CN104744506A - Method for preparing tri-(2, 4-di-tertiary butyl phenyl) phosphite ester antioxidant - Google Patents
Method for preparing tri-(2, 4-di-tertiary butyl phenyl) phosphite ester antioxidant Download PDFInfo
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- CN104744506A CN104744506A CN201410226433.9A CN201410226433A CN104744506A CN 104744506 A CN104744506 A CN 104744506A CN 201410226433 A CN201410226433 A CN 201410226433A CN 104744506 A CN104744506 A CN 104744506A
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Abstract
The invention relates to a method for preparing a tri-(2, 4-di-tertiary butyl phenyl) phosphite ester antioxidant. The method comprises the following steps: by taking 2, 4-di-tertiary phenol and phosphorus trichloride as raw materials and an aromatic compound as a reaction solvent, carrying out reaction at 25-60 DEG C under the action of ethanol amine catalysts; then raising the temperature to 100-130 DEG C and reacting for 1-4 hours at the temperature; distilling at a reduced pressure, removing the reaction solvent, and adding lower alcohol as a solvent to crystallize; and severely stirring for a certain time, and filtering to obtain tri-(2, 4-di-tertiary butyl phenyl) phosphite ester.
Description
Technical field
The present invention relates to the method that one prepares three-(2,4-di-tert-butyl-phenyl) phosphorous acid esters, belong to field of fine chemical.
Background technology
Irgasfos 168, chemical name is three-(2,4-di-tert-butyl-phenyl) phosphorous acid ester, a kind ofly use very general phosphite antioxidant, have good high temperature resistant, volatility is low, the advantage such as nontoxic, antioxidant effect is excellent, usually as auxiliary antioxidant and phenolic antioxidant conbined usage, is applied to the product such as plastics, rubber.
Current most three-(2,4-di-tert-butyl-phenyl) phosphorous acid ester preparations use phosphorus trichloride, 2,4-DTBP as raw material, synthesizes under the effect of basic catalyst.
DE2950694 patent reports in the reaction system of toluene and aqueous sodium hydroxide solution, and at the temperature of 25-30 DEG C, using phosphorus trichloride and 2,4-DTBP as raw material, within a short period of time can obtain product.Although the time of this method reaction is shorter, considers phosphorus trichloride to water electrode for responsive, be hydrolyzed, and can have discharged a large amount of heats when phosphorus trichloride reacts with water, this kind of method can more difficult control, is more difficultly applied in the industrial production.
Chinese patent 201010123726.6 reports the preparation of a kind of 168 and reduces the method for residual HCl in product.This patent adopts phosphorus trichloride and 2,4-DTBP as raw material, and pyridine, as catalyzer, synthesizes irgasfos 168 through esterification.After esterification terminates, add the absorption agent of triethylamine as HCl residual in the thick product of three-(2,4-di-tert-butyl-phenyl) phosphorous acid ester, effectively improve the thermotolerance of product.
When Wang Wei outstanding person etc. has selected DMAP (DMAP) as catalyzer, the productive rate of 95% can be obtained, far away higher than employing N, dinethylformamide (DMF) as during catalyzer 80.5% productive rate, but the cost ratio DMF of DMAP is expensive, the production cost of irgasfos 168 can increase, and has certain difficulty in actual applications.
Chen Wei etc., using phosphorus trichloride and 2,4-DTBP as raw material, select triethylamine as catalyzer, at 140-150 DEG C, carry out esterification, can obtain the productive rate of about 95%.
Summary of the invention
The present invention is that one prepares three-(2,4-di-tert-butyl-phenyl) method of phosphite antioxidant, it is characterized in that the method is with phosphorus trichloride, 2,4-DTBP is as raw material, and aromatic compound is as reaction solvent, under the effect of weakly alkaline catalyzer, at 25 ~ 60 DEG C of reaction 1 ~ 4h, be then warming up to 100 ~ 130 DEG C, react 1 ~ 4h at such a temperature; After reaction terminates, underpressure distillation, removing reaction solvent, adds lower alcohol and carries out crystallization as solvent, after stirring certain hour, filters, is dried by obtained solid sample, obtain three-(2,4-di-tert-butyl-phenyl) phosphorous acid esters.
In preparation method of the present invention, the molar weight ratio of 2,4-DTBP and phosphorus trichloride is 3.0 ~ 3.5; The dropping temperature of phosphorus trichloride is 25 ~ 60 DEG C, and time for adding is 0-60min.
Weakly alkaline catalyzer of the present invention has referred to alcamines catalyzer, and its add-on is the 0.8%-5.7% of phosphorus trichloride add-on.
Alcamines catalyzer of the present invention refers to one or more mixing in thanomin, diethanolamine or trolamine.
Aromatic compound of the present invention refers to one or more mixing in toluene, dimethylbenzene, chlorobenzene.
Lower alcohol of the present invention refers to straight chain alcohol or the branched-chain alcoho of C1-C4, is specially one or more mixing in methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol or the trimethyl carbinol.
The invention has the beneficial effects as follows:
The ethanolamines catalysts adopted in the present invention, has good catalytic activity to the synthesis of three-(2,4-di-tert-butyl-phenyl) phosphorous acid esters, and price inexpensively, toxicity is lower, is applicable to suitability for industrialized production, is conducive to the production cost reducing technique.
Embodiment
To come that the present invention is described further below by specific embodiment, but scope of the present invention is not confined to embodiment.
Embodiment 1:
In the 250mL there-necked flask that constant pressure funnel, thermometer be housed, add people 24g2,4-DI-tert-butylphenol compounds, 15mL toluene, thanomin 0.10g, be warming up to 60 DEG C, in 60min, slowly drip 5ml contain 4.5gPCl
3toluene solution, drip terminate, insulation reaction 4h at such a temperature, is warming up to 130 DEG C, reacts 4h at such a temperature.Underpressure distillation, removing reaction solvent, obtains three-(2,4-di-tert-butyl-phenyl) phosphorous acid ester crude products.Add 30ml methyl alcohol, vigorous stirring is about 3h, and filter, obtained solid sample is carried out drying, obtains white powder product, productive rate is 85.1%.
Embodiment 2:
In the 250mL there-necked flask that constant pressure funnel, thermometer be housed, add people 22g2,4-DI-tert-butylphenol compounds, 15mL dimethylbenzene, diethanolamine 0.12g, be warming up to 25 DEG C, directly add 5ml and contain 4.5g PCl
3xylene solution, at 25 DEG C, react 4h, be warming up to 100 DEG C, react 4h at such a temperature.Underpressure distillation, removing reaction solvent, obtains three-(2,4-di-tert-butyl-phenyl) phosphorous acid ester crude products.Add 30ml ethanol, vigorous stirring is about 1h, and filter, obtained solid sample is carried out drying, obtains white powder product, productive rate is 76.2%.
Embodiment 3:
In the 250mL there-necked flask that constant pressure funnel, thermometer be housed, add people 21g2,4-DI-tert-butylphenol compounds, 15mL chlorobenzene, trolamine 0.2g, be warming up to 40 DEG C, slowly add 5ml and contain 4.5g PCl
3chlorobenzene solution, at 40 DEG C, react 3h, be warming up to 120 DEG C, react 3h at such a temperature.Underpressure distillation, removing reaction solvent, obtains three-(2,4-di-tert-butyl-phenyl) phosphorous acid ester crude products.Add 30ml propyl alcohol, vigorous stirring is about 2h, and filter, obtained solid sample is carried out drying, obtains white powder product, productive rate is 83.8%.
Embodiment 4:
In the 250mL there-necked flask that constant pressure funnel, thermometer be housed, add people 21g2,4-DI-tert-butylphenol compounds, 15mL toluene, diethanolamine 0.3g, be warming up to 40 DEG C, in 30min, slowly add 5ml contain 4.5g PCl
3toluene solution, at 40 DEG C, react 1h, be warming up to 110 DEG C, react 4h at such a temperature.Underpressure distillation, removing reaction solvent, obtains three-(2,4-di-tert-butyl-phenyl) phosphorous acid ester crude products.Add 30ml Virahol, vigorous stirring is about 1h, and filter, obtained solid sample is carried out drying, obtains white powder product, productive rate is 85.9%.
Embodiment 5:
In the 250mL there-necked flask that constant pressure funnel, thermometer be housed, add people 21g2,4-DI-tert-butylphenol compounds, 15mL toluene, diethanolamine 0.3g, be warming up to 40 DEG C, in 40min, slowly add 5ml contain 4.5g PCl
3toluene solution, at 40 DEG C, react 4h, be warming up to 120 DEG C, react 1h at such a temperature.Underpressure distillation, removing reaction solvent, obtains three-(2,4-di-tert-butyl-phenyl) phosphorous acid ester crude products.Add 30ml isopropylcarbinol, vigorous stirring is about 1h, and filter, obtained solid sample is carried out drying, obtains white powder product, productive rate is 83.3%.
Embodiment 6:
In the 250mL there-necked flask that constant pressure funnel, thermometer be housed, add people 25g2,4-DI-tert-butylphenol compounds, 15mL toluene, trolamine 0.3g, be warming up to 60 DEG C, in 50min, slowly add 5ml contain 4.5g PCl
3toluene solution, at 60 DEG C, react 1h, be warming up to 120 DEG C, react 2h at such a temperature.Underpressure distillation, removing reaction solvent, obtains three-(2,4-di-tert-butyl-phenyl) phosphorous acid ester crude products.Add 30ml isopropylcarbinol, vigorous stirring is about 2h, and filter, obtained solid sample is carried out drying, obtains white powder product, productive rate is 87.3%.
Embodiment 7:
In the 250mL there-necked flask that constant pressure funnel, thermometer be housed, add people 22g2,4-DI-tert-butylphenol compounds, 15mL toluene, trolamine 0.15g, be warming up to 50 DEG C, in 40min, slowly add 5ml contain 4.5g PCl
3toluene solution, at 50 DEG C, react 4h, be warming up to 120 DEG C, react 4h at such a temperature.Underpressure distillation, removing reaction solvent, obtains three-(2,4-di-tert-butyl-phenyl) phosphorous acid ester crude products.Add the 30ml trimethyl carbinol, vigorous stirring is about 2h, and filter, obtained solid sample is carried out drying, obtains white powder product, productive rate is 88.8%.
Embodiment 8:
In the 250mL there-necked flask that constant pressure funnel, thermometer be housed, add people 22g2,4-DI-tert-butylphenol compounds, 15mL toluene, trolamine 0.15g, be warming up to 45 DEG C, in 50min, slowly add 5ml contain 4.5g PCl
3toluene solution, at 45 DEG C, react 3h, be warming up to 130 DEG C, react 4h at such a temperature.Underpressure distillation, removing reaction solvent, obtains three-(2,4-di-tert-butyl-phenyl) phosphorous acid ester crude products.Add the 30ml trimethyl carbinol, vigorous stirring is about 2h, and filter, obtained solid sample is carried out drying, obtains white powder product, productive rate is 85.9%.
Embodiment 9:
In the 250mL there-necked flask that constant pressure funnel, thermometer be housed, add people 20g2,4-DI-tert-butylphenol compounds, 15mL toluene, trolamine 0.15g, be warming up to 45 DEG C, in 50min, slowly add 5ml contain 4.5g PCl
3toluene solution, at 45 DEG C, react 1h, be warming up to 130 DEG C, react 2h at such a temperature.Underpressure distillation, removing reaction solvent, obtains three-(2,4-di-tert-butyl-phenyl) phosphorous acid ester crude products.Add 30ml n-propyl alcohol, vigorous stirring is about 1h, and filter, obtained solid sample is carried out drying, obtains white powder product, productive rate is 81.9%.
Embodiment 10:
In the 250mL there-necked flask that constant pressure funnel, thermometer be housed, add people 21g2,4-DI-tert-butylphenol compounds, 15mL toluene, trolamine 0.15g, be warming up to 40 DEG C, in 30min, slowly add 5ml contain 4.5g PCl
3toluene solution, at 40 DEG C, react 3h, be warming up to 130 DEG C, react 1h at such a temperature.Underpressure distillation, removing reaction solvent, obtains three-(2,4-di-tert-butyl-phenyl) phosphorous acid ester crude products.Add 30ml n-propyl alcohol, vigorous stirring is about 2h, and filter, obtained solid sample is carried out drying, obtains white powder product, productive rate is 80.1%.
Claims (6)
1. prepare three-(2 for one kind, 4-di-tert-butyl-phenyl) method of phosphite antioxidant, it is characterized in that the method is with phosphorus trichloride, 2,4-DTBP is as raw material, and aromatic compound is as reaction solvent, under the effect of weakly alkaline catalyzer, at 25 ~ 60 DEG C of reaction 1 ~ 4h, be then warming up to 100 ~ 130 DEG C, react 1 ~ 4h at such a temperature; After reaction terminates, underpressure distillation, removing reaction solvent, adds lower alcohol and carries out crystallization as solvent, after stirring 1 ~ 3h, filters, is dried by obtained solid sample, obtain three-(2,4-di-tert-butyl-phenyl) phosphorous acid esters.
2. in the preparation method described in claim 1, the molar weight ratio of 2,4-DTBP and phosphorus trichloride is 3.0 ~ 3.5; The dropping temperature of phosphorus trichloride is 25 ~ 60 DEG C, and time for adding is 0-60min.
3. the weakly alkaline catalyzer described in claim 1 has referred to alcamines catalyzer, and its add-on is the 0.8%-5.7% of phosphorus trichloride add-on.
4. alcamines catalyzer according to claim 3 refers to one or more mixing in thanomin, diethanolamine or trolamine.
5. the aromatic compound described in claim 1 refers to one or more mixing in toluene, dimethylbenzene, chlorobenzene.
6. the lower alcohol described in claim 1 refers to straight chain alcohol or the branched-chain alcoho of C1-C4, is specially one or more mixing in methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol or the trimethyl carbinol.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108467406A (en) * | 2018-04-04 | 2018-08-31 | 江苏极易新材料有限公司 | 168 new technique for synthesizing route of antioxidant |
| CN110483569A (en) * | 2019-08-09 | 2019-11-22 | 万华化学集团股份有限公司 | A kind of polycarbonate antioxidant, preparation method and a kind of polycarbonate compositions |
| CN110590834A (en) * | 2019-09-23 | 2019-12-20 | 黄河三角洲京博化工研究院有限公司 | Preparation method of antioxidant 168 |
| CN113651849A (en) * | 2021-07-23 | 2021-11-16 | 江苏常青树新材料科技股份有限公司 | Polymeric phenol-free low-odor phosphite ester and preparation method thereof |
| CN115043875A (en) * | 2022-05-27 | 2022-09-13 | 山东三丰新材料有限公司 | Diphosphite antioxidant and preparation method thereof |
| CN115651012A (en) * | 2022-11-16 | 2023-01-31 | 江苏极易新材料有限公司 | Synthesis method of low-acid value tris (2,4-di-tert-butylphenyl) phosphite |
-
2014
- 2014-05-22 CN CN201410226433.9A patent/CN104744506A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108467406A (en) * | 2018-04-04 | 2018-08-31 | 江苏极易新材料有限公司 | 168 new technique for synthesizing route of antioxidant |
| CN110483569A (en) * | 2019-08-09 | 2019-11-22 | 万华化学集团股份有限公司 | A kind of polycarbonate antioxidant, preparation method and a kind of polycarbonate compositions |
| CN110483569B (en) * | 2019-08-09 | 2022-02-18 | 万华化学集团股份有限公司 | Polycarbonate antioxidant, preparation method and polycarbonate composition |
| CN110590834A (en) * | 2019-09-23 | 2019-12-20 | 黄河三角洲京博化工研究院有限公司 | Preparation method of antioxidant 168 |
| CN110590834B (en) * | 2019-09-23 | 2022-03-04 | 黄河三角洲京博化工研究院有限公司 | Preparation method of antioxidant 168 |
| CN113651849A (en) * | 2021-07-23 | 2021-11-16 | 江苏常青树新材料科技股份有限公司 | Polymeric phenol-free low-odor phosphite ester and preparation method thereof |
| CN115043875A (en) * | 2022-05-27 | 2022-09-13 | 山东三丰新材料有限公司 | Diphosphite antioxidant and preparation method thereof |
| CN115043875B (en) * | 2022-05-27 | 2024-03-19 | 山东三丰新材料有限公司 | Bisphosphite antioxidant and preparation method thereof |
| CN115651012A (en) * | 2022-11-16 | 2023-01-31 | 江苏极易新材料有限公司 | Synthesis method of low-acid value tris (2,4-di-tert-butylphenyl) phosphite |
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Application publication date: 20150701 |