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

doi:10.11944/j.issn.1000-0518.2017.02.160203

摘要/Abstract

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

赖华, 刘兴, 朱小明, 龙婉君, 李想, 熊平生. 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[J]. 应用化学, 2017, 34(2): 151-157.

LAI Hua, LIU Xing, ZHU Xiaoming, LONG Wanjun, LI Xiang, XIONG Pingsheng. Optimization of Esterification and Acylation on Synthesis of Flame Retardant 9,10-Dihydro-9-oxa-10-phosphaphen-anthrene-10-oxide[J]. Chinese Journal of Applied Chemistry, 2017, 34(2): 151-157.

参考文献

[1]	JIANG Jianzhong,CAI Chun. Synthesis and Application of a Novel Flame Retardant Intermediate DOPO[J]. Jiangsu Chem Ind,2004,32(1):12-15(in Chinese). 蒋建中,蔡春. 新型阻燃剂中间体DOPO合成与应用概述[J]. 江苏化工,2004,32(1):12-15.
[2]	Wang C S,Shieh J Y. Synthesis and Properties of Epoxy Resins Containing 2-(6-Oxid-6H-dibenz[c,e][1,2]oxa-phosphorin-6-yl) 1,4-benzenediol[J]. Polymer,1998,39(23):5819-5826.
[3]	Neisius M N,Lutz M,Rentsch D,et al.Synthesis of DOPO-Based Phosphonamidates and Their Thermal Properties[J]. Ind Eng Chem Res,2014,53(8):2889-2896.
[4]	Kim W J,Hoang D Q,Vothi H,et al.Synthesis, Flame Retardancy, and Thermal Degradation Behaviors of Novel Organo-phosphorus Compounds Derived from 9,10-Dihydro- 9-oxa-10-phosphaphenanthrene-10-oxide(DOPO)[J]. Macromol Res,2016,24(1):66-73.
[5]	YOU Geyun,CHENG Zhiquan,PENG Hao,et al.Research Progress on Synthesis and Application of Cyclotriphosphazene-based Flame Retardants[J]. Chinese J Appl Chem,2014,31(9):993-1009(in Chinese). 游歌云,程之泉,彭浩,等. 环三磷腈类阻燃剂的合成及应用研究进展[J]. 应用化学,2014,31(9):993-1009.
[6]	XIONG Yanbing. Recent Research Advances of DOPO Viewed from Correlated Patent Applications at Domestic[J]. Plast Addit,2015,(4):15-19(in Chinese). 熊燕兵. 从国内最新专利申请看DOPO的阻燃研究进展[J]. 塑料助剂,2015,(4):15-19.
[7]	ZHI Xiaoqiong,HUANG Jie,TANG Anbin,et al.Comparison and Selection of the Preparation Methods of DOPO[J]. Insul Mater,2005,(3):55-59(in Chinese). 支肖琼,黄杰,唐安斌,等. DOPO 制备方法的比较与选择[J]. 绝缘材料,2005,(3):55-59.
[8]	MA Qingfeng,KANG Huibao,WANG Lisheng. Synthesis of 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide as a New Flame Retardant Intermediate[J]. Adv Fine Petrochem,2002,3(1):46-48(in Chinese). 马庆丰,康惠宝,王利生. 新型阻燃剂中间体9,10-二氢-9氧杂-10-膦杂菲-10-氧化物的合成[J]. 精细石油化工进展,2002,3(1):46-48.
[9]	QIAN Lijun,ZHOU Zhengmao. Study on Synthesis of Fire Retardant Monomer 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide[C]//Proceedings of 2007 National Flame Retardant Conference. Beijing:Beijing Institute of Technology,2007:13-18(in Chinese). 钱立军,周政懋. 9,10-二氢-9氧杂-10-膦杂菲-10-氧化物的合成工艺及工业化研究[C]//2007中国阻燃学术年会会议论文集. 北京:北京理工大学,2007:13-18.
[10]	CHEN Xiuli,WANG Xinlong. Synthesis of High-purity Reactive Flame Retardent DOPO by One-pot Method[J]. Plast Addit,2006,(1):23-27(in Chinese). 陈秀丽,王新龙. “一锅”法合成高纯度反应型含磷阻燃剂 DOPO[J]. 塑料助剂,2006,(1):23-27.
[11]	XIONG Tao,CHEN Zhuxing,WEI Wenbin,et al. Synthesis and Purification Method of 9, 10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide:CN, 201310002453.3[P],2013-01-05(in Chinese). 熊涛,陈祖兴,魏文彬,等. 一种9,10-二氢-9氧杂-10-膦杂菲-10-氧化物的合成及其提纯方法:中国,201310002453.3[P],2013-01-05.
[12]	ZHANG Xue,MA Huijuan,LI Yonggang,et al.Synthesis and Investigation of Flame Retardant DOPO[J]. J Hubei Univ(Nat Sci),2014,36(4):351-353(in Chinese). 张雪,马会娟,李永刚,等. 反应型阻燃剂中间体DOPO合成研究[J]. 湖北大学学报(自然科学版),2014,36(4):351-353.
[13]	YE Ruhan. Study and Application of NMR of Phosphorous-containing Compounds[D]. Guangzhou:Guangdong University of Technology,2011(in Chinese). 叶汝汉. 含磷化合物核磁共振谱图的研究与应用[D]. 广东:广东工业大学,2011.
[14]	Buysch H,Glock V. Process for Preparing 6-Oxo-(6H)-dibenz-[c,e][1,2]-oxaphosphorins(ODOPs):US,5650530[P],1997-7-22.
[15]	Abranyi-Balogh P,Keglevich G. Practical Synthesis of 6-Chloro-dibenzo[c,e][1,2]-oxaphosphorine[J]. Synth Commun,2011,41(10):1421-1426.