammonia soln of a certain amount of pH=9 simultaneously, controlling whole dropping process pH value perseverance is 9, dropping terminate rear continuation stir certain hour, left at room temperature ageing, filter and with deionized water wash to can't detect Cl
-ion, in 120 DEG C of dry 12h, then in atmosphere protection box-type furnace roasting 3h at 700 DEG C, obtained modified metal-oxide type solid super-strong acid WO
3/ B
2o
3-ZrO
2, stand-by.
Synthesis ethyl p-hydroxybenzoate:
3.45g P-hydroxybenzoic acid, 10.5ml dehydrated alcohol and 0.49g modified metal-oxide type solid super-strong acid WO is added in reaction vessel
3/ B
2o
3-ZrO
2, heat temperature raising, carries out esterification under reflux conditions.After reaction terminates, filter with Separation and Recovery solid super acid catalyst, filtrate removes excess ethyl alcohol through rotary evaporation, obtains product ethyl p-hydroxybenzoate, productive rate 92.6%.
The solid super acid catalyst reclaimed to can be recycled after vacuum-drying through manipulation of regeneration.
The solid super acid catalyst reclaimed in the present invention is through manipulation of regeneration and can be recycled after vacuum-drying, the present invention adopts the modified metal-oxide type solid super-strong acid of high catalytic activity to be used for catalyzing and synthesizing ethyl p-hydroxybenzoate as catalyzer, not only catalytic effect is remarkable, environmentally friendly, and solid super-strong acid reclaiming is easy, and high reactivity can be kept to reuse.Thus on the basis of Optimal reaction conditions, propose the green synthesis process of ethyl p-hydroxybenzoate, there is good prospects for commercial application, higher economic benefit and social benefit can be produced.
Embodiment 2
Embodiment 2 is with the difference of embodiment 1: in reaction vessel, add 3.45g P-hydroxybenzoic acid, 10.5ml dehydrated alcohol and 0.58g modified metal-oxide type solid super-strong acid WO
3/ B
2o
3-ZrO
2, heat temperature raising, carries out esterification under reflux conditions.After reaction terminates, filter with Separation and Recovery solid super acid catalyst, filtrate removes excess ethyl alcohol through rotary evaporation, obtains product ethyl p-hydroxybenzoate, productive rate 91.8%.
The solid super acid catalyst reclaimed to can be recycled after vacuum-drying through manipulation of regeneration.
Embodiment 3
Embodiment 3 is with the difference of embodiment 1: in reaction vessel, add 3.45g P-hydroxybenzoic acid, 12.0ml dehydrated alcohol and 0.49g modified metal-oxide type solid super-strong acid WO
3/ B
2o
3-ZrO
2, heat temperature raising, carries out esterification under reflux conditions.After reaction terminates, filter with Separation and Recovery solid super acid catalyst, filtrate removes excess ethyl alcohol through rotary evaporation, obtains product ethyl p-hydroxybenzoate, productive rate 91.0%.
The solid super acid catalyst reclaimed to can be recycled after vacuum-drying through manipulation of regeneration.
Embodiment 4
Embodiment 4 is with the difference of embodiment 1: the modified metal-oxide type solid super-strong acid WO adding 3.45g P-hydroxybenzoic acid, 10.5ml dehydrated alcohol and 0.49g reclaiming in reaction vessel
3/ B
2o
3-ZrO
2, heat temperature raising, carries out esterification under reflux conditions.After reaction terminates, filter with Separation and Recovery solid super acid catalyst, filtrate removes excess ethyl alcohol through rotary evaporation, obtains product ethyl p-hydroxybenzoate, productive rate 92.3%.
The solid super acid catalyst reclaimed to can be recycled after vacuum-drying through manipulation of regeneration.
Comparative example 1
3.45g P-hydroxybenzoic acid, 10.5ml dehydrated alcohol and 0.49g metal oxide-loaded type solid super-strong acid WO is added in reaction vessel
3/ ZrO
2, heat temperature raising, carries out esterification under reflux conditions.After reaction terminates, filter with Separation and Recovery solid super acid catalyst, filtrate removes excess ethyl alcohol through rotary evaporation, obtains product ethyl p-hydroxybenzoate, productive rate 72.1%.
The solid super acid catalyst reclaimed to can be recycled after vacuum-drying through manipulation of regeneration.
As seen from the above-described embodiment, in ethyl p-hydroxybenzoate building-up reactions, with modified metal-oxide type solid super-strong acid WO
3/ B
2o
3-ZrO
2target product productive rate is obtained higher as catalyzer.
More than show and describe ultimate principle of the present invention, principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and application claims protection domain is defined by appending claims, specification sheets and equivalent thereof.
Claims (4)
1. a method for modified metal-oxide type Synthesis of Ethyl-p-Hydroxyl-Benzoate with Solid Super Strong Acid as Catalyst, is characterized in that comprising the steps:
(1) with modified metal-oxide type solid super-strong acid for catalyzer, by P-hydroxybenzoic acid and excess ethyl alcohol heat temperature raising, under reflux temperature 75-85 DEG C condition, carry out esterification, part ethanol and water generation reaction azeotropic are taken out of;
(2) after reaction in 3-4 hour terminates, filter with Separation and Recovery solid super acid catalyst, filtrate is yellow oily, through rotary evaporation removing excess ethyl alcohol, and obtained ethyl p-hydroxybenzoate.
2. the method for modified metal-oxide type Synthesis of Ethyl-p-Hydroxyl-Benzoate with Solid Super Strong Acid as Catalyst according to claim 1, is characterized in that: in step (1), described metal-oxide solid super-strong acid is tungstic oxide/zirconium dioxide WO
3/ ZrO
2; Described modified metal-oxide type solid super-strong acid is tungstic oxide/boron trioxide-zirconium dioxide WO
3/ B
2o
3-ZrO
2.
3. the method for modified metal-oxide type Synthesis of Ethyl-p-Hydroxyl-Benzoate with Solid Super Strong Acid as Catalyst according to claim 1, is characterized in that: in step (1), the molar ratio of described P-hydroxybenzoic acid and ethanol is 1: 5-9.
4. the method for modified metal-oxide type Synthesis of Ethyl-p-Hydroxyl-Benzoate with Solid Super Strong Acid as Catalyst according to claim 1, it is characterized in that: in step (1), the mass ratio that feeds intake of described P-hydroxybenzoic acid and modified metal-oxide type solid super-strong acid is 6-10: 1.
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| CN201410523176.5A CN104326915A (en) | 2014-09-30 | 2014-09-30 | Method for synthesizing ethyl p-hydroxybenzoate through catalysis of modified metal oxide type solid super acid |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418415A (en) * | 2015-11-02 | 2016-03-23 | 西安近代化学研究所 | Method for preparing 3,3,3-trifluoro ethyl propionate |
| CN111995842A (en) * | 2020-08-25 | 2020-11-27 | 华北科技学院 | Solid super acid, preparation method thereof and flame-retardant epoxy resin |
| CN113522323A (en) * | 2021-08-20 | 2021-10-22 | 南昌大学 | Eu-P-W composite catalyst and preparation method and application thereof |
| CN115385790B (en) * | 2022-09-08 | 2023-11-24 | 江苏正丹化学工业股份有限公司 | Synthesis method of tetraoctyl pyromellitate |
-
2014
- 2014-09-30 CN CN201410523176.5A patent/CN104326915A/en active Pending
Non-Patent Citations (3)
| Title |
|---|
| LILIAN OSIGLIO ET AL.: "Borated zirconia modified with ammonium metatungstate as catalyst in alcohol acetylation", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》 * |
| 梁久来等: "对羟基苯甲酸乙酯合成新法", 《现代化工》 * |
| 谢小红: "复合氧化物固体催化剂B2O3/WO3-ZrO2的制备及应用", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418415A (en) * | 2015-11-02 | 2016-03-23 | 西安近代化学研究所 | Method for preparing 3,3,3-trifluoro ethyl propionate |
| CN105418415B (en) * | 2015-11-02 | 2017-08-08 | 西安近代化学研究所 | A kind of preparation method of 3,3,3 trifluoroacetic acid ethyl ester |
| CN111995842A (en) * | 2020-08-25 | 2020-11-27 | 华北科技学院 | Solid super acid, preparation method thereof and flame-retardant epoxy resin |
| CN111995842B (en) * | 2020-08-25 | 2023-04-25 | 华北科技学院 | Solid super acid, preparation method thereof and flame-retardant epoxy resin |
| CN113522323A (en) * | 2021-08-20 | 2021-10-22 | 南昌大学 | Eu-P-W composite catalyst and preparation method and application thereof |
| CN113522323B (en) * | 2021-08-20 | 2022-06-24 | 南昌大学 | Eu-P-W composite catalyst and preparation method and application thereof |
| CN115385790B (en) * | 2022-09-08 | 2023-11-24 | 江苏正丹化学工业股份有限公司 | Synthesis method of tetraoctyl pyromellitate |
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Application publication date: 20150204 |