CN102432870B - Synthesis method of dendritic complex main antioxidant - Google Patents
Synthesis method of dendritic complex main antioxidant Download PDFInfo
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- CN102432870B CN102432870B CN2011102539094A CN201110253909A CN102432870B CN 102432870 B CN102432870 B CN 102432870B CN 2011102539094 A CN2011102539094 A CN 2011102539094A CN 201110253909 A CN201110253909 A CN 201110253909A CN 102432870 B CN102432870 B CN 102432870B
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Abstract
The invention relates to a synthesis method of a dendritic complex main antioxidant. The synthesis method comprises the following steps of: taking 1.0 substituted dendritic polyamide-amine and beta-(3,5-ditertbutyl-4-hydroxyl phenyl) propionyl chloride which adopts quadrol as a core as a raw material, taking K2CO3 as an accelerating agent, taking benzene and water as solvents, carrying out amidating condensation reaction, and by filtering under pressure, obtaining a dendritic complex main antioxidant crude product; then adding trichloromethane into the crude product, and filtering; and adding benzene into the filtrate, precipitating out white solid under the low temperature, filtering under pressure, carrying out low-temperature vacuum drying and obtaining the dendritic complex main antioxidant. In the synthesis method, the reaction condition is moderate, the purification of a product is easy, the reaction is of a basic reaction type, and the industrialization is easy to realize; and the synthesized antioxidant has the structural characteristics of two types of main antioxidants such as hindered phenol and amine, and has higher antioxygenic property.
Description
Technical field
The present invention relates to a kind of synthetic method of dendroid composite antioxidant, specifically take organic substance as raw material, at K
2cO
3for promotor, under the condition that benzene and water mixed solvent exist, by the synthetic class novel high polymer material auxiliary agent of simple organic synthesis.
Background technology
Oxidation inhibitor is a kind of important auxiliary agent that can make polymer stabilizing, and its application almost relates to all polymer products.Phenolic antioxidant is the kind antioxidant pollution-free in all oxidation inhibitor, that nondiscoloration is best.Account at present 50% left and right of consumption at China's phenolic antioxidant, 2,6 di t butyl phenol (BHT) is as basic kind, dominate still, but because the molecular weight of BHT is relatively low, volatility is large, and the shortcoming such as yellowing variable color is arranged, consumption reduces year by year.Improve year by year and take the relatively hindered phenol kind consumption ratio of high molecular that has that the Irganox 1010 of Switzerland Ciba-Geigy company and Irganox 1076 be representative, become the leading product on phenolic antioxidant market.2002, Helena Bergenudda has proposed a kind of novel oxidation inhibitor, it is hyperbranched phenolic antioxidant, this kind antioxidant is that hyperbranched macromolecular is carried out to anti-oxidant modification, make it there are a plurality of antioxidant groups, improve its anti-oxidant activity, but this kind antioxidant has good antioxidant property in squalane, but because consistency is poor, antioxidant property is inferior to anti-oxidant Irganox 1010 in polyolefine material.2006, the people such as Yang Hongjun adopt dendritic macromole 1.0 PAMAMs and β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl chloride is raw material, the employing trichloromethane is solvent, and triethylamine is acid binding agent, a synthetic class dendritic phenolic antioxidant, but due to 1.0 generation the dendroid polyamide-amide poorly soluble in trichloromethane, graft reaction is incomplete, generates y-bend, trident by product, causes the yield of target product lower.
Summary of the invention
In order to solve the problem existed in background technology, the present invention adopts a kind of simple synthetic method to synthesize dendritic complex main antioxidant, and the method adopts K
2cO
3the aqueous solution and benzene are the reaction mixed solvent, the method for purifying and adopting low-temperature sludge to wash out, and the reaction conditions gentleness of the method, product is purified easily, and product yield is higher, reacts for basic reaction type, is easy to realize industrialization.
The technical solution adopted in the present invention content is: the synthetic method of this dendritic complex main antioxidant with 1.0 generation dendritic polyamide-amine and β-(3,5-di-tert-butyl-hydroxy phenyl) propionyl chloride for raw material, with K
2cO
3for promotor, benzene and water are solvent, under 15 ~ 45 ℃, react 1 ~ 12h, and reaction mixture, through negative pressure filtration, obtains the thick product of dendritic complex main antioxidant; Then add trichloromethane in thick product, filter; Add benzene in filtrate, 0 ~ 20 ℃ of lower Precipitation 1 ~ 5h, negative pressure filtration, 20 ~ 40 ℃ of lower vacuum-drying 2 ~ 6h, obtain dendritic complex main antioxidant.
In above-mentioned dendritic complex main antioxidant synthetic, 1.0 generation dendritic polyamide-amine with the amount of substance of β-(3,5-di-tert-butyl-hydroxy phenyl) propionyl chloride than being 1:(4 ~ 12), promotor K
2cO
3for the 20-70% of reaction raw materials total mass, the volume fraction of solvent benzol is 60 ~ 90%, and the volume fraction of aqueous solvent is 10 ~ 30%, and temperature of reaction is 0 ~ 25 ℃, and the reaction times is 1 ~ 12h; In thick product purification process, slightly product dissolves 8 ~ 16 times that the quality of solvent for use trichloromethane is thick quality product, the quality of Precipitation solvent for use benzene is thick quality product 15 ~ 35 times, temperature during Precipitation is 0 ~ 20 ℃, time is 1 ~ 3h, temperature during solid vacuum-drying is 20 ~ 40 ℃, and the time is 2 ~ 6h.
The invention has the beneficial effects as follows: the present invention adopt surface have many active function groups, symmetrical configuration 1.0 generation dendritic polyamide-amine, utilize its end group amido can carry out the function base and transform this characteristic, by simple organic reaction, a synthetic class dendritic complex main antioxidant.Due to adopted 1.0 generation end group be amido dendritic polyamide-amine and β-(3,5-di-tert-butyl-hydroxy phenyl) propionyl chloride are raw material, K
2cO
3for promotor, benzene and water are reaction solvent, and temperature of reaction is lower, and operation is also than being easier to; And the character of target product and the nature difference of reaction raw materials are larger, adopt the method for Precipitation, overcome the product difficult problem of purifying.This kind antioxidant symmetrical configuration, contain a plurality of phenolic hydroxyl group antioxidant groups, and molecule contains the amine antioxidant groups, it is complex type antioxidant in a kind of molecule, overcome the deficiency of phenolic antioxidant and amine antioxidants, can be widely used in being applicable to the multiple synthetic resins such as polyethylene, polypropylene, polystyrene, ABS.
the accompanying drawing explanation:
The building-up reactions equation that Fig. 1 is dendritic complex main antioxidant;
The yield that Fig. 2 is dendritic complex main antioxidant is with the change curve of reaction raw materials mol ratio;
The yield that Fig. 3 is dendritic complex main antioxidant is with the change curve of temperature of reaction;
The yield that Fig. 4 is dendritic complex main antioxidant is with the change curve in reaction times;
The yield that Fig. 5 is dendritic complex main antioxidant is with the change curve of promotor massfraction.
embodiment:
Below in conjunction with embodiment, the invention will be further described:
Embodiment 1: accurately take 1.0 dendritic polyamides of 1.0g-amine and 2g K
2cO
3be dissolved in 7ml distilled water, slowly drip while stirring the benzole soln 35ml that contains 3g β-(3,5-di-tert-butyl-hydroxy phenyl) propionyl chloride under 0 ℃, under 25 ℃ of conditions, react 15h, negative pressure filtration, obtain the thick product of dendritic complex main antioxidant; Then add the 50ml trichloromethane in thick product, stir 30min, filter; Add 150ml benzene in filtrate, 5 ℃ of lower Precipitation 1h, negative pressure filtration, 30 ℃ of lower vacuum-drying 3h, obtain dendritic complex main antioxidant.The reaction raw materials mol ratio on the impact of the yield of dendritic complex main antioxidant as Fig. 2.When 1.0 generation dendritic polyamide-amine and the amount of substance of β-(3,5-di-tert-butyl-hydroxy phenyl) propionyl chloride than for 1:6 the time, the yield of dendritic complex main antioxidant reaches 70.1%.
Embodiment 2: accurately take 1.0 dendritic polyamides of 1.0g-amine and 2g K
2cO
3be dissolved in 7ml distilled water, slowly drip while stirring the benzole soln 35ml that dissolves 3g β-(3,5-di-tert-butyl-hydroxy phenyl) propionyl chloride under 0 ℃, under 15 ~ 45 ℃ of conditions, react 15h, negative pressure filtration, obtain the thick product of dendritic complex main antioxidant; Then add the 50ml trichloromethane in thick product, stir 30min, filter; Add 150ml benzene in filtrate, 5 ℃ of lower Precipitation 1h, negative pressure filtration, 30 ℃ of lower vacuum-drying 3h, obtain dendritic complex main antioxidant.Temperature of reaction on the impact of the yield of dendritic complex main antioxidant as Fig. 3.When temperature of reaction is 25 ℃, the yield of dendritic complex main antioxidant reaches 70.5%.
Embodiment 3: accurately take 1.0 dendritic polyamides of 1.0g-amine and 2g K
2cO
3be dissolved in 7ml distilled water, slowly drip while stirring the benzole soln 35ml that dissolves 3g β-(3,5-di-tert-butyl-hydroxy phenyl) propionyl chloride under 0 ℃, under 25 ℃ of conditions, react 1 ~ 12h, negative pressure filtration, obtain the thick product of dendritic complex main antioxidant; Then add the 50ml trichloromethane in thick product, stir 30min, filter; Add 150ml benzene in filtrate, 5 ℃ of lower Precipitation 1h, negative pressure filtration, 30 ℃ of lower vacuum-drying 3h, obtain dendritic complex main antioxidant.Temperature of reaction on the impact of the yield of dendritic complex main antioxidant as Fig. 4.When the reaction times, be 5h, the yield of tree-shaped compound primary antioxidant reaches 70.5%.
Embodiment 4: accurately take 1.0 dendritic polyamides of 1.0g-amine and 0.8 ~ 2.8g K
2cO
3be dissolved in 7ml distilled water, slowly drip while stirring the benzole soln 35ml that dissolves 3g β-(3,5-di-tert-butyl-hydroxy phenyl) propionyl chloride under 0 ℃, under 25 ℃ of conditions, react 15h, negative pressure filtration, obtain the thick product of dendritic complex main antioxidant; Then add the 50ml trichloromethane in thick product, stir 30min, filter; Add 150ml benzene in filtrate, 5 ℃ of lower Precipitation 1h, negative pressure filtration, 30 ℃ of lower vacuum-drying 3h, obtain dendritic complex main antioxidant.Promotor K
2cO
3the massfraction that accounts for raw material on the impact of the yield of dendritic complex main antioxidant as Fig. 5.As promotor K
2cO
3consumption is 2.0g, also account for raw material heavy amount 50% the time, the yield of dendritic complex main antioxidant reaches 70.6%.
Embodiment 5: accurately take 1.0 dendritic polyamides of 1.0g-amine and 2g K
2cO
3be dissolved in 7ml distilled water, slowly drip while stirring the benzole soln 35ml that dissolves 3g β-(3,5-di-tert-butyl-hydroxy phenyl) propionyl chloride under 0 ℃, under 25 ℃ of conditions, react 15h, negative pressure filtration, obtain the thick product of dendritic complex main antioxidant; Then add the 50ml trichloromethane in thick product, stir 30min, filter; Add 150ml benzene in filtrate, 5 ℃ of lower Precipitation 1h, negative pressure filtration, 30 ℃ of lower vacuum-drying 3h, obtain dendritic complex main antioxidant, and yield reaches 70.2%.
Embodiment 6: 2 ~ 5 data with reference to the accompanying drawings, when 1.0 generation dendritic polyamide-amine and the amount of substance of β-(3,5-di-tert-butyl-hydroxy phenyl) propionyl chloride than being 1:5, promotor K
2cO
3for 50% of reaction raw materials quality, the volume fraction of solvent benzol is 83.3%, and the volume fraction of aqueous solvent is 16.7%, and temperature of reaction is 25 ℃, and the reaction times is 5h; The consumption that dissolves thick product solvent for use trichloromethane is 50ml, the consumption of Precipitation solvent for use benzene is 150ml, temperature during Precipitation is 5 ℃, time is 1h, temperature during solid vacuum-drying is 30 ℃, time is 3h, and the yield of the synthetic dendritic complex main antioxidant obtained is 70.8%.This oxidation inhibitor is applied in polyolefin resin, when addition is 0.2%, the oxidation induction period of polyvinyl resin is 34.0 min, and the oxidation induction period of acrylic resin is 3.3 min, far above the polyolefin resin that does not add oxidation inhibitor (polyethylene is 1.9 min, and polypropylene is 0.5 min).
Claims (2)
1. the synthetic method of a dendritic complex main antioxidant is characterized in that: the quadrol of take is core 1.0 generation the dendroid polyamide-amide and β-(3,5-di-tert-butyl-hydroxy phenyl) propionyl chloride be raw material, K
2cO
3for promotor, benzene and water are solvent, carry out the amidation condensation reaction, through negative pressure filtration, obtain the thick product of dendritic complex main antioxidant; Then add trichloromethane in thick product, filter; Add benzene in filtrate, Precipitation white solid under low temperature, negative pressure filtration, low-temperature vacuum drying, obtain dendritic complex main antioxidant;
Wherein 1.0 generation the dendroid polyamide-amide and the mol ratio of β-(3,5-di-tert-butyl-hydroxy phenyl) propionyl chloride be 1:(4-12), promotor K
2cO
320-70% for the reaction raw materials total mass;
In the amidation condensation reaction, the volume fraction of solvent for use benzene in whole system is 60 ~ 90%, and the volume fraction of solvent for use water in whole system is 10 ~ 30%; The temperature of amidation condensation reaction is 0 ~ 25 ℃, and the reaction times is 1 ~ 12h; In thick product purification process, the quality that thick product dissolves the solvent for use trichloromethane is thick quality product 8 ~ 16 times, the quality of Precipitation solvent for use benzene is thick quality product 15 ~ 35 times; In thick product purification process, temperature during Precipitation is 0 ~ 20 ℃, and the time is 1 ~ 3h; In thick product purification process, temperature during solid vacuum-drying is 20 ~ 40 ℃, and the time is 2 ~ 6h.
2. according to the synthetic method of dendritic complex main antioxidant claimed in claim 1, it is characterized in that: 1.0 generation the dendroid polyamide-amide and the mol ratio of β-(3,5-di-tert-butyl-hydroxy phenyl) propionyl chloride be 1:6, promotor K
2cO
3for 50% of reaction raw materials total mass; The temperature of amidation condensation reaction is 25 ℃, and the reaction times is 5h; In thick product purification process, temperature during Precipitation is 5 ℃, and the time is 1h; In thick product purification process, temperature during solid vacuum-drying is 30 ℃, and the time is 3h.
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| CN114316247A (en) * | 2020-09-29 | 2022-04-12 | 上海抚佳精细化工有限公司 | Modified macromolecular antioxidant, and synthesis method and application thereof |
| CN117186571B (en) * | 2023-10-09 | 2024-03-29 | 广东银豪塑胶制品有限公司 | Ageing-resistant PVC colloidal particle and preparation method thereof |
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| CN1931837A (en) * | 2005-09-16 | 2007-03-21 | 上海医药工业研究院 | Prepn process of cadotril |
| CN101704948A (en) * | 2009-12-02 | 2010-05-12 | 大庆石油学院 | Method for synthesizing dendritic phenolic antioxidant |
| CN102030851A (en) * | 2009-09-25 | 2011-04-27 | 中国石油化工股份有限公司 | Modified polyacrylamide and preparation method thereof |
| CN102093248A (en) * | 2010-12-22 | 2011-06-15 | 蚌埠丰原医药科技发展有限公司 | Method for preparing N-(2-Methylphenyl)-2-(propylamino)propa-namide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1931837A (en) * | 2005-09-16 | 2007-03-21 | 上海医药工业研究院 | Prepn process of cadotril |
| CN102030851A (en) * | 2009-09-25 | 2011-04-27 | 中国石油化工股份有限公司 | Modified polyacrylamide and preparation method thereof |
| CN101704948A (en) * | 2009-12-02 | 2010-05-12 | 大庆石油学院 | Method for synthesizing dendritic phenolic antioxidant |
| CN102093248A (en) * | 2010-12-22 | 2011-06-15 | 蚌埠丰原医药科技发展有限公司 | Method for preparing N-(2-Methylphenyl)-2-(propylamino)propa-namide |
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Inventor after: Li Cuiqin Inventor after: Wang Jun Inventor after: Li Haiyan Inventor after: Li Jie Inventor after: Zhang Rongming Inventor after: Shi Chunxia Inventor after: Chen Shuai Inventor before: Wang Jun Inventor before: Li Cuiqin Inventor before: Li Haiyan Inventor before: Li Jie Inventor before: Zhang Rongming Inventor before: Shi Chunxia Inventor before: Chen Shuai |
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Granted publication date: 20131211 Termination date: 20170831 |