应用化学 ›› 2017, Vol. 34 ›› Issue (2): 151-157.DOI: 10.11944/j.issn.1000-0518.2017.02.160203

• 研究论文 • 上一篇    下一篇

阻燃剂9,10-二氢-9-氧杂-10-膦杂菲-10-氧化物合成中酯化反应和酰基化反应的优化

赖华a*(),刘兴a,朱小明a,龙婉君a,李想a,熊平生b   

  1. a衡阳师范学院 化学与材料科学学院,功能金属有机材料湖南省普通高等学校重点实验室 湖南 衡阳 421008
    b衡阳师范学院 城市与旅游学院 湖南 衡阳 421008
  • 收稿日期:2016-05-16 接受日期:2016-09-05 出版日期:2017-01-18 发布日期:2017-01-18
  • 通讯作者: 赖华
  • 基金资助:
    国家自然科学基金资助项目(41471153);湖南省自然科学基金项目(2016JJ6013);衡阳师范学院科学基金项目(13B30);衡阳市科学技术发展计划(2014KJ19)资助

Optimization of Esterification and Acylation on Synthesis of Flame Retardant 9,10-Dihydro-9-oxa-10-phosphaphen-anthrene-10-oxide

LAI Huaa*(),LIU Xinga,ZHU Xiaominga,LONG Wanjuna,LI Xianga,XIONG Pingshengb   

  1. aKey Laboratory of Functional Organometallic Materials of College of Hu'nan Province,College of Chemisty and Material Science
    bCollege of City and Tourism,Hengyang Normal University,Hengyang,Hu'nan 421008,China
  • Received:2016-05-16 Accepted:2016-09-05 Published:2017-01-18 Online:2017-01-18
  • Contact: LAI Hua
  • Supported by:
    Supported by the National Natural Science Foundation of China(No.41471153), Hu'nan Provincial Natural Science Foundation of China(No.2016JJ6013), Scientific Research Foundation of Hengyang Normal University, China(No.13B30), Project of Science and Technology Bureau of Hengyang City, China(No.2014KJ19)

摘要:

有机磷杂环化合物9,10-二氢-9-氧杂-10-膦杂菲-10-氧化物(DOPO)因性能优异而作为无卤阻燃剂得到广泛应用。 为了提升和改进DOPO的合成,不少文献对合成中的4个反应,即酯化反应、酰基化反应、水解反应和关环反应进行了大量研究,但是由于缺少合适的分析方法和仪器,对酯化反应和酰基化反应仍没有得出明确的结论。 本文则采用了核磁共振磷谱以及测量反应产物HCl吸收碱液的温度变化两种方法,精确地得到了酯化反应和酰基化反应的优化条件。 首先采用核磁共振磷谱,讨论了酯化反应温度、原料配比和加料方式对酯化反应产物组成的影响,得出了邻苯基苯氧基二氯化磷(CC)含量高的工艺条件:反应温度80 ℃,PCl3过量25%~50%,采用邻苯基苯酚(OPP)加入PCl3的反滴法;并得出酯化反应产物的组成直接决定了6-氯-(6氢)-二苯并-(c,e)-氧磷杂己环(CDOP)在酰基化反应产物中的含量。 另通过测量HCl吸收碱液的温度变化,间接表征酰基化反应的反应速度,由此得出合适的酰基化反应温度和催化剂用量。 结果为:当催化剂固定为0.2 g时,酰基化反应在150 ℃几乎不反应,随温度升高,反应变快,180 ℃下4 h完全,190 ℃下1.5 h即可完成;温度180 ℃下,1~1.5 g/1 mol OPP的催化剂较为合适,酰基化反应在3~4 h结束。

关键词: 阻燃剂, 二氢-氧杂-膦杂菲-氧化物, 酯化反应, 酰基化反应

Abstract:

9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO), a versatile heterocyclic organophosphorus compound, is widely used for halogen-free fire retarding. In order to improve the synthesis process of DOPO, much effort has been devoted to analyzing these four reactions:esterification, acylation, hydrolysis and cyclization. However, due to the absence of suitable methods or instruments for analysis, it only led to some ambiguous results. In this paper, 31P nuclear magnetic resonance(31P NMR) and measuring the temperature of alkali solutions for HCl absorption were adopted to characterize the reactions to obtain precise optimized conditions for esterification and acylation. By 31P NMR, the effect of esterification temperature, the ratio of o-phenylphenol(OPP) to PCl3 and the addition order of reactants on the component content of products from esterification was discussed, and conditions for the highest content of o-phenyl ester phenoxy phosphorus dichloride(CC) were revealed as 80 ℃, a feeding order of adding OPP into PCl3 with 25%~50% extra PCl3. The dependence of the content of 6-chloro-dibenzo[c.e][1,2]-oxaphosphorine(CDOP) in products from acylation on the component content of products from esterification was also established. The acylation was investigated by measuring temperature change of aqueous NaOH when it absorbed HCl released from the reaction to give desirable reaction temperature and dosage of catalysis. In the present work, when 0.2 g catalyst is used, acylation of 0.2 mol esterified products does not proceed at 150 ℃, but has increased rate at higher temperatures and can finish in 4 h at 180 ℃ and 1.5 h at 190 ℃; a catalyst dosage of 1~1.5 g catalyst per mol OPP is practicable for acylation at 180 ℃ which can complete in 3~4 h.

Key words: flame retardant, dihydro-oxa-phosphaphen-anthrene-oxide(DOPO), esterification, acylation