CN102381968A - Method for preparing antioxidant of bisphenol monoacryate - Google Patents
Method for preparing antioxidant of bisphenol monoacryate Download PDFInfo
- Publication number
- CN102381968A CN102381968A CN2011102797611A CN201110279761A CN102381968A CN 102381968 A CN102381968 A CN 102381968A CN 2011102797611 A CN2011102797611 A CN 2011102797611A CN 201110279761 A CN201110279761 A CN 201110279761A CN 102381968 A CN102381968 A CN 102381968A
- Authority
- CN
- China
- Prior art keywords
- methyl
- methylene
- butyl phenol
- oxidation inhibitor
- bis
- 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.)
- Pending
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for preparing antioxidant of bisphenol monoacryate. The method comprises the following steps: 1) dissolving 2,2'-methylene di(4-methyl-6-t-butyl phenol) and an amine catalyst in an organic solvent under the room temperature, and reducing the temperature lower than 10 DEG C; 2) adding an acryloyl chloride solution in a mixture from the step 1), and increasing the reaction temperature to 40-60 DEG C, insulating for 3-10 hours; wherein, the mol ratio of 2,2'-methylene di(4-methyl-6-t-butyl phenol) to amine catalyst is 1:1-2; the mol ratio of 2,2'-methylene di(4-methyl-6-t-butyl phenol) to acryloyl chloride is 1:1-2. The method of the invention has the advantages of simple process and high yield.
Description
Technical field
The present invention relates to a kind of preparation method of bisphenolmonoacryates oxidation inhibitor.
Background technology
Oxidation inhibitor can suppress or delay the compound of polymkeric substance and the degraded of other oxidation operations for some; Its application in coating, plastics etc. very extensively; The commercial oxidation inhibitor of large-scale application has: antioxidant 1010, oxidation inhibitor 168, antioxidant 1076, oxidation inhibitor 242 or the like; The characteristics that some oxidation inhibitor have are to have bigger steric hindrance, all contain phenolic hydroxyl group in the structure simultaneously.
2-(the 2-hydroxyl-3-tertiary butyl-5-methyl-benzyl)-4-methyl-6-tert butyl phenyl acrylate is a kind of bisphenolmonoacryates oxidation inhibitor, and trade name is an oxidation inhibitor 3052, compares with other oxidation inhibitor; It has good antioxidant effect; When adding in the plastic substrate, mobility is very low, therefore; Its better performances, existing compound method is complicated, synthetic effect is relatively poor, productive rate is lower.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of bisphenolmonoacryates oxidation inhibitor.
The technical scheme that the present invention taked is:
A kind of preparation method of bisphenolmonoacryates oxidation inhibitor may further comprise the steps:
1) under the room temperature, with 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol) is dissolved in the organic solvent with amines catalyst, and is cooled to below 10 ℃;
2) acrylate chloride solution is added in the mixture of step 1), and temperature of reaction is increased to 40-60 ℃, insulation 3-10h;
Wherein, 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol) is 1:1-2 with the mol ratio of amines catalyst; 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol) is 1:1-2 with the mol ratio of acrylate chloride.
Described amines catalyst is a kind of in Trimethylamine 99, triethylamine, tripropyl amine, Tributylamine, tri-isobutylamine, triamylamine, tri-isoamylamine, trihexylamine, three heptyl amices, trioctylamine, tri-iso-octylamine, the TNA trinonylamine.
Described amines catalyst is a triethylamine.
Through step 1) and step 2) after, also comprise step 2) the product washing, distillation, recrystallization, the exsiccant purification step that obtain.
2,2 '-methylene-bis (4-methyl-6-tert butyl phenol) is 1:1-1.5 with the mol ratio of amines catalyst.
2,2 '-methylene-bis (4-methyl-6-tert butyl phenol) is 1:1-1.5 with the mol ratio of acrylate chloride.
The invention has the beneficial effects as follows: preparing method's technology of the present invention is simple, productive rate is higher.
Description of drawings
Fig. 1 is the nuclear magnetic spectrum of products therefrom.
Embodiment
A kind of preparation method of bisphenolmonoacryates oxidation inhibitor may further comprise the steps:
1) under the room temperature, with 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol) is dissolved in the organic solvent with amines catalyst, and is cooled to below 10 ℃;
2) acrylate chloride solution is added in the mixture of step 1), and temperature of reaction is increased to 40-60 ℃, insulation 3-10h;
3) with step 2) products therefrom washing, underpressure distillation, recrystallization, drying, product.
Wherein, in the step 1), 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol) is 1:1-2 with the mol ratio of amines catalyst; Preferably, 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol) is 1:1-1.5 with the mol ratio of amines catalyst; 2, the 2 '-methylene-bis (4-methyl-6-tert butyl phenol) and the amount ratio of organic solvent are 1mol:1-1.7L;
Step 2) in, acrylate chloride solution is the benzole soln of acrylate chloride or is the toluene solution of acrylate chloride that the volumetric molar concentration of acrylate chloride is 2-4mol/L;
2,2 '-methylene-bis (4-methyl-6-tert butyl phenol) is 1:1-2 with the mol ratio of acrylate chloride, and is preferred, 2, and 2 '-methylene-bis (4-methyl-6-tert butyl phenol) is 1:1-1.5 with the mol ratio of acrylate chloride.
Do further explanation below in conjunction with specific embodiment:
Embodiment 1
1) under the room temperature, with 2 of 0.3mol, 2 '-methylene-bis (4-methyl-6-tert butyl phenol) is dissolved in the toluene of 300ml with the 0.4mol triethylamine, opens and stirs, and is cooled to below 10 ℃ after the solid dissolving;
The toluene solution (200ml) that 2) will contain the 0.4mol acrylate chloride is added drop-wise in 30-40min in the mixture of step 1), after being added dropwise to complete, temperature of reaction is risen to 40-45 ℃ in 10-15min, insulation reaction 7h;
3) after reaction was accomplished, zero(ppm) water carried out 3 washings, and underpressure distillation, recrystallization, drying obtain title product.
1) under the room temperature, with 2 of 0.3mol, 2 '-methylene-bis (4-methyl-6-tert butyl phenol) is dissolved in the toluene of 400ml with the 0.3mol triethylamine, opens and stirs, and is cooled to below 10 ℃ after the solid dissolving;
The toluene solution (150ml) that 2) will contain the 0.3mol acrylate chloride is added drop-wise in 30-40min in the mixture of step 1), after being added dropwise to complete, temperature of reaction is risen to 50-55 ℃ in 10-15min, insulation reaction 10h;
3) after reaction was accomplished, zero(ppm) water carried out 3 washings, and underpressure distillation, recrystallization, drying obtain title product.
Embodiment 3
1) under the room temperature, with 2 of 0.3mol, 2 '-methylene-bis (4-methyl-6-tert butyl phenol) is dissolved in the toluene of 500ml with the 0.45mol triethylamine, opens and stirs, and is cooled to below 10 ℃ after the solid dissolving;
The toluene solution (100ml) that 2) will contain the 0.4mol acrylate chloride is added drop-wise in 30-40min in the mixture of step 1), after being added dropwise to complete, temperature of reaction is risen to 55-60 ℃ in 10-15min, insulation reaction 3h;
3) after reaction was accomplished, zero(ppm) water carried out 4 washings, and underpressure distillation, recrystallization, drying obtain title product.
The product that embodiment 1 obtains
1The HNMR nuclear magnetic spectrogram is as shown in Figure 1, can find out, has generated title product 2-(the 2-hydroxyl-3-tertiary butyl-5-methyl-benzyl)-4-methyl-6-tert butyl phenyl acrylate really.In addition, productive rate＞80%.
Among the present invention, related reaction equation is shown in (I):
Claims (6)
1. the preparation method of a bisphenolmonoacryates oxidation inhibitor is characterized in that: may further comprise the steps:
1) under the room temperature, with 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol) is dissolved in the organic solvent with amines catalyst, and is cooled to below 10 ℃;
2) acrylate chloride solution is added in the mixture of step 1), and temperature of reaction is increased to 40-60 ℃, insulation 3-10h;
Wherein, 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol) is 1:1-2 with the mol ratio of amines catalyst; 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol) is 1:1-2 with the mol ratio of acrylate chloride.
2. the preparation method of a kind of bisphenolmonoacryates oxidation inhibitor according to claim 1 is characterized in that: described amines catalyst is a kind of in Trimethylamine 99, triethylamine, tripropyl amine, Tributylamine, tri-isobutylamine, triamylamine, tri-isoamylamine, trihexylamine, three heptyl amices, trioctylamine, tri-iso-octylamine, the TNA trinonylamine.
3. the preparation method of a kind of bisphenolmonoacryates oxidation inhibitor according to claim 1 is characterized in that: described amines catalyst is a triethylamine.
4. the preparation method of a kind of bisphenolmonoacryates oxidation inhibitor according to claim 1 is characterized in that: through step 1) and step 2) after, also comprise step 2) the product washing, distillation, recrystallization, the exsiccant purification step that obtain.
5. the preparation method of a kind of bisphenolmonoacryates oxidation inhibitor according to claim 1 is characterized in that: 2, and 2 '-methylene-bis (4-methyl-6-tert butyl phenol) is 1:1-1.5 with the mol ratio of amines catalyst.
6. the preparation method of a kind of bisphenolmonoacryates oxidation inhibitor according to claim 1 is characterized in that: 2, and 2 '-methylene-bis (4-methyl-6-tert butyl phenol) is 1:1-1.5 with the mol ratio of acrylate chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102797611A CN102381968A (en) | 2011-09-20 | 2011-09-20 | Method for preparing antioxidant of bisphenol monoacryate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102797611A CN102381968A (en) | 2011-09-20 | 2011-09-20 | Method for preparing antioxidant of bisphenol monoacryate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102381968A true CN102381968A (en) | 2012-03-21 |
Family
ID=45821864
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011102797611A Pending CN102381968A (en) | 2011-09-20 | 2011-09-20 | Method for preparing antioxidant of bisphenol monoacryate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102381968A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012141A (en) * | 2012-12-17 | 2013-04-03 | 上海应用技术学院 | (E)-3-hydroxy-5-(hydroxystyryl)-2-phenyl chloroacetate compound and preparation method thereof |
| CN103012142A (en) * | 2012-12-17 | 2013-04-03 | 上海应用技术学院 | (E)-4-(3,5-dihydroxystyryl)-2-phenyl chloroacetate compound and preparation method thereof |
| CN108409556A (en) * | 2018-03-30 | 2018-08-17 | 吉林化工学院 | A kind of preparation method of one pot process bisphenol monoester kind antioxidant |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4562281A (en) * | 1983-12-14 | 1985-12-31 | Sumitomo Chemical Company, Limited | Production of bisphenol derivatives |
| EP0500323A2 (en) * | 1991-02-18 | 1992-08-26 | Sumitomo Chemical Company, Limited | Production of bisphenol monoester |
| CN101693662A (en) * | 2009-10-14 | 2010-04-14 | 山西万化科技有限公司 | Preparation method of heat-resisting stabilizing agent of bisphenolmonoacryates |
| CN101792390A (en) * | 2010-03-12 | 2010-08-04 | 江苏工业学院 | Preparation method of bisphenol monocarboxylic ester compound antioxidant |
-
2011
- 2011-09-20 CN CN2011102797611A patent/CN102381968A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4562281A (en) * | 1983-12-14 | 1985-12-31 | Sumitomo Chemical Company, Limited | Production of bisphenol derivatives |
| EP0500323A2 (en) * | 1991-02-18 | 1992-08-26 | Sumitomo Chemical Company, Limited | Production of bisphenol monoester |
| CN101693662A (en) * | 2009-10-14 | 2010-04-14 | 山西万化科技有限公司 | Preparation method of heat-resisting stabilizing agent of bisphenolmonoacryates |
| CN101792390A (en) * | 2010-03-12 | 2010-08-04 | 江苏工业学院 | Preparation method of bisphenol monocarboxylic ester compound antioxidant |
Non-Patent Citations (1)
| Title |
|---|
| 杜飞等: "2-(2-羟基-5-甲基-3-叔丁基苯甲基)-4-甲基-6-叔丁基苯基乙酸酯的合成", 《精细石油化工》, vol. 28, no. 3, 18 May 2011 (2011-05-18), pages 23 - 27 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012141A (en) * | 2012-12-17 | 2013-04-03 | 上海应用技术学院 | (E)-3-hydroxy-5-(hydroxystyryl)-2-phenyl chloroacetate compound and preparation method thereof |
| CN103012142A (en) * | 2012-12-17 | 2013-04-03 | 上海应用技术学院 | (E)-4-(3,5-dihydroxystyryl)-2-phenyl chloroacetate compound and preparation method thereof |
| CN108409556A (en) * | 2018-03-30 | 2018-08-17 | 吉林化工学院 | A kind of preparation method of one pot process bisphenol monoester kind antioxidant |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108395382B (en) | Method for synthesizing perfluoroisobutyronitrile | |
| CN103694469B (en) | A kind of covalent organic frame material of thioether functionalization and synthetic method thereof | |
| CN101613341B (en) | Synthetic method of key intermediate of rosuvastatin calcium side chain | |
| CN102381968A (en) | Method for preparing antioxidant of bisphenol monoacryate | |
| CN108329194B (en) | Method for preparing isopulegol from citronellal and recovery method of catalyst of isopulegol | |
| CN107266451B (en) | Preparation method of rebuximab intermediate | |
| CN103589420B (en) | Green organic electroluminescent material and preparation method thereof | |
| CN101973932B (en) | Preparation method of bisacodyl | |
| CN104744305A (en) | Synthesis method of 2,4-dichloro-3-cyan-5-fluorobenzoic acid | |
| CN111423891A (en) | Synthesis method of 4- (trans-3-pentene) -4' -alkylcyclohexyl biphenyl liquid crystal compound | |
| EP3309142A1 (en) | Method for preparing citalopram glycol intermediate | |
| CN102336656B (en) | High-selectivity synthesis method of benzoyl formic acid | |
| CN104496909A (en) | Dicaryon benzimidazole ionic salt as well as preparation method and application thereof | |
| CN102120726B (en) | New preparation method of (2E)-2-cyano-3-(3,4-dihydroxy-5-nitrobenzene)-N,N-diethyl-2-acrylamide | |
| CN112321428A (en) | Synthesis method of R- (+) -2- (4-hydroxyphenoxy) ethyl propionate | |
| CN109810037B (en) | Method for preparing 2-thiobenzenesulfonylmethyl-3-phenyl methyl acrylate compound by tin catalysis | |
| CN107338043A (en) | A kind of new racemic chirality organic boron nitrogen fluorescent chemicals and preparation method thereof | |
| CN103614134B (en) | Organic electroluminescent material and preparation method thereof | |
| CN101987825B (en) | Method for preparing 2-amino-3-methyl-4-methoxy acetophenone | |
| CN110015944A (en) | A kind of synthetic method of highly selective luliconazole intermediate | |
| CN108084024A (en) | Loxoprofen sodium intermediate 2-（4- 2-bromomethylphenyls）Major impurity and its preparation and separation method in propionic acid Lipase absobed | |
| Camps et al. | Reduction of alkyl 2, 4-alkadienoates with sodium dithionite under phase transfer conditions | |
| CN113801009B (en) | Method for catalyzing gallic acid methylation by using ionic liquid | |
| WO2000064855A1 (en) | Epimerization reaction for the production of r-fluoxetine | |
| CN108822060B (en) | 3-aryl substituted oxetane and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20120321 |