| The research and development of phosphite esters antioxidant is the hydrolysis resistance and the high molecular weight. These products have the characteristics of low volatility, high resistance to precipitation and have the outstanding processing stability. With the rapid development of polymer material industry, it is increasing for the demand of phosphite esters antioxidant.Three kind of high molecular weight of phosphite esters antioxidants had been synthesized in this thesis. The influencing factors of synthesis process were investigated in the research which will provide important theoretical basis for the future industrial production.The synthesis of antioxidant 168 catalyzed by DMF has been studied through esterification reaction of 2,4-diterbutylphenol and phosphorus trichloride. The effects of the main factors on the reaction were studied by uniform test design method, and the process conditions were optimized. The optimum results were as follows: with the molar ratio of 2,4-diterbutylphenol to phosphorus trichloride was 3.0:1.0, the reaction should be lasted for 3.5h under the condition of 50℃ and then the temperature of the reaction should be heated up to 130℃ to react for 3.5h again, the dosage of catalyst was 0.1% accounting for the mass of 2,4-diterbutylphenol, the yield of antioxidant 168 was over 92%.The intermediate of antioxidant HP-10 and antioxidant TTEA, was synthesized by esterification reaction of phosphorus trichloride and bisphenol which was synthesized by condensation reaction of 2,4-diterbutylphenol and formaldehyde. Then the intermediate react with isooctyl alcohol to prepare antioxidant HP-10, and react with triethanolamine to prepare antioxidant TTEA. The optimized process conditions were as follows:(1)Synthesis of 2,2’-methylenebis(4,6-di-tert-butylphenol). The molar ratio of 2,4-diterbutylphenol to paraformaldehyde was 1.0:1.0, the reaction time was 8.0h under the reaction temperature were 70℃, the dosage of catalyst was 1.3% accounting for the mass of 2,4-diterbutylphenol, the dosage of emulsifier was 1.0% accounting for the mass of 2,4-diterbutylphenol, the yield of bisphenol was over 97%.(2) Synthesis of intermediate. The molar ratio of phosphorus trichloride to bisphenol was 1.3:1.0, the reaction time was 6.0h under the reaction temperature of 35℃, the molar ratio of acid binding agent to bisphenol was 2.2:1.0, the yield of intermediate was over 70%.(3) Synthesis of antioxidant HP-10. The molar ratio of intermediate to isooctyl alcohol was 2.0:2.3, the reaction time was 3.0h under the reaction temperature of 90℃, the molar ratio of acid binding agent to intermediate was 2.3:2.0, the yield of antioxidant HP-10 was over 75%.(4) Synthesis of antioxidant TTEA. The molar ratio of intermediate to triethanolamine was 3.2:1.0, the reaction time was 6.0h under the room temperature, the molar ratio of acid binding agent to intermediate was 3.6:1.0, the yield of antioxidant TTEA was over 44%.In this thesis, the structure of the target compounds were characterized by IR and NMR, and analyzed by some other technological means. |
