【作者】 李秀云；

【导师】 王月欣； 李效军；

【作者基本信息】 河北工业大学 ， 应用化学， 2006， 硕士

【摘要】 NA-11和NA-21是性能优异的聚丙烯成核剂。本文以2,4-二叔丁基苯酚、甲醛和三氯氧磷为主要原料,经缩合、酯化和中和成盐等反应制备了聚丙烯成核剂NA-11和NA-21。 在缩合反应中,本文采用单因素实验法,考察了缩合试剂、催化剂和乳化剂的种类及用量、反应温度、反应时间和后处理方法等因素对双酚收率及质量的影响,确定了较适宜的反应条件。在此条件下,以2,4-二叔丁基苯酚计双酚的收率为97.2%,熔点为147.8℃。 在酯化反应中,本文采用非极性的环己烷作溶剂实现了磷酸酯的合成,并确定了较优的反应条件。在此条件下,以双酚计磷酸酯的收率为76.1%,熔点为342.14℃。 本文首次尝试在乙腈、吡啶等极性溶剂体系实现磷酸酯合成的可能性,通过优化反应条件确定了合成磷酸酯的新方法,以双酚计磷酸酯的收率分别达到了90.5%和98.7%。 在中和成盐反应中,考察了不同规格的乙醇作为溶剂的反应效果,结果显示:50mL 95%乙醇中适宜的磷酸酯用量为8g,氢氧化钠投入理论量,以磷酸酯计钠盐收率为83.2%;50mL无水乙醇中适宜的磷酸酯投入量为8g,氢氧化钠投入理论量,以磷酸酯计钠盐收率为72.0%,显著低于以95%乙醇作溶剂的情况。 本文在文献调研和多次实验的基础上尝试了合成钠盐的新方法,即以价廉易得的水作溶剂实现了NA-11的合成,收率显著提高,以磷酸酯计钠盐收率达到了97.7%。 NA-11的应用实验结果表明,本文合成的产品质量达到了日本旭电化公司产品的水平。 本文以上述自制的NA-11为原料制备出了NA-21,实验结果表明:结晶氯化铝与NA-11的适宜摩尔比为1∶2,氯化铝溶液的滴加温度为40℃,在NA-11投料量为8.14g时,适宜的甲醇用量为54mL。在此条件下,以钠盐计NA-21的收率为97.1%,熔点为217.5℃。 此外,本文尝试了以磷酸酯为原料一锅法制备NA-21的新方法,结果表明:以甲醇为溶剂,磷酸酯、氢氧化钠和氯化铝的适宜摩尔比为1∶1∶0.5,以磷酸酯计NA-21的收率为95.3%,熔点为200.5℃,此法操作更为简便。更多还原

【Abstract】 In this thesis, the nucleating agents NA-11 and NA-21 for polypropylene were prepared by condensation of 2,4-bis-tert-butylphenol and formaldehyde, esterification, hydrolysis and neutralization reactions.In the condensation reaction, the factors affecting the yield and quality of 2,2’-methylene-bis（4,6-ditertbutylphenol）, such as the choice and dosage of condensation agent, catalyst and emulsifying agent, reaction temperature, reaction time and treatment method etc. were investigated through single factor experiments and the optimum experimental conditions were gained. Under the optimum conditions, the yield of the intermediate was 97.2% base on 2,4-bis-tert-butylphenol and the melting point was 147.8℃.In esterification reaction, 2,2’-methylene-bis（4,6-ditertbutylphenol） phosphate was synthesized in cyclohexane as solvent. The optimal condition of reaction was determined. In this conditions, the yield of the phosphate was 76.1% based on 2,2’-methylene-bis（4,6-ditertbutyl phenol） and the melting point was 342.14℃.The paper tried to synthesize phosphate in polar solvents （acetonitrile, pyridine）, which is different from previous methods. The results showed that this method was possible and the yield of phosphate reached 90.5% and 98.7% based on 2,2’-methylene-bis（4,6-ditertbutylphenol）, respectively.In neutralization reaction, the results were as follows: the yield of the product is 83.2% based on 2,2’-methylene-bis（4,6-ditertbutylphenol） phosphate under the reaction conditions of the suitable amount of phosphate of 8g in 50mL 95% ethanol and the theoretical amount of sodium hydroxide;the yield of the product is 72.0% under the reaction condition of the suitable amount of phosphate of 8g in 50mL absolute ethyl alcohol and the theoretical amount of sodium hydroxide, which is lower than the above evidently. A new method for synthesizing NA-11 from phosphate was proposed based on numerous literature and experiments, which was used H₂O as solvent. As a result, the yield of the product increased remarkably to 97.7% based on 2,2’-methylene-bis（4,6-ditertbutylphenol） phosphate.The applying experiments indicated that the quality of NA-11 product reached the level of Asahi Denka’s.NA-21 was prepared from NA-11. From the experimental results we concluded that the molar ratio of AlGbto NA-11, dropping temperature, methanol dosage were 1:2, 40°C, 54mL, respectively. The yield of NA-21 was 97.1% based on NA-11 under the above conditions and the melting point was 217.5°C.Furthermore, a new method of preparing NA-21 from phosphate was initiated. It was found that the suitable molar ratio of phosphate, sodium hydroxide to AICI3 was 1:1:0.5 when methanol was the solvent. Under the optimal condition the yield of NA-21 was 95.3% based on 2,2’-methylene-bis（4,6-ditertbutylphenol） phosphate and the melting point was 200.5 °C . Compared to the above means, this method was more convenient.更多还原