CN112279751B - Method for synthesizing bisphenol compound by using solid acid as catalyst - Google Patents
Method for synthesizing bisphenol compound by using solid acid as catalyst Download PDFInfo
- Publication number
- CN112279751B CN112279751B CN202011178332.0A CN202011178332A CN112279751B CN 112279751 B CN112279751 B CN 112279751B CN 202011178332 A CN202011178332 A CN 202011178332A CN 112279751 B CN112279751 B CN 112279751B
- Authority
- CN
- China
- Prior art keywords
- cation exchange
- exchange resin
- solid acid
- compound
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for synthesizing a bisphenol compound by using solid acid catalysis, which comprises the following steps: under the action of a solid acid catalyst, performing condensation reaction on ketone and phenol to prepare a bisphenol compound, wherein the molar ratio of the ketone to the phenol is 4-8. The solid acid catalyst provided by the invention can be effectively used for synthesizing bisphenol compounds, such as bis-OPP-A, bisphenol A and the like, and has the advantages of stable process, mild reaction conditions, simple catalyst preparation process, easiness in separation of reaction liquid from the catalyst, high selectivity of target substances and capability of effectively solving the defects in the prior art.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a method for synthesizing a bisphenol compound by using solid acid catalysis.
Background
2, 2-bis (3-phenyl-4-hydroxyphenyl) propane (called bis OPP-A for short) has a benzene ring substituent, is a novel high polymer monomer, belongs to one of bisphenol compounds, and is a monomer for synthesizing special polycarbonate and special epoxy resin. The special polycarbonate has high mechanical property and stability, is widely applied in the fields of automobiles and aerospace, has high mechanical strength, good electrical insulation property and excellent heat resistance, and is widely applied to the fields of adhesives, electronic instruments, aerospace, aviation and the like.
At present, the research reports on the synthesis of the bis-OPP-A at home and abroad are relatively less, most of the studies are carried out by using hydrochloric acid, concentrated sulfuric acid and p-toluenesulfonic acid based on a homogeneous catalysis system, the post-treatment is more troublesome, the amount of generated waste water is large, and the catalyst cannot be recycled; meanwhile, the use of a large amount of strong acid can seriously corrode equipment, and the economic benefit is poor.
The foreign patent WO2016/009359A1 discloses a method for synthesizing bis-OPP-a by using mercaptopropionic acid as a cocatalyst and concentrated sulfuric acid, hydrochloric acid, IER (ion exchange resin) and DBSA (dodecylbenzene sulfonic acid) as main catalysts respectively under the conditions of o-phenylphenol and acetone (molar ratio of 3.
Disclosure of Invention
The invention aims to provide a method for synthesizing a bisphenol compound by using solid acid catalysis, which solves the problem of the prior art based on a homogeneous catalysis process.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a method for synthesizing bisphenol compounds by using solid acid catalysis comprises the following steps: under the action of a solid acid catalyst, carrying out condensation reaction on ketone and phenol to prepare a bisphenol compound, wherein the molar ratio of the ketone to the phenol is 4-8, the solid acid catalyst is macroporous cation exchange resin modified by a mercapto compound, the molar ratio of the macroporous cation exchange resin to the ketone is 0.5-1.5.
Further, the preparation method of the sulfhydryl compound modified macroporous cation exchange resin comprises the following steps:
(1) Loading a calculated amount of sulfhydryl compound on macroporous cation exchange resin by adopting an ion exchange method, specifically, putting the calculated amount of cation exchange resin into a container, adding deionized water until the resin is completely suspended in the water under the condition of stirring, then dropwise adding a sulfhydryl compound aqueous solution into the cation exchange resin while stirring, continuously stirring for 1-2 hours after the dropwise adding is finished, removing an upper-layer aqueous solution, and washing the resin to be neutral;
(2) Drying the modified cation exchange resin in a vacuum drying oven at 60-70 ℃ for 24-48h to obtain the bisphenol compound.
Further, the sulfhydryl compound is any one or more of 2, 2-dimethyl thiazolidine, 2- (2-pyridyl) ethanethiol and cysteamine hydrochloride.
Further, the bisphenol compound is OPP-A, the ketone is acetone, and the phenol is o-phenylphenol;
or the bisphenol compound is bisphenol A, the ketone is acetone, and the phenol is phenol.
Compared with the prior art, the invention has the beneficial technical effects that: the solid acid catalyst provided by the invention can be effectively used for synthesizing bisphenol compounds, such as bis-OPP-A, bisphenol A and the like, and has the advantages of stable process, mild reaction conditions, simple catalyst preparation process, easiness in separation of reaction liquid from the catalyst, high selectivity of target substances and capability of effectively solving the defects in the prior art. In addition, the catalyst is easy to recycle, and the production cost can be obviously reduced.
Detailed Description
The technical solution and the effect of the present invention are further illustrated by the following synthesis example of OPP-A, but the scope of the present invention is not limited to the contents listed in the examples.
Example 1
Weighing 24g of cation exchange resin a (the dry-wet ratio of the resin a is 44.5%), washing the cation exchange resin a with deionized water for a plurality of times in an exchange column until the washing liquid is neutral, putting the cation exchange resin in a beaker, adding a small amount of deionized water to ensure that the resin can be suspended in the liquid, slowly dripping 1.412g of 2, 2-dimethyl thiazolidine in the beaker under the stirring condition, reacting at room temperature for 1 hour, filtering the solution after the reaction is finished, washing the resin in the ion exchange column to be neutral, and drying the resin in a vacuum drying box for 24 hours.
Example 2
Weighing 28g of cation exchange resin b (the dry-wet ratio of the resin b is 42.87%), washing the cation exchange resin b in an exchange column for several times by deionized water until the washing liquid is neutral, putting the cation exchange resin in a beaker, adding a small amount of deionized water, slowly dropwise adding 1.507g of cysteamine hydrochloride solution in the beaker under the stirring condition, reacting at room temperature for 2 hours, filtering the solution after the reaction is finished, washing the resin in the ion exchange column to be neutral, and drying the resin in a vacuum drying oven for 36 hours.
Example 3
Weighing 25g of cation exchange resin c (the dry-to-wet ratio of the resin c is 43.93%), washing the cation exchange resin c in an exchange column for several times by deionized water until the washing liquid is neutral, putting the cation exchange resin in a beaker, adding a small amount of deionized water, slowly dripping 1.942g of 2- (2-pyridyl) ethanethiol into the beaker under the stirring condition, controlling the reaction temperature to be room temperature, controlling the reaction time to be 1.5 hours, filtering the solution after the reaction is finished, and drying the solution in a vacuum drying oven for 48 hours.
Example 4
Weighing 17.7g of cation exchange resin d (the dry-wet ratio of the resin d is 48 percent), washing the cation exchange resin d with deionized water in an exchange column for a plurality of times until the washing liquid is neutral, putting the cation exchange resin in a beaker, adding a small amount of deionized water, slowly dripping 0.9449g of 2- (2-pyridyl) ethanethiol in the beaker under the stirring condition, reacting at room temperature for 1.5 hours, filtering the solution after the reaction is finished, and drying the solution in a vacuum drying oven for 36 hours.
Example 5
Weighing 12.5g of cation exchange resin d (the dry-wet ratio of the resin d is 48%), washing the cation exchange resin d with deionized water in an exchange column for a plurality of times until the washing liquid is neutral, putting the cation exchange resin into a beaker, adding a small amount of deionized water, slowly dripping 1.167g of 2- (2-pyridyl) ethanethiol into the beaker under the stirring condition, controlling the reaction temperature to be room temperature and the reaction time to be 2 hours, filtering the solution after the reaction is finished, and drying the solution in a vacuum drying oven for 48 hours.
Example 6
Weighing 16.7g of cation exchange resin d (the dry-wet ratio of the resin d is 43.37 percent), washing the cation exchange resin d with deionized water in an exchange column for a plurality of times until the washing liquid is neutral, putting the cation exchange resin into a beaker, adding a small amount of deionized water, slowly dropwise adding 2.0748g of 2- (2-pyridyl) ethanethiol into the beaker under the stirring condition, wherein the reaction temperature is room temperature, the reaction time is 1 hour, filtering the solution after the reaction is finished, and drying the solution in a vacuum drying oven for 24 hours.
Example 7
Weighing 40.2g of cation exchange resin d (the dry-wet ratio of the resin d is 48%), washing the cation exchange resin d with deionized water in an exchange column for a plurality of times until the washing liquid is neutral, putting the cation exchange resin in a beaker, adding a small amount of deionized water, slowly dripping 3.12g of 2- (2-pyridyl) ethanethiol in the beaker under the stirring condition, reacting at room temperature for 1 hour, filtering the solution after the reaction is finished, and drying the solution in a vacuum drying oven for 24 hours.
Example 8
Weighing 32g of cation exchange resin d (the dry-wet ratio of the resin d is 48 percent), washing the cation exchange resin d with deionized water in an exchange column for a plurality of times until the washing liquid is neutral, putting the cation exchange resin in a beaker, adding a small amount of deionized water, slowly dripping 3.36g of 2- (2-pyridyl) ethanethiol in the beaker under the stirring condition, reacting at room temperature for 1.5 hours, filtering off the solution after the reaction is finished, and drying the solution in a vacuum drying oven for 24 hours.
Comparative example 1
Weighing 34g of gel type cation exchange resin e (the dry-wet ratio of the resin e is 45%), washing the gel type cation exchange resin e with deionized water in an exchange column for a plurality of times until the washing liquid is neutral, putting the gel type cation exchange resin in a beaker, adding a small amount of deionized water, slowly dripping 3.36g of 2- (2-pyridyl) ethanethiol into the beaker under the stirring condition, reacting at room temperature for 2 hours, filtering the solution after the reaction is finished, and drying the solution in a vacuum drying oven for 24 hours.
Comparative example 2
Weighing 44.9g of gel type cation exchange resin f (the dry-wet ratio of the resin f is 43 percent), washing the gel type cation exchange resin f with deionized water for a plurality of times in an exchange column until the washing liquid is neutral, putting the gel type cation exchange resin into a beaker, adding a small amount of deionized water, slowly dripping 3.12g of 2- (2-pyridyl) ethanethiol into the beaker under the stirring condition, controlling the reaction temperature to be room temperature and the reaction time to be 2 hours, filtering off the solution after the reaction is finished, and drying the solution in a vacuum drying oven for 48 hours.
Example 9
30g of o-phenylphenol was added to a four-necked flask equipped with a stirrer and a thermometer, 10g of the modified cation exchange resin prepared in example 1 was weighed, heated, mixed and stirred until the reactants were melted, the reaction temperature was controlled at 60 ℃, 2.559g of an accurately weighed acetone solution was slowly dropped into the reaction vessel dropwise (about 30 minutes) using a constant pressure dropping funnel, and the reaction temperature was raised to 80 ℃ after the completion of the dropping of acetone. After 12h of reaction, the yield was 38% calculated as acetone.
Example 10
30g of o-phenylphenol was added to a four-necked flask equipped with a stirrer and a thermometer, 10g of the modified cation exchange resin prepared in example 2 was weighed, heated, mixed and stirred until the reactants were melted, the reaction temperature was controlled at 60 ℃, 2.559g of an accurately weighed acetone solution was slowly dropped into the reaction vessel dropwise (about 15 minutes) using a constant pressure dropping funnel, and the reaction temperature was raised to 80 ℃ after the completion of the dropping of acetone. After 24h of reaction, the yield was 41% calculated as acetone.
Example 11
30g of o-phenylphenol was added to a four-necked flask equipped with a stirrer and a thermometer, 10g of the modified cation exchange resin prepared in example 3 was weighed, heated, mixed and stirred until the reactants were melted, the reaction temperature was controlled at 60 ℃, 2.559g of an accurately weighed acetone solution was slowly dropped into the reaction vessel dropwise (about 15 minutes) using a constant pressure dropping funnel, and the reaction temperature was raised to 80 ℃ after the completion of the dropping of acetone. After 24h of reaction, the yield was 48% calculated as acetone.
Example 12
7.7g of the catalyst prepared in example 4 and 15g of o-phenylphenol were charged in a four-necked flask equipped with a stirrer and a thermometer, heated, mixed and stirred until the reactants melted, the reaction temperature was controlled at 60 ℃ and 1.28g of an accurately weighed acetone solution (about 10 minutes) was slowly dropped into the reaction vessel by a constant pressure dropping funnel, and the reaction temperature was raised to 90 ℃ after the completion of the dropping of the acetone. After 24h of reaction, the yield was 43% calculated as acetone.
Example 13
4.4g of the catalyst prepared in example 5 and 15g of o-phenylphenol were charged into a four-necked flask equipped with a stirrer and a thermometer, and after heating, mixing and stirring were carried out until the reactants melted, the reaction temperature was controlled at 60 ℃, 1.28g of an accurately weighed acetone solution was slowly dropped into the reaction vessel by means of a constant-pressure dropping funnel (for about 10 minutes), and the reaction temperature was raised to 90 ℃ after the completion of the dropping of acetone. After 8h of reaction, the yield was 33% calculated as acetone.
Example 14
6.6g of the catalyst prepared in example 6 and 30g of o-phenylphenol were charged into a four-necked flask equipped with a stirrer and a thermometer, and after the reactants were heated, mixed and stirred until they were melted, 2.559g of an accurately weighed acetone solution (about 15 minutes) was slowly added dropwise to the reaction vessel using a constant-pressure dropping funnel while controlling the reaction temperature at 60 ℃ and the reaction temperature was raised to 90 ℃ after the addition of acetone. After 24h of reaction, the yield was 32% calculated as acetone.
Example 15
13.2g of the catalyst prepared in example 7 and 60g of o-phenylphenol were charged into a four-necked flask equipped with a stirrer and a thermometer, heated, mixed and stirred until the reactants melted, the reaction temperature was controlled at 60 ℃, 2.559g of an accurately weighed acetone solution (15 minutes) was slowly dropped into the reaction vessel by a constant pressure dropping funnel, and the reaction temperature was raised to 90 ℃ after the completion of the dropping of the acetone. After 27h of reaction, the yield was 62% calculated as acetone.
Example 16
15.4g of the catalyst prepared in example 8 and 30g of o-phenylphenol were charged into a four-necked flask equipped with a stirrer and a thermometer, heated, mixed and stirred until the reactants melted, the reaction temperature was controlled at 60 ℃, 2.559g of an accurately weighed acetone solution (15 minutes) was slowly dropped into the reaction vessel by a constant pressure dropping funnel, and the reaction temperature was raised to 90 ℃ after the completion of the dropping of the acetone. After 24h of reaction, the yield was 43% calculated as acetone.
Comparative example 3
15.4g of the catalyst prepared in comparative example 1 and 30g of o-phenylphenol were charged into a four-necked flask equipped with a stirrer and a thermometer, and after heating, mixing and stirring were carried out until the reactants melted, the reaction temperature was controlled at 60 ℃, 2.559g of an accurately weighed acetone solution was slowly dropped into the reaction vessel (for 15 minutes) using a constant-pressure dropping funnel, and the reaction temperature was raised to 90 ℃ after the completion of the acetone dropping. After 24h of reaction, the yield was 5% calculated as acetone.
Comparative example 4
19.2g of the catalyst prepared in comparative example 2 and 60g of o-phenylphenol were charged into a four-necked flask equipped with a stirrer and a thermometer, and after heating, mixing and stirring were carried out until the reactants melted, the reaction temperature was controlled at 60 ℃, 2.559g of an accurately weighed acetone solution (for 15 minutes) was slowly dropped into the reaction vessel through a constant-pressure dropping funnel, and the reaction temperature was raised to 90 ℃ after the completion of the acetone dropping. After 24h of reaction, the yield was 8% calculated as acetone.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and their concepts should be equivalent or changed within the technical scope of the present invention.
The present invention is not limited to the above embodiments, and those skilled in the art can implement the present invention in other embodiments according to the disclosure of the present invention, or make simple changes or modifications on the design structure and idea of the present invention, and fall into the protection scope of the present invention. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
Claims (2)
1. A method for synthesizing bisphenol compounds by using solid acid catalysis is characterized in that: the method comprises the following steps: under the action of a solid acid catalyst, carrying out condensation reaction on ketone and phenol to prepare a bisphenol compound, wherein the molar ratio of the ketone to the phenol is 4-8, the solid acid catalyst is macroporous cation exchange resin modified by a mercapto compound, the molar ratio of the macroporous cation exchange resin to the ketone is 0.5-1.5;
the sulfhydryl compound is any one or more of 2, 2-dimethyl thiazolidine, 2- (2-pyridyl) ethanethiol and cysteamine hydrochloride;
the bisphenol compound is OPP-A, the ketone is acetone, and the phenol is o-phenylphenol.
2. The method for the synthesis of bisphenol compounds catalyzed by solid acid according to claim 1, wherein: the preparation method of the sulfhydryl compound modified macroporous cation exchange resin comprises the following steps:
(1) Loading a calculated amount of sulfhydryl compound on macroporous cation exchange resin by adopting an ion exchange method, specifically, putting the calculated amount of cation exchange resin into a container, adding deionized water until the resin is completely suspended in water under the stirring condition, then dropwise adding a sulfhydryl compound aqueous solution into the cation exchange resin while stirring, continuously stirring for 1-2 hours after dropwise adding, removing an upper-layer aqueous solution, and washing the resin to be neutral;
(2) Drying the modified cation exchange resin in a vacuum drying oven at 60-70 ℃ for 24-48h to obtain the bisphenol compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011178332.0A CN112279751B (en) | 2020-10-29 | 2020-10-29 | Method for synthesizing bisphenol compound by using solid acid as catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011178332.0A CN112279751B (en) | 2020-10-29 | 2020-10-29 | Method for synthesizing bisphenol compound by using solid acid as catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112279751A CN112279751A (en) | 2021-01-29 |
| CN112279751B true CN112279751B (en) | 2022-11-01 |
Family
ID=74372742
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011178332.0A Active CN112279751B (en) | 2020-10-29 | 2020-10-29 | Method for synthesizing bisphenol compound by using solid acid as catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112279751B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113333026A (en) * | 2021-06-08 | 2021-09-03 | 中石化南京化工研究院有限公司 | Solid acid catalyst for synthesizing bis-OPP-A and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101003466A (en) * | 2007-01-19 | 2007-07-25 | 哈尔滨工程大学 | Method for synthesizing bisphenol fluorine by catalysis of highly acidic cation exchange resin |
| CN103509501A (en) * | 2012-06-28 | 2014-01-15 | 施敏打硬株式会社 | Solidification compound and solidification catalyst |
| CN108570019A (en) * | 2018-05-31 | 2018-09-25 | 大连理工大学 | A kind of novel acid ionic liquid and its catalytic applications |
| CN111559959A (en) * | 2020-05-23 | 2020-08-21 | 盐城师范学院 | Synthetic method of p-trifluoromethylphenol |
-
2020
- 2020-10-29 CN CN202011178332.0A patent/CN112279751B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101003466A (en) * | 2007-01-19 | 2007-07-25 | 哈尔滨工程大学 | Method for synthesizing bisphenol fluorine by catalysis of highly acidic cation exchange resin |
| CN103509501A (en) * | 2012-06-28 | 2014-01-15 | 施敏打硬株式会社 | Solidification compound and solidification catalyst |
| CN108570019A (en) * | 2018-05-31 | 2018-09-25 | 大连理工大学 | A kind of novel acid ionic liquid and its catalytic applications |
| CN111559959A (en) * | 2020-05-23 | 2020-08-21 | 盐城师范学院 | Synthetic method of p-trifluoromethylphenol |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112279751A (en) | 2021-01-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5302774A (en) | Process for the production of bisphenols | |
| US8575281B2 (en) | Sulfonic acid group-containing carbonaceous material | |
| US8575374B1 (en) | Ionic liquids processing of biomass to reducing sugars and other dehydration products | |
| EP0324080B1 (en) | A method for the purification of ion exchange resins used in the production of bisphenol a | |
| CN108689838B (en) | Method for preparing formic ether by catalyzing esterification of formic acid and olefin through swellable acidic polyion liquid | |
| CN112279751B (en) | Method for synthesizing bisphenol compound by using solid acid as catalyst | |
| CN103570504A (en) | Method of producing methylphenol by gas-phase alkylation of phenol and methanol | |
| JPWO2008123530A1 (en) | Method for producing solid acid catalyst comprising sulfonic acid group-containing carbonaceous material and use thereof | |
| CN103570505A (en) | Method of producing methylphenol by using molecular sieve as catalyst | |
| CN101786017A (en) | Preparation method of solid-acid catalyst | |
| Wang et al. | ZnCl2-modified ion exchange resin as an efficient catalyst for the bisphenol-A production | |
| CN111032607A (en) | Aromatic alcohol sulfonate-containing bisphenol composition and method for producing same, polycarbonate resin and method for producing same, and method for producing bisphenol | |
| DE3727641A1 (en) | ION EXCHANGERS MODIFIED WITH THIAZOLINES | |
| CN113248441A (en) | Dual-functional ionic liquid, preparation method thereof and application thereof in catalytic synthesis of bisphenol compound | |
| US4528395A (en) | Process for esterifying 3,5-di-tert-butyl-4-hydroxybenzoic acid | |
| CN101003466A (en) | Method for synthesizing bisphenol fluorine by catalysis of highly acidic cation exchange resin | |
| CN102850303B (en) | New application and using method of mesoporous solid acid catalyst | |
| CN108218699A (en) | The method that presence of acidic ionic liquid catalyst synthesizes the positive hexadecyl ester of 3,5- di-tert-butyl-4-hydroxybenzoic acids | |
| CN107698429B (en) | A kind of method of functionalized ion liquid catalytic synthesis of bisphenol fluorene | |
| CN113333026A (en) | Solid acid catalyst for synthesizing bis-OPP-A and preparation method and application thereof | |
| CN114920648B (en) | Synthesis method and catalyst of 3- (3-oxo-2-amyl) cyclopentyl dimethyl malonate | |
| US2522940A (en) | Process for the production of phenolphthalein | |
| CN107188804B (en) | Method for catalytically synthesizing methyl oleate by using composite phosphotungstate | |
| EP0249102A2 (en) | Ion exchange resin modified with mercaptoamines | |
| CN1986509A (en) | Bisphenol fluorene synthesizing process catalyzed with solid supported heteropolyacid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |