CN1911939A - Preparation method of phosphite ester kind antioxidant - Google Patents
Preparation method of phosphite ester kind antioxidant Download PDFInfo
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- CN1911939A CN1911939A CN 200610029517 CN200610029517A CN1911939A CN 1911939 A CN1911939 A CN 1911939A CN 200610029517 CN200610029517 CN 200610029517 CN 200610029517 A CN200610029517 A CN 200610029517A CN 1911939 A CN1911939 A CN 1911939A
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Abstract
The present invention relates to preparation process of phosphite antioxidant, and the preparation process includes the first two-step synthesis comprising catalytic condensation and catalytic substitution and the subsequent hydrolysis resisting treatment to obtain bis(2.4-ditert-butyl phenyl)pentaerythritol diphosphite product. Compared with available technology, the antioxidant product of the present invention has the features of high purity up to 98 %, low acid value not higher than 0.5 mg KOH/g, and long storage life over 6 months.
Description
Technical field
The present invention relates to a kind of preparation field of antioxidant, particularly a kind of preparation method of phosphite ester kind antioxidant.
Background technology
Two (2.4-di-tert-butyl-phenyl) pentaerythritol diphosphites is a kind of high-performance solid auxiliary antioxidant with phosphorous acid esters of extensive use, the polymkeric substance hydroperoxide that it generates in can decomposing macromolecular material thermo-oxidative ageing chain reaction, thereby interrupt or weaken the thermo-oxidative ageing process of macromolecular material, simultaneously can also supply with body as hydrogen atom makes the Hinered phenols primary antioxidant obtain hydrogen atom from it after catching free radical and regenerates, produce significant heterogeneity synergistic effect, and therefore make it become the stablizer of polyolefine processing.Especially for polypropylene processing at high temperature, can suppress xanthochromia and control melting index to change within the specific limits, thereby guarantee the use properties after the processing.
The preparation of at present two (2.4-di-tert-butyl-phenyl) pentaerythritol diphosphites, usually adopt one-step preparation process, 24 phenol, dimethylbenzene, tetramethylolmethane and the catalyzer of specified amount are dropped into reactor, drip phosphorus trichloride and carry out building-up reactions, about 30 ℃ of control dropping temperature; Then, extract hydrogen chloride gas that reaction generates, steam reaction dimethylbenzene, obtain two (2.4-di-tert-butyl-phenyl) pentaerythritol diphosphites crude products; Crude product after filtration, crystallization, obtain the suspension of solid content about 20%, drying is handled the finished product that obtains purity about 97% again.For example U.S. Pat 5917076 discloses the method for two (2.4-di-tert-butyl-phenyl) pentaerythritol diphosphites of a kind of preparation, and this patent still adopts one-step technology, and is similar with above-mentioned present one-step technology.
The shortcoming of one-step preparation process mainly is: reaction is not easy to control, by-products content is more poor than anti-hydrolysis ability higher, finished product.
Summary of the invention
Purpose of the present invention is exactly that a kind of two-step approach that provides prepares the method for phosphite ester kind antioxidant in order to overcome the weak point that above-mentioned prior art exists.
Purpose of the present invention can be achieved through the following technical solutions: a kind of preparation method of phosphite ester kind antioxidant, it is characterized in that, it is synthetic that this method adopts catalyzing and condensing and catalysis to replace two-step approach, obtains two (2.4-di-tert-butyl-phenyl) pentaerythritol diphosphites products through anti-hydrolysis treatment again.
Described method comprises following processing step: at first solvent, tetramethylolmethane, catalyzer are dropped into reactor, control reaction temperature and time, drip phosphorus trichloride and carry out the catalyzing and condensing reaction; After generating intermediate, add the 2.4-DI-tert-butylphenol compounds again and carry out the catalysis substitution reaction, generate two (2.4-di-tert-butyl-phenyl) pentaerythritol diphosphites; Constantly extract the hydrogen chloride gas that is generated in the substitution reaction process; After finishing reaction, remove remaining phosphorus trichloride, steam reaction and use solvent, obtain two (2.4-di-tert-butyl-phenyl) pentaerythritol diphosphites crude products; At last, the suspension that obtains through crystallization filters with drying treatment again and promptly obtains the finished product.
Described the first step reaction control temperature is that control dropping phosphorus trichloride temperature is 5～50 ℃, and the second step reaction control temperature is that control adds 2.4-DI-tert-butylphenol compounds temperature at 60～100 ℃.
Described catalyzer is a kind of alkylamide material.
Described solvent can be organic alkane, aromatic hydrocarbons or their mixture.
Described suspension solid content is 20% weight～40% weight.
Described steam the reaction can recycle with recovered solvent in solvent and the crystallisation process.
Compared with prior art, characteristics of the present invention are: adopt catalyzing and condensing and catalysis to replace the two-step approach synthesis and preparation process, has the reaction times weak point, easy control of reaction system, by product generates few, aftertreatment is technical advance such as realizations easily, two (2.4-di-tert-butyl-phenyl) the pentaerythritol diphosphites oxidation inhibitor finished products that make by this technology have purity height (〉=98%), acid number low (≤0.5mgKOH/g), the storage time grows the characteristics of (〉=6 months).
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
In the 2L four-hole boiling flask that thermometer, electronic stirring, reflux exchanger and gas export mouth are housed; under nitrogen protection; the petroleum benzene, 200g tetramethylolmethane, the 4g dimethyl formamide that add 400g, control dropping temperature drip phosphorus trichloride and carry out the catalyzing and condensing reaction at 24 ± 1 ℃.Improve then after the temperature of reaction to 80 ℃, add 24 phenol and carry out the catalysis substitution reaction, and constantly extract the hydrogen chloride gas that reaction generates, after the insulation reaction 5 hours, further remove hydrogen chloride gas and remove remaining phosphorus trichloride, steam reaction benzene, obtain two (2.4-di-tert-butyl-phenyl) pentaerythritol diphosphites crude products.Crude product crystallization in the methyl alcohol that contains 10% benzene of having an appointment obtains the suspension of solid content 25.7%.Suspension adds a small amount of hydrolysis-resisting agent through vacuum filtration, and drying obtains finished product again.These product are through high pressure liquid chromatographic analysis, and purity is 99.0%; Its acid number of titrimetry is 0.28mgKOH/g.
Embodiment 2
Solvent, tetramethylolmethane and the catalyzer of specified amount are dropped into reactor, drip phosphorus trichloride and carry out the catalyzing and condensing reaction, equipment and reinforced process are with example 1, and control drips the temperature of phosphorus trichloride at 24 ± 1 ℃.And the temperature that adds 24 phenol is 90 ± 2 ℃, carries out the catalysis substitution reaction.After the insulation reaction 4 hours, extract hydrogen chloride gas that reaction generates, remove remaining phosphorus trichloride, steam reaction solvent, two (2.4-di-tert-butyl-phenyl) the pentaerythritol diphosphites crude products that obtain.The finished product that this crude product obtains after crystallization, filtration, anti-hydrolysis treatment, drying.This product purity is 99.0%, and acid number is 0.30mgKOH/g.
Embodiment 3
Solvent, tetramethylolmethane and the catalyzer of specified amount are dropped into reactor, drip phosphorus trichloride and carry out the catalyzing and condensing reaction, equipment and reinforced process are with example 1, and control drips the temperature of phosphorus trichloride at 24 ± 1 ℃.And the temperature that adds 24 phenol is 80 ± 2 ℃, carries out the catalysis substitution reaction.After the insulation reaction 5 hours, extract hydrogen chloride gas that reaction generates, remove remaining phosphorus trichloride, steam reaction solvent, two (2.4-di-tert-butyl-phenyl) the pentaerythritol diphosphites crude products that obtain.The crystallization in the alcohol solvent that contains 10% benzene of this crude product obtains solid content and is 28.2% suspension.Suspension adds a small amount of hydrolysis-resisting agent through vacuum filtration, and drying obtains finished product again.This product purity is 98.5%, and acid number is 0.22mgKOH/g.
Claims (7)
1. the preparation method of a phosphite ester kind antioxidant is characterized in that, it is synthetic that this method adopts catalyzing and condensing and catalysis to replace two-step approach, obtains two (2.4-di-tert-butyl-phenyl) pentaerythritol diphosphites products through anti-hydrolysis treatment again.
2. the preparation method of a kind of phosphite ester kind antioxidant according to claim 1, it is characterized in that, described method comprises following processing step: at first solvent, tetramethylolmethane, catalyzer are dropped into reactor, control reaction temperature and time, drip phosphorus trichloride and carry out the catalyzing and condensing reaction; After generating intermediate, add the 2.4-DI-tert-butylphenol compounds again and carry out the catalysis substitution reaction, generate two (2.4-di-tert-butyl-phenyl) pentaerythritol diphosphites; Constantly extract the hydrogen chloride gas that is generated in the substitution reaction process; After finishing reaction, remove remaining phosphorus trichloride, steam reaction and use solvent, obtain two (2.4-di-tert-butyl-phenyl) pentaerythritol diphosphites crude products; At last, the suspension that obtains through crystallization filters with drying treatment again and promptly obtains the finished product.
3. the preparation method of a kind of phosphite ester kind antioxidant according to claim 2, it is characterized in that, described the first step reaction control temperature is that control dropping phosphorus trichloride temperature is 5～50 ℃, and the second step reaction control temperature is that control adds 2.4-DI-tert-butylphenol compounds temperature at 60～100 ℃.
4. the preparation method of a kind of phosphite ester kind antioxidant according to claim 2 is characterized in that, described catalyzer is a kind of alkylamide material.
5. the preparation method of a kind of phosphite ester kind antioxidant according to claim 2 is characterized in that, described solvent can be organic alkane, aromatic hydrocarbons or their mixture.
6. the preparation method of a kind of phosphite ester kind antioxidant according to claim 2 is characterized in that, described suspension solid content is 20% weight～40% weight.
7. the preparation method of a kind of phosphite ester kind antioxidant according to claim 2 is characterized in that, described steam the reaction can recycle with recovered solvent in solvent and the crystallisation process.
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| CN200610029517A CN1911939B (en) | 2006-07-28 | 2006-07-28 | Preparation method of phosphite ester kind antioxidant |
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| CN200610029517A CN1911939B (en) | 2006-07-28 | 2006-07-28 | Preparation method of phosphite ester kind antioxidant |
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| CN1911939A true CN1911939A (en) | 2007-02-14 |
| CN1911939B CN1911939B (en) | 2010-05-12 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101182330B (en) * | 2007-04-11 | 2010-05-26 | 山东省临沂市三丰化工有限公司 | Method for preparing pentaerythrite bisphosphite anti-oxidant |
| CN101418018B (en) * | 2007-10-26 | 2011-07-06 | 中国石油化工股份有限公司 | Method for preparing pentaerythritol bis-phosphite antioxidant |
| CN103319537A (en) * | 2012-03-22 | 2013-09-25 | 中国石油天然气股份有限公司 | Bifunctional-group-containing pentaerythritol ester antioxidant compound and synthesis method thereof |
| CN108250240A (en) * | 2018-03-16 | 2018-07-06 | 江苏极易新材料有限公司 | A kind of 626 synthesis technology of antioxidant |
| CN114920778A (en) * | 2022-06-21 | 2022-08-19 | 营口风光新材料股份有限公司 | Method for improving purity of bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite |
| CN115947754A (en) * | 2022-12-28 | 2023-04-11 | 江苏极易新材料有限公司 | Synthesis method of low-acid value tris (2, 4-di-tert-butylphenyl) phosphite |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0159294B1 (en) * | 1984-04-17 | 1988-11-17 | Ciba-Geigy Ag | Process for preparing cyclic phosphorous-acid esters |
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2006
- 2006-07-28 CN CN200610029517A patent/CN1911939B/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101182330B (en) * | 2007-04-11 | 2010-05-26 | 山东省临沂市三丰化工有限公司 | Method for preparing pentaerythrite bisphosphite anti-oxidant |
| CN101418018B (en) * | 2007-10-26 | 2011-07-06 | 中国石油化工股份有限公司 | Method for preparing pentaerythritol bis-phosphite antioxidant |
| CN103319537A (en) * | 2012-03-22 | 2013-09-25 | 中国石油天然气股份有限公司 | Bifunctional-group-containing pentaerythritol ester antioxidant compound and synthesis method thereof |
| CN103319537B (en) * | 2012-03-22 | 2015-12-02 | 中国石油天然气股份有限公司 | Bifunctional-group-containing pentaerythritol ester antioxidant compound and synthesis method thereof |
| CN108250240A (en) * | 2018-03-16 | 2018-07-06 | 江苏极易新材料有限公司 | A kind of 626 synthesis technology of antioxidant |
| CN114920778A (en) * | 2022-06-21 | 2022-08-19 | 营口风光新材料股份有限公司 | Method for improving purity of bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite |
| CN114920778B (en) * | 2022-06-21 | 2024-05-10 | 营口风光新材料股份有限公司 | Method for improving purity of bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite |
| CN115947754A (en) * | 2022-12-28 | 2023-04-11 | 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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| CN1911939B (en) | 2010-05-12 |
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