CN100572350C - Oxidation inhibitor 2, the preparation method of 2 '-methylene-bis (4-methyl-6-tert butyl phenol) - Google Patents
Oxidation inhibitor 2, the preparation method of 2 '-methylene-bis (4-methyl-6-tert butyl phenol) Download PDFInfo
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- CN100572350C CN100572350C CNB200710059665XA CN200710059665A CN100572350C CN 100572350 C CN100572350 C CN 100572350C CN B200710059665X A CNB200710059665X A CN B200710059665XA CN 200710059665 A CN200710059665 A CN 200710059665A CN 100572350 C CN100572350 C CN 100572350C
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Abstract
The present invention proposes a kind of oxidation inhibitor 2, the preparation method of 2 '-methylene-bis (4-methyl-6-tert butyl phenol).With the 2-tertiary butyl-4-methylphenol, Paraformaldehyde 96, solid super-strong acid SO
4 2-/ TiO
2After catalyzer, normal heptane and tensio-active agent Span-80 mix in reactor, stir and be warming up to 70～86 ℃, reaction 4～8h, heat filtering goes out catalyst S O
4 2-/ TiO
2, filtrate is cooled to room temperature, the product antioxidant 2246 is separated out, and filters to obtain antioxidant 2246.Material proportion is: the mass ratio of Paraformaldehyde 96 and the 2-tertiary butyl-4-methylphenol is 0.1～0.4: 1; SO
4 2-/ TiO
2With the mass ratio of the 2-tertiary butyl-4-methylphenol be 0.1～0.5: 1; The mass ratio of normal heptane and the 2-tertiary butyl-4-methylphenol is 2.4～4: 1; The mass ratio of Span-80 and the 2-tertiary butyl-4-methylphenol is 0.015～0.03: 1.Catalyzer of the present invention is more cheap, and catalyzer is easy to separate, excellent catalytic effect, and the three wastes are less.
Description
Technical field
The invention belongs to the preparation method who hinders the phenolic antioxidant compounds, proposed especially a kind of oxidation inhibitor 2,2 '-preparation method of methylene-bis (4-methyl-6-tert butyl phenol) (industrial abbreviation antioxidant 2246).
Background technology
Antioxidant 2246 is one of important oxidation inhibitor kind, is being widely used aspect the antioxygen of polymkeric substance.
The preparation method of antioxidant 2246 has multiple, as (1) methylal method.In the presence of an acidic catalyst, the 2-tertiary butyl-4-methylphenol and methylal reaction can prepare antioxidant 2246, and methylal not only is a bridging agent but also be solvent, and the methylal consumption is more.An acidic catalyst that this method is used mostly is liquid catalysts such as sulfuric acid, and therefore, it is very difficult to remove catalyzer in the resultant, has a large amount of industrial waste acids simultaneously and produces contaminate environment.Methylal is more expensive.(2) formaldehyde method.At 75～90 ℃ and have under an acidic catalyst existence condition, the 2-tertiary butyl-4-methylphenol and formaldehyde are carried out the bridging reaction in the milk sap that contains tensio-active agent and organic solvent, obtain antioxidant 2246.Owing to use formalin, produced the waste water that contains tensio-active agent and organic solvent in a large number in the reaction process, the utilization ratio of formaldehyde is not high.(3) Paraformaldehyde 96 method.Use aliphatics organic solvents such as normal heptane, octane-iso, octane, Paraformaldehyde 96 is a bridging agent, and solid acid is a catalyzer, adds tensio-active agent, in reaction more than 60 ℃.React the after-filtration that finishes and remove catalyzer, cooling filtrate promptly obtains purer antioxidant 2246.The catalyzer that uses mainly contains acidic ion exchange resin etc.This method is used solid polyformaldehyde, reacts in organic solvent, and wastewater discharge seldom.But acidic ion exchange resin catalyst is more expensive.
Take all factors into consideration the various synthetic methods of antioxidant 2246, can see in the formaldehyde method with an organic solvent, tensio-active agent and water, severe reaction conditions has a large amount of waste water that contains organic solvent and tensio-active agent to produce after reaction finishes, the aftertreatment difficulty, contaminate environment.In the methylal method, methylal is more expensive, and the high purity methylal is difficult to obtain.Paraformaldehyde 96 is as bridging agent, catalyzed reaction in organic solvent, but acidic ion exchange resin catalyst is more expensive.
Summary of the invention
The present invention mainly improves the synthesis technique of antioxidant 2246.Adopt solid super-strong acid SO cheap and that be easy to obtain
4 2-/ TiO
2As catalyzer, in organic solvent,, generate antioxidant 2246 with the 2-tertiary butyl-4-methylphenol and polyformaldehyde reaction, catalyzer is easy to separate, excellent catalytic effect, the three wastes are less.
The present invention is with solid super-strong acid SO
4 2-/ TiO
2As catalyzer, in the organic solvent normal heptane,, generate antioxidant 2246 with the 2-tertiary butyl-4-methylphenol and polyformaldehyde reaction.Reaction equation is as follows:
The elementary operation process is:
With the 2-tertiary butyl-4-methylphenol, Paraformaldehyde 96, solid super-strong acid SO
4 2-/ TiO
2After catalyzer, normal heptane and tensio-active agent Span-80 mix in reactor, stir and be warming up to 70～86 ℃, reaction 4～8h, heat filtering goes out catalyst S O
4 2-/ TiO
2, filtrate is cooled to room temperature, the product antioxidant 2246 is separated out, and filters to obtain antioxidant 2246.
Filtration is obtained the filtrate reconcentration of antioxidant 2246, separate out the residue antioxidant 2246, the product that obtains is dry again, obtain the white powder antioxidant 2246.
Better material proportion is:
The mass ratio of Paraformaldehyde 96 and the 2-tertiary butyl-4-methylphenol is 0.1～0.4: 1
SO
4 2-/ TiO
2With the mass ratio of the 2-tertiary butyl-4-methylphenol be 0.1～0.5: 1
The mass ratio of normal heptane and the 2-tertiary butyl-4-methylphenol is 2.4～4: 1
The mass ratio of Span-80 and the 2-tertiary butyl-4-methylphenol is 0.015～0.03: 1
The present invention is with solid super-strong acid SO
4 2-/ TiO
2As catalyzer, in the organic solvent normal heptane,, generate antioxidant 2246 with the 2-tertiary butyl-4-methylphenol and polyformaldehyde reaction.Catalyzer is more cheap, and catalyzer is easy to separate, excellent catalytic effect, and the three wastes are less.
Embodiment
Embodiment 1
In the four-hole bottle of 250mL, add the 32.8g 2-tertiary butyl-4-methylphenol, 3.9g Paraformaldehyde 96,4.0g solid catalyst SO
4 2-/ TiO
2, 68g normal heptane, 0.5g Span-80.Stirring is warming up to 86 ℃, reaction 6.0h, and heat filtering is told solid catalyst SO
4 2-/ TiO
2Filtrate is reduced to room temperature, and the product antioxidant 2246 is separated out, and filters to obtain product.Filtrate poured into steam partial solvent in the water distilling apparatus, separate out product 2246 again.The product that obtains for twice is dry in the lump, the white powder antioxidant 2246, yield is 80.1%, fusing point: 126～130 ℃.
Embodiment 2
In the four-hole bottle of 250mL, add the 32.8g 2-tertiary butyl-4-methylphenol, 13g Paraformaldehyde 96,16g solid catalyst SO
4 2-/ TiO
2, 109g normal heptane, 0.9g Span-80.Stirring is warming up to 84～86 ℃, reaction 8h, and heat filtering goes out solid catalyst SO
4 2-/ TiO
2Filtrate is reduced to room temperature, and the product antioxidant 2246 is separated out, and filters to obtain product.With the filtrate evaporation concentration, separate out portioned product 2246 again.With the product drying that obtains for twice, the white powder antioxidant 2246, yield is 82.1%, fusing point: 127～130 ℃.
Embodiment 3
In the four-hole bottle of 250mL, add the 32.8g 2-tertiary butyl-4-methylphenol, 9g Paraformaldehyde 96,6g solid catalyst SO
4 2-/ TiO
2, 95g normal heptane, 0.8g Span-80.Stirring is warming up to 75～78 ℃, reaction 4h, and heat filtering is removed solid catalyst SO
4 2-/ TiO
2Filtrate is reduced to room temperature, and the product antioxidant 2246 is separated out, and filters to obtain the product drying, gets the white powder antioxidant 2246, and yield is 80.0%, fusing point: 126～129 ℃.
Embodiment 4
In the four-hole bottle of 250mL, add the 32.8g 2-tertiary butyl-4-methylphenol, 6.5g Paraformaldehyde 96,4.0g solid catalyst SO
4 2-/ TiO
2, 68g normal heptane, 0.5g Span-80.Stirring is warming up to 70 ℃, reaction 6.0h, and heat filtering goes out solid catalyst SO
4 2-/ TiO
2Filtrate is reduced to room temperature, and the product antioxidant 2246 is separated out, and filters to obtain product.Solvent in the filtrate is partly steamed, separate out product 2246 again.The product that obtains for twice is dry in the lump, the white powder antioxidant 2246, yield is 80.1%, fusing point: 126～130 ℃.
The present invention is not limited to the technology described in the embodiment; its description is illustrative; and it is nonrestrictive; authority of the present invention is limited by claim; based on present technique field personnel according to the present invention can change, technology related to the present invention that method such as reorganization obtains, all within protection scope of the present invention.
Claims (2)
1, a kind of oxidation inhibitor 2,2 '-preparation method of methylene-bis (4-methyl-6-tert butyl phenol), it is characterized in that, with the 2-tertiary butyl-4-methylphenol, Paraformaldehyde 96, solid super-strong acid SO
4 2-/ TiO
2After catalyzer, normal heptane and tensio-active agent Span-80 mix in reactor, stir and be warming up to 70～86 ℃, reaction 4～8h, heat filtering goes out catalyst S O
4 2-/ TiO
2, filtrate is cooled to room temperature, product oxidation inhibitor 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol) separates out, filter obtain oxidation inhibitor 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol).
2, oxidation inhibitor 2,2 as claimed in claim 1 '-preparation method of methylene-bis (4-methyl-6-tert butyl phenol), it is characterized in that described material proportion is:
The mass ratio of Paraformaldehyde 96 and the 2-tertiary butyl-4-methylphenol is 0.1～0.4: 1
SO
4 2-/ TiO
2With the mass ratio of the 2-tertiary butyl-4-methylphenol be 0.1～0.5: 1
The mass ratio of normal heptane and the 2-tertiary butyl-4-methylphenol is 2.4～4: 1
The mass ratio of Span-80 and the 2-tertiary butyl-4-methylphenol is 0.015～0.03: 1.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200710059665XA CN100572350C (en) | 2007-09-18 | 2007-09-18 | Oxidation inhibitor 2, the preparation method of 2 '-methylene-bis (4-methyl-6-tert butyl phenol) |
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|---|---|---|---|
| CNB200710059665XA CN100572350C (en) | 2007-09-18 | 2007-09-18 | Oxidation inhibitor 2, the preparation method of 2 '-methylene-bis (4-methyl-6-tert butyl phenol) |
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| CN101139262A CN101139262A (en) | 2008-03-12 |
| CN100572350C true CN100572350C (en) | 2009-12-23 |
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| CN103170320A (en) * | 2013-04-02 | 2013-06-26 | 常州大学 | Preparation method of stratified columnar titanium dioxide photocatalyst |
| CN112500536A (en) * | 2020-12-31 | 2021-03-16 | 常州市五洲化工有限公司 | Preparation method of long-acting anti-tarnishing anti-aging agent |
| CN114516783B (en) * | 2022-03-10 | 2023-03-03 | 江苏极易新材料有限公司 | Synthetic method of antioxidant |
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Effective date of registration: 20201126 Address after: 226321, Jiangsu, Nantong province two Tongzhou District town industrial concentration area Patentee after: Nantong New Fengwei Machinery Technology Co.,Ltd. Address before: 300072 Tianjin City, Nankai District Wei Jin Road No. 92, Tianjin University Patentee before: Tianjin University |