CN101717326A - Method for synthesizing antioxidant 1,3,5-trimethyl-2,4,6-tri(3,5-di-tert-butyl-4-hydroxybenzyl)benzene - Google Patents
Method for synthesizing antioxidant 1,3,5-trimethyl-2,4,6-tri(3,5-di-tert-butyl-4-hydroxybenzyl)benzene Download PDFInfo
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- CN101717326A CN101717326A CN200910220445A CN200910220445A CN101717326A CN 101717326 A CN101717326 A CN 101717326A CN 200910220445 A CN200910220445 A CN 200910220445A CN 200910220445 A CN200910220445 A CN 200910220445A CN 101717326 A CN101717326 A CN 101717326A
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Abstract
The invention discloses a method for preparing antioxidant 1,3,5-trimethyl-2,4,6-tri(3,5-di-tert-butyl-4-hydroxybenzyl)benzene by using solid superacid as catalyst, wherein 1,3,5-trihalo methyl-2,4,6-trimethyl benzene and 2,6-do-tert-butylphenol, as raw materials, are subject to alkylation in inert solvent under the action of solid superacid-type catalyst SO42-/MXOY, so as to prepare target products. The method simplifies operating process, achieves mild reaction conditions, has the characteristics of easy separation of products, good reusability of the catalyst, small environmental pollution and the like, and is suitable for industrial production.
Description
Technical field
The invention belongs to the preparation method of oxidation inhibitor, in particular, relate to a kind of oxidation inhibitor 1,3,5-trimethylammonium-2,4, the synthetic method of 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene.
Background technology
Effect such as synthetic resins and goods thereof are synthetic at it, be heated inevitably in processing and the application process, oxygen, light, heavy metal ion and mechanical shearing and degrading, cause that goods are aging, variable color and mechanical property reduce until losing use value fully, thereby must add processing aid such as oxidation inhibitor in material.
Oxidation inhibitor can delay or stop synthetic materials oxidation or autoxidation process, thereby prolongs the work-ing life of material.Principal item has Hinered phenols, phosphorous acid esters, thioether class and a spot of metallic ion passivation agent, some amine and dithiocarbamate etc. at present.
1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene (oxidation inhibitor-330) is a kind of Hinered phenols antioxidant, is applicable to the antioxygen stabilization of various polymkeric substance and organic materials, particularly cooperates with auxiliary antioxidants such as phosphorous acid ester, monothioester class, benzofuranone, carbon radicals trapping agents to have good synergy; In high temperature process and require the application scenario of high anti-extractibility to give the processing stability of goods excellence and good lasting stability.Be applicable to the manufacture field of the goods such as polyolefin pipe, injection-molded item, electric wire of high temperature process.In addition, because its good colour nontoxic, that do not pollute, can keep plastics can be used for the wrapping material with Food Contact.With traditional oxidation inhibitor ratio, have efficient, low toxicity, characteristics such as pollution-free, thereby these product have great application prospect industrial.
As existing preparation method, in the United States Patent (USP) in early days (US:3026264), having introduced with the vitriol oil is catalyzer 2, and 6-di-t-butyl-4-hydroxy-benzyl alcohol and sym-trimethylbenzene are the method for feedstock production oxidation inhibitor-330, and yield is about 60%.Under the reaction principle:
Since this method in reaction process, use 2,6-di-t-butyl-4-hydroxy-benzyl alcohol be difficult in market, obtain the supply, and with the vitriol oil as catalyzer, greatly limited application.
U.S.'s ethyl corporation has carried out improving (US:4340767) to this reaction process, add subsidiaries such as Paraformaldehyde 96, acetic acid in reaction, by removing the water that generates in the reaction, product is through recrystallization several times, its fusing point can reach 242～244 ℃, and yield can reach about 70%.
Introduced under sulfuric acid catalysis in United States Patent (USP) (US 4754007), with 2,6-di-tert-butyl-4-hydroxyl benzyl ether and sym-trimethylbenzene be raw material, prepare down the method for oxidation inhibitor-330 at low temperature (5 ℃).Composition principle is as follows:
As improvement to this method, in United States Patent (USP) (US:5292669), introduced with methylsulphonic acid as catalyzer, with 2,6-di-tert-butyl-4-hydroxyl benzyl ether and sym-trimethylbenzene reaction, preparation oxidation inhibitor-330, yield is 74%.Such preparation method exists 2, and 6-di-tert-butyl-4-hydroxyl benzyl ether is difficult to supply industrial, and catalyzer methylsulphonic acid defective such as cost an arm and a leg makes it be difficult to use in large-scale production.
Having introduced with 2,6 di t butyl phenol, trioxymethylene and sym-trimethylbenzene in Japanese Patent (JP 56-092235) is the method for raw material one-step synthesis, but according to 2, the 6-DI-tert-butylphenol compounds is calculated, yield only is 42%, and unstable product quality, can't carry out suitability for industrialized production.
Recently, (fine chemistry industry, 2008 such as Chen Yang, 25 (8), be catalyzer p.806-809), with mesitylene and 3 with quaternary ammonium salt pyridines acidic functional ionic liquid, 5-di-t-butyl-4-hydroxyl benzyl methyl ether is a raw material, has synthesized oxidation inhibitor-330, and yield can reach 89.6%.The purpose of improve reaction yield in the hope of reaching, simplifying last handling process.
Summary of the invention
The present invention is intended to overcome the deficiencies in the prior art part and provides a kind of raw material to obtain facility, yield height, reaction safety; environmental protection efficacy is good; operating process is easy, and product is easy to separate steady quality; be suitable for the oxidation inhibitor 1 of large-scale production; 3,5-trimethylammonium-2,4; the synthetic method of 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene.
For achieving the above object, the present invention is achieved in that
Oxidation inhibitor 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) synthetic method of benzene, it is with 1,3,5-trihalogenmethyl-2,4,6-Three methyl Benzene and 2,6 di t butyl phenol are raw material, carry out alkylated reaction in inert solvent, thereby make target product.
As a kind of preferred version, the present invention carries out alkylated reaction under the effect of solid super acid catalyst, thereby makes target product.
As another kind of preferred version, solid super acid catalyst of the present invention is SO
4 2-/ M
XO
Y
Further, M of the present invention
XO
YBe TiO
2, ZrO
2, Fe
2O
3, Al
2O
3, SnO
2, Sb
2O
3In one or more mixtures.
Further, of the present invention 1,3,5-trihalogenmethyl-2,4, the mol ratio of 6-Three methyl Benzene and 2,6 di t butyl phenol is: 1: 3～6.
In addition, temperature of reaction of the present invention can be controlled in 20～150 ℃.
Secondly, the reaction times of the present invention can be controlled in 3～15 hours.
Once more, solid super acid catalyst of the present invention can be 1,3 by percentage to the quality, 5-trihalogenmethyl-2,4,5～30% of 6-Three methyl Benzene.
Inert solvent of the present invention is acetonitrile, ethyl acetate, methylene dichloride, trichloromethane, tetracol phenixin, the mixture of one or more in the chlorobenzene.
The invention solves sulfuric acid and must carry out liquid waste disposal as Catalyst Production oxidation inhibitor-330, technological process is numerous and diverse, and shortcoming such as product performance instability.In the reaction process related intermediate and Preparation of Catalyst simple, be easy to get, because formaldehydeless participation reaction, so avoided the pollution of the use of formaldehyde to environment.Because process choice is good, quality product is controlled easily, and is easy and simple to handle, safe and reliable, is fit to large-scale production.
Embodiment
The invention will be further described below in conjunction with embodiment.Protection scope of the present invention not only is confined to the statement of following content.
The present invention adopts under solid superacid as catalyst, with 1,3, and 5-trihalogenmethyl-2,4,6-Three methyl Benzene (II) and 2,6 di t butyl phenol (III) they are raw material, carry out alkylated reaction and prepare oxidation inhibitor-330 in inert solvent.Reaction principle is as follows:
In the novel method of above-mentioned preparation oxidation inhibitor-330,1,3,5-trihalogenmethyl-2,4,6-Three methyl Benzene (II), the mol ratio of 2,6 di t butyl phenol (III) is: 1: 3～6, be preferably: 1: 3.5～4.5.
The catalyst solid super acids is SO
4 2-/ M
XO
Y, M wherein
XO
YBe meant TiO
2, ZrO
2, Fe
2O
3, Al
2O
3, SnO
2, Sb
2O
3In one or more mixtures.As SO
4 2-/ TiO
2-ZrO
2, SO
4 2-/ TiO
2-Fe
2O
3, SO
4 2-/ ZrO
2-Fe
2O
3, SO
4 2-/ ZrO
2-Al
2O
3Deng, be preferably SO
4 2-/ TiO
2, SO
4 2-/ ZrO
2, SO
4 2-/ TiO
2-ZrO
2, SO
4 2-/ TiO
2-Fe
2O
3Its consumption (mass percent) is 1,3,5-trihalogenmethyl-2,4,5～30%, preferred 10～25% of 6-Three methyl Benzene (II).
Related intermediate 1,3 among the embodiment, 5-trichloromethyl-2,4,6-Three methyl Benzene (Journalof Molecular Catalysis A:Chemical, 2008, Vol.294, p.68-73) and 1,3,5-trisbromomethyl-2,4, the 6-Three methyl Benzene (Synthesis, 1994, p.132) and solid super acid catalyst (Applied Catalysis A; General, 1999,176 (1), p.27; Use chemical industry, 2008,37 (9), p.1039; Industrial Catalysis, 2008,16 (7), p.21) can be synthetic or from market, buy with reference to corresponding literature method.
Embodiment 1
In three mouthfuls of reaction flasks of the 250mL that has mechanical stirrer and prolong, add 1,3,5-trisbromomethyl-2,4,6-Three methyl Benzene (39.9 grams, 0.1 mole), 2,6 di t butyl phenol (72.1 grams, 0.35 mole), super acidic catalyst SO
4 2-/ TiO
2(7 gram) and methylene dichloride (100mL) stir, and in 50 ℃ of following reflux 8 hours, are cooled to room temperature, add entry (50mL), and the separation organic layer is through anhydrous Na
2SO
4After the drying, concentrate and reclaim solvent, obtain the white powder solid, use the sherwood oil recrystallization, get white crystals 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene (oxidation inhibitor-330) 63.7g, productive rate is 82.3%.Fusing point is 242～244 ℃.Product is 99.4% through liquid chromatogram measuring purity.
Embodiment 2
In three mouthfuls of reaction flasks of the 250mL that has mechanical stirrer and prolong, add 1,3,5-trisbromomethyl-2,4,6-Three methyl Benzene (39.9 grams, 0.1 mole), 2,6 di t butyl phenol (72.1 grams, 0.35 mole), super acidic catalyst SO
4 2-/ ZrO
2(5 gram) and ethyl acetate (120mL) stir, and in 80 ℃ of following reflux 6 hours, are cooled to room temperature, add entry (100mL), and the separation organic layer is through anhydrous Na
2SO
4After the drying, concentrate and reclaim solvent, obtain the white powder solid, use the sherwood oil recrystallization, get white crystals (oxidation inhibitor-330) 65.8g, productive rate is 85%.Fusing point is 240～243 ℃.Product is 99.5% through liquid chromatogram measuring purity.
Embodiment 3
In three mouthfuls of reaction flasks of the 250mL that has mechanical stirrer and prolong, add 1,3,5-trisbromomethyl-2,4,6-Three methyl Benzene (39.9 grams, 0.1 mole), 2,6 di t butyl phenol (82.4 grams, 0.4 mole), super acidic catalyst SO
4 2-/ TiO
2-Fe
2O
3(5 gram) and acetonitrile (100mL) stir, and in 85 ℃ of following reflux 8 hours, are cooled to room temperature, add entry (100mL), and the separation organic layer is through anhydrous Na
2SO
4After the drying, concentrate and reclaim solvent, obtain the white powder solid, use the sherwood oil recrystallization, get white crystals (oxidation inhibitor-330) 60.4g, productive rate is 78%.Fusing point is 241～243 ℃.Product is 99.2% through liquid chromatogram measuring purity.
Embodiment 4
In three mouthfuls of reaction flasks of the 250mL that has mechanical stirrer and prolong, add 1,3,5-trisbromomethyl-2,4,6-Three methyl Benzene (39.9 grams, 0.1 mole), 2,6 di t butyl phenol (92.7 grams, 0.45 mole), super acidic catalyst SO
4 2-/ TiO
2-ZrO
2(6 gram) and chlorobenzene (100mL) stir, and in 140 ℃ of following reflux 10 hours, are cooled to room temperature, add entry (60mL), and the separation organic layer is through anhydrous Na
2SO
4After the drying, concentrate and reclaim solvent, obtain the white powder solid, use the sherwood oil recrystallization, get white crystals (oxidation inhibitor-330) 56.9g, productive rate is 73.5%.Fusing point is 240～242 ℃.Product is 99.1% through liquid chromatogram measuring purity.
Embodiment 5
In three mouthfuls of reaction flasks of the 250mL that has mechanical stirrer and prolong, add 1,3,5-trichloromethyl-2,4,6-Three methyl Benzene (26.6 grams, 0.1 mole), 2,6 di t butyl phenol (82.4 grams, 0.4 mole), super acidic catalyst SO
4 2-/ TiO
2(6 gram) and ethyl acetate (100mL) stir, and in 80 ℃ of following reflux 13 hours, are cooled to room temperature, add entry (60mL), and the separation organic layer is through anhydrous Na
2SO
4After the drying, concentrate and reclaim solvent, obtain the white powder solid, use the sherwood oil recrystallization, get white crystals (oxidation inhibitor-330) 54.2g, productive rate is 70.6%.Fusing point is 240～243 ℃.Product is 99.1% through liquid chromatogram measuring purity.
Embodiment 6
In three mouthfuls of reaction flasks of the 250mL that has mechanical stirrer and prolong, add 1,3,5-trichloromethyl-2,4,6-Three methyl Benzene (26.6 grams, 0.1 mole), 2,6 di t butyl phenol (92.7 grams, 0.45 mole), super acidic catalyst SO
4 2-/ TiO
2-ZrO
2(7 gram) and acetonitrile (100mL) stir, and in 80 ℃ of following reflux 16 hours, are cooled to room temperature, add entry (50mL), and the separation organic layer is through anhydrous Na
2SO
4After the drying, concentrate and reclaim solvent, obtain the white powder solid, use the sherwood oil recrystallization, get white crystals (oxidation inhibitor-330) 56g, productive rate is 73%.Fusing point is 241～243 ℃.Product is 98.3% through liquid chromatogram measuring purity.
Be with being appreciated that, more than about specific descriptions of the present invention, only be used to the present invention is described and be not to be subject to the described technical scheme of the embodiment of the invention, those of ordinary skill in the art is to be understood that, still can make amendment or be equal to replacement the present invention, to reach identical technique effect; Use needs as long as satisfy, all within protection scope of the present invention.
Claims (10)
1. oxidation inhibitor 1,3,5-trimethylammonium-2,4, the synthetic method of 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, it is characterized in that, with 1,3,5-trihalogenmethyl-2,4,6-Three methyl Benzene and 2,6 di t butyl phenol are raw material, in inert solvent, carry out alkylated reaction, thereby make target product.
2. oxidation inhibitor 1,3 as claimed in claim 1,5-trimethylammonium-2,4, the synthetic method of 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene is characterized in that: under the effect of solid super acid catalyst, carry out alkylated reaction, thereby make target product.
3. oxidation inhibitor 1,3 as claimed in claim 2,5-trimethylammonium-2,4, the synthetic method of 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, it is characterized in that: described solid super acid catalyst is SO
4 2-/ M
XO
Y
4. oxidation inhibitor 1,3 as claimed in claim 3,5-trimethylammonium-2,4, the synthetic method of 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene is characterized in that: described M
XO
YBe TiO
2, ZrO
2, Fe
2O
3, Al
2O
3, SnO
2, Sb
2O
3In one or more mixtures.
5. as the arbitrary described oxidation inhibitor 1,3 of claim 1～4,5-trimethylammonium-2,4, the synthetic method of 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene is characterized in that: described 1,3,5-trihalogenmethyl-2,4, the mol ratio of 6-Three methyl Benzene and 2,6 di t butyl phenol is: 1: 3～6.
6. oxidation inhibitor 1,3 as claimed in claim 5,5-trimethylammonium-2,4, the synthetic method of 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, it is characterized in that: temperature of reaction is at 20～150 ℃.
7. oxidation inhibitor 1,3 as claimed in claim 6,5-trimethylammonium-2,4, the synthetic method of 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, it is characterized in that: the reaction times was at 3～15 hours.
8. as claim 2,3 or 4 described oxidation inhibitor 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) synthetic method of benzene is characterized in that: by percentage to the quality, described solid super acid catalyst is 1,3,5-trihalogenmethyl-2,4,5～30% of 6-Three methyl Benzene.
9. oxidation inhibitor 1 as claimed in claim 8,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) synthetic method of benzene is characterized in that: described inert solvent is one or more the mixture in acetonitrile, ethyl acetate, methylene dichloride, trichloromethane, tetracol phenixin, the chlorobenzene.
10. oxidation inhibitor 1,3 as claimed in claim 9,5-trimethylammonium-2,4, the synthetic method of 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, it is characterized in that: described inert solvent is acetonitrile, methylene dichloride or chlorobenzene.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102399136A (en) * | 2011-10-18 | 2012-04-04 | 池州万维化工有限公司 | Preparation method for 1,3,5-trimethyl-2,4,6-tri(3,5-di-tert-butyl-4-hydroxybenzyl)benzene as hindered phenol antioxidant |
| CN102503778A (en) * | 2011-10-28 | 2012-06-20 | 淮安嘉诚高新化工股份有限公司 | Synthesis method of antioxidant 330 |
| CN102992963A (en) * | 2012-12-19 | 2013-03-27 | 利安隆（天津）化工有限公司 | Preparation method of hindered phenol antioxidant 330 |
| CN104292141A (en) * | 2014-08-18 | 2015-01-21 | 华南理工大学 | Macromolecular hindered phenol antioxidant containing thioether and carbamate groups and preparation method and application thereof |
| CN104788292A (en) * | 2015-03-19 | 2015-07-22 | 东北石油大学 | Synthesis method for hindered phenolic compound antioxidant 330 |
| CN108341734A (en) * | 2018-03-25 | 2018-07-31 | 王强 | A method of catalysis prepares 2,6- dimethylnaphthalenes |
| CN110734580A (en) * | 2018-07-20 | 2020-01-31 | 中国石油天然气股份有限公司 | compounds containing hindered phenol and pentaerythritol structure, synthesis method thereof and application thereof as antioxidant |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3026264A (en) * | 1960-07-11 | 1962-03-20 | Shell Oil Co | Substituted benzenes |
-
2009
- 2009-12-04 CN CN 200910220445 patent/CN101717326B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3026264A (en) * | 1960-07-11 | 1962-03-20 | Shell Oil Co | Substituted benzenes |
Non-Patent Citations (2)
| Title |
|---|
| SAMAH SIMAAN ET AL.,: "Tris(arylmethyl)Derivatives of 1,3,5-Trimethoxy- and 1,3,5-Triethylbenzene", 《J.O.C.》 * |
| 郑彬等: "固体超强酸SO42-/TiO2催化合成壬基二苯胺", 《化工进展》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102399136A (en) * | 2011-10-18 | 2012-04-04 | 池州万维化工有限公司 | Preparation method for 1,3,5-trimethyl-2,4,6-tri(3,5-di-tert-butyl-4-hydroxybenzyl)benzene as hindered phenol antioxidant |
| CN102399136B (en) * | 2011-10-18 | 2013-12-11 | 池州万维化工有限公司 | Preparation method for 1,3,5-trimethyl-2,4,6-tri(3,5-di-tert-butyl-4-hydroxybenzyl)benzene as hindered phenol antioxidant |
| CN102503778A (en) * | 2011-10-28 | 2012-06-20 | 淮安嘉诚高新化工股份有限公司 | Synthesis method of antioxidant 330 |
| CN102503778B (en) * | 2011-10-28 | 2014-02-12 | 淮安嘉诚高新化工股份有限公司 | Synthesis method of antioxidant 330 |
| CN102992963A (en) * | 2012-12-19 | 2013-03-27 | 利安隆（天津）化工有限公司 | Preparation method of hindered phenol antioxidant 330 |
| CN102992963B (en) * | 2012-12-19 | 2014-10-22 | 天津利安隆新材料股份有限公司 | Preparation method of hindered phenol antioxidant 330 |
| CN104292141A (en) * | 2014-08-18 | 2015-01-21 | 华南理工大学 | Macromolecular hindered phenol antioxidant containing thioether and carbamate groups and preparation method and application thereof |
| CN104292141B (en) * | 2014-08-18 | 2016-03-02 | 华南理工大学 | Macromole hindered phenol antioxygen of Sulfide-containing Hindered and carbamate groups and preparation method thereof and application |
| CN104788292A (en) * | 2015-03-19 | 2015-07-22 | 东北石油大学 | Synthesis method for hindered phenolic compound antioxidant 330 |
| CN104788292B (en) * | 2015-03-19 | 2016-08-24 | 东北石油大学 | A kind of synthetic method of hindered phenol compound antioxidant 330 |
| CN108341734A (en) * | 2018-03-25 | 2018-07-31 | 王强 | A method of catalysis prepares 2,6- dimethylnaphthalenes |
| CN108341734B (en) * | 2018-03-25 | 2021-07-20 | 广东和汇新材料有限公司 | Method for preparing 2, 6-dimethylnaphthalene by catalysis |
| CN110734580A (en) * | 2018-07-20 | 2020-01-31 | 中国石油天然气股份有限公司 | compounds containing hindered phenol and pentaerythritol structure, synthesis method thereof and application thereof as antioxidant |
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