10-（异丙基．2-醇）-9，10-二氢-9-氧杂-10-膦杂菲-10-氧化物的合成

以9,10-二氢-9．氧杂-10-膦杂菲-10-氧化物（DOPO）和丙酮为原料,合成10-（异丙基-2-醇）-9,10-二氢．9-氧杂．10．膦杂菲．10-氧化物。考察了原料摩尔比、反应温度和反应时间对产物收率的影响。结果表明,较优工艺条件为：n（丙酮）：n（DOPO）=12：1,反应温度为50℃,反应时间为30min时,DOPO的转化率为99％,目标产物收率为90％。     

10-(异丙基-2-醇)-9,10-二氢-9-氧杂-10-膦杂菲-10-氧化物的合成

以9,10-二氢-9-氧杂-10-膦杂菲-10-氧化物(DOPO)和丙酮为原料,合成10-(异丙基-2-醇)-9,10-二氢-9-氧杂-10-膦杂菲-10-氧化物。考察了原料摩尔比、反应温度和反应时间对产物收率的影响。结果表明,较优工艺条件为:n(丙酮)∶n(DOPO)=12∶1,反应温度为50℃,反应时间为30 min时,DOPO的转化率为99%,目标产物收率为90%。     

DOPO阻燃环氧树脂研究进展

综述了近年来用于阻燃环氧树脂的9,10-二氢-9-氧杂-10-膦菲-10-氧化物(DOPO)的协效阻燃体系、阻燃机理及反应活性方面的研究进展,并对今后DOPO阻燃领域的研究方向作出了展望。     

DAM-DOPO的合成及其阻燃性能

以9,10-二氢-9-氧杂-10-膦酰杂菲-10-氧化物（DOPO）、甲醛和二乙醇胺为原料,强酸性阳离子交换树脂作催化剂,分两步合成了新型反应型阻燃剂9,10-二氢-9氧杂-10-\[N,N-二(羟乙基)氨甲基\]-10-膦杂菲-10-氧化物（DAM-DOPO）,并制备了DAM-DOPO阻燃剂阻燃聚氨酯泡沫（PUF）,采用红外光谱、核磁共振等分析手段对DAM-DOPO进行了表征,同时通过极限氧指数值测定、水平燃烧试验和CAL 117D实验评估了阻燃PUF的阻燃性能。结果表明,合成的DAM-DOPO阻燃剂熔点为165~167 ℃;添加12 份（质量份,下同）DAM-DOPO阻燃的PUF的极限氧指数为26.5 %,阻燃性能通过GB 8410—2006标准和CAL TB 117D实验。     

10-(2,5-二羟基苯基)-9,10-二氢-9-氧杂-10-膦菲-10-氧化物的合成

以三氯化磷、邻苯基苯酚和对苯醌为主要原料,通过三步反应合成了含磷阻燃剂10-(2,5-二羟基苯基)-9,10-二氢-9-氧杂-10-膦菲-10-氧化物(ODOPB)。首先将酯化、酰基化、水解反应连续进行,得到了中间体2-(2-羟基苯基)苯基膦酸(HPPA),收率92.5%。然后HPPA分子内脱水成环反应得到9,10-二氢-9-氧杂-10-膦菲-10-氧化物(DOPO),收率93.2%。最后DOPO与对苯醌进行加成反应得到ODOPB,收率90.2%。三步合成总收率77.8%。HPPA的合成原料配比为n(三氯化磷)∶n(邻苯基苯酚)=1.3,以三氯化磷部分加入部分滴加的方式,且n(直接加入三氯化磷)∶n(滴加三氯化磷)=5.5,于150~200℃滴加反应。用红外光谱、元素分析、核磁氢谱、质谱对产物进行了表征。ODOPB已在覆铜板环氧树脂中成功应用,该合成方法已申请国家专利,正在进行产品中试。     

新型膦菲类阻燃剂的研究与应用

简要介绍了新型膦菲类阻燃剂9,10-二氢-9-氧杂-10-膦菲-10-氧化物(DOPO)及其衍生物的合成,综述了近年来国内外膦菲类阻燃剂的研究与应用进展情况。着重对合成的膦菲类阻燃剂新品种及其用做热塑性和热固性材料阻燃剂所显示的特性做了详细的介绍。     

DOPO基反应型阻燃剂的合成与应用研究进展

按酚类、丙烯酸酯类、胺类、苄醇类、脂肪醇类、环氧化合物类、酐和酸类等，对9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物（DOPO）基反应型阻燃剂的合成与应用研究进行了综述。     

磷酸酯类阻燃剂DOPO合成工艺的改进

为解决因采用高温反应所引起的9，10-二氢-9-氧杂-10磷杂菲-10氧化物（DOPO）。产品质量问题，首先采用在170-180℃下、8h反应的一步法合成中间产物6-氯-6氢-二苯并[c，e][1，2]-氧杂膦（CDOP），以简化反应过程，并减少副反应的发生，然后在过量水存在的条件下充分进行水解反应，并采用有机溶剂对水解产物进行提纯，以避免使用高真空；最后在116—125℃的低温进行的脱水反应。以防止产物发生分解，从而得到高纯度、高收率的产品DOPO。     

DOPO–肉桂酰胺阻燃剂制备及其在PLA中应用

以9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)、肉桂酰胺为原料合成了一种氮磷复合型阻燃剂(DOPO–CDE),通过傅立叶变换红外光谱、核磁共振氢谱对合成产物结构进行了鉴定,显示DOPO–CDE成功制备。研究了原料配比、反应温度、反应时间对阻燃剂产率的影响,发现在DOPO:肉桂酰胺物质的量之比为1.5∶1,反应温度140℃,反应时间10 h时,产率可达38.13%。此外,通过热重表征,发现合成阻燃剂比DOPO热稳定性有了明显提高。在聚乳酸(PLA)中添加质量分数5%的DOPO和质量分数5%的DOPO–CDE得到两种阻燃复合材料,并分别测试其极限氧指数(LOI)和拉伸性能。结果表明,添加DOPO和DOPO–CDE的PLA阻燃复合材料的LOI由PLA的20.1%分别提高到26.4%和27.4%;添加DOPO–CDE的PLA阻燃复合材料拉伸强度和断裂伸长率分别达到55.1 MPa和8.7%,比添加DOPO的复合材料分别提高了13.6%和123.1%。     

阻燃剂DOPO及其衍生物在环氧树脂中的应用

综述了9,10-二氢-9-氧杂-10-膦菲-10-氧化物(DOPO)及其衍生物作为阻燃剂、固化剂引入环氧树脂提高环氧树脂阻燃和热稳定性的国内外研究进展,并指出了今后该领域简化工艺、降低成本的发展方向。     

有机磷系化合物反应阻燃聚乳酸的机理与性能

介绍9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)及其衍生物10-(2,5-二羟基苯基)-10-氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO-HQ)分别反应阻燃聚乳酸(PLA)的机理和对PLA力学性能、阻燃性能、耐热性能的影响。结果表明,少量DOPO对PLA有良好的阻燃效果,少量过氧化二异丙苯(DCP)与DOPO-HQ并用能有效改善PLA的阻燃性能和热稳定性能。5%DOPO-HQ/0.5%DCP阻燃PLA具有良好的综合性能,拉伸强度为49.37MPa,断裂伸长率为5.03%,氧指数为32%,试样热失重5%、50%时的温度分别提高38、36℃。     

两种含磷阻燃剂的合成及其结构表征

采用邻苯基苯酚及三氯化磷为原料,氯化锌为催化剂,以“一锅法”合成了新型含磷阻燃剂9,10-二氢-9氧杂-10-磷杂菲-10-氧化物(DOPO)及10-(2’,5’-二羟基苯基)-9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(ODOPB),并通过红外光谱、1H核磁谱、元素分析等对这两种化合物进行结构鉴定。合成DOPO的方法,不采用有机溶剂,因而安全、环保、产品纯度高达99.5%,满足所有应用的要求。     

新型含三嗪结构氧杂膦菲阻燃剂的合成

以三聚氯氰、对羟基苯甲醛和9,10-二氢-9-氧杂-10-膦菲-10-氧化物(DOPO)为主要原料,经两步反应合成了一种新型含三嗪结构氧杂膦菲阻燃剂PN-FR。第一步反应以三聚氯氰、对羟基苯甲醛为原料,二氯甲烷和水为混合溶剂,相转移催化剂作用下回流反应2 h,得2,4,6-三(4-醛基苯氧基)-1,3,5-三嗪(ZJT),收率98.8%;第二步在n(DOPO)∶n(ZJT)∶n(催化剂)=3.2∶1∶0.8,66℃回流反应3 h条件下得目标产物PN-FR,收率95.8%。用FTIR、EA、1HNMR、LC/MS、TG和DSC对中间体和产物作了结构表征和热性能分析。将该阻燃剂初步应用于环氧树脂绝缘层压板的阻燃,当阻燃剂质量分数为15%时,绝缘层压板氧指数达到36.2,通过UL-94 V-0级测试。该文研究工作的新颖性,已为四川省科学技术信息研究所2006年10月26日出具的第A0601512号《科技查新报告》所证实。     

Reversibility of hydration and dehydration reactions of a phosphaphenanthrene oxide (DOPO) pendent group on polyamide

The cyclic phosphorous group, 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide‐10‐yl (DOPO), attached on a polyamide PA–DOPO could be hydrated to give its open‐chained form with phosphinic acid groups (PA–DOPO–HD). The open‐chained phosphinic acid groups could be reformed to its cyclic DOPO form through thermal dehydration. The occurrence of the hydration and thermal‐dehydration reactions and the chemical structure of the polyamides were demonstrated with FTIR, ³¹P NMR, and thermal analysis. PA–DOPO–HD exhibited similar inherent viscosity and better organosolubility than the original polyamide PA–DOPO. Copyright © 2003 Society of Chemical Industry     

DOPO纯度的分析

以CDCl3为溶剂、TMS为内标,测定9,10-二氢-9-氧杂-10-膦杂菲-10-氧化物（DOPO）的核磁共振氢谱,选定DOPO、邻苯基苯酚（OPP）和2′-羟基联苯基-2-次磷酸（HPAA）特征质子峰作为定量峰,通过面积归一化法计算DOPO的绝对含量,该方法测定结果误差小于0.3%,具有准确、简便、快速等优点,可为DOPO的纯度分析提供参考。     

New strategy towards flame retardancy through design,synthesis, characterization,and fire performance of a chain extender in polyamide 6 composites

A novel flame‐retardant chain extension agent (9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide)‐3,5‐triglycidyl isocyanurate defined as DOPO‐TGIC was synthesized, and its chemical structure was well characterized and confirmed. The effect of DOPO‐TGIC as a synergistic agent on the flame retardancy, rheology, thermal and mechanical properties of polyamide 6/aluminum diethylphosphinate (PA6/AlPi) composites were investigated in details. The results demonstrated that PA6/AlPi/DOPO‐TGIC composites (1.6 mm) successfully passed UL‐94 V‐0 rating with the limiting oxygen index value of 30.5% when the total loading amount of AlPi/DOPO‐TGIC was 10 wt%. In order to achieve the equal flame‐retardant level, the individual AlPi was required 14 wt%. The incorporated DOPO‐TGIC improved the complex viscosity of PA6/AlPi/DOPO‐TGIC composites due to the chain extending reaction between epoxide groups in DOPO‐TGIC and the terminal groups of PA6 matrix. The mechanical performance of PA6/AlPi/DOPO‐TGIC composites was also improved compared with that of PA6/AlPi composites. DOPO‐TGIC stimulated to the formation of more sufficient and compact char layer during combustion. The higher melt viscosity and compact char layer of PA6 composites effectively constrained the volatilization of flammable gases, thus the heat release was reduced. Consequently, the introduction of DOPO‐TGIC simultaneously enhanced the flame retardant and mechanical properties of PA6/AlPi/DOPO‐TGIC composites compared with that of PA6/AlPi composites. POLYM. ENG. SCI., 59:E206–E215, 2019. © 2018 Society of Plastics Engineers     

Flame retardant performance of a carbon source containing DOPO derivative in PET and epoxy

The combination of gas‐phase and condensed‐phase action will contribute to high quality flame retardant. A novel 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO)‐based flame retardant (DOPO‐DOPC), which contains carbon source was synthesized in favor of conducting the effect of gas‐phase as well as promoting the char formation in condensed‐phase. The chemical structure of DOPO‐DOPC was characterized by nuclear magnetic resonance (NMR) and Fourier transform infrared spectroscopy (FTIR). DOPO–DOPC was used as an additive in poly(ethylene terephthalate) (PET) and epoxy resin (EP). The flame retardancy of PET/DOPO‐DOPC and EP/DOPO‐DOPC composites were studied by limiting oxygen index (LOI) and UL‐94 test. The results showed that the incorporation of DOPO–DOPC into PET or EP could obviously improve their flame retardancy. The LOI values of modified PET or EP, which contained 10 wt % DOPO‐DOPC reached 42.8 and 31.7%, respectively. The thermogravimetric analysis (TGA) results revealed that DOPO–DOPC enhanced the formation of char residues. The Laser Raman spectroscopy (LRS) was used to investigate the carbon structure of thermal oxidation residues. Because of the combination of the gas phase flame retardant effect of DOPO moiety and the promoting formation of char residues in condensed phase, the PET and EP composites exhibited significant improvement toward flame retardancy. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44639.     

Cage–ladder-structure,phosphorus-containing polyhedral oligomeric silsesquinoxanes as promising reactive-type flame retardants for epoxy resin

We synthesized a novel cage–ladder-structure, phosphorus-containing polyhedral oligomeric silsesquinoxane (CLEP–DOPO–POSS) via the hydrolytic condensation of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO)–vinyl trimethoxysilane (VTMS) with 2-(3,4-epoxycyclohexyl) ethyl trimethoxysilane and then incorporated it into epoxy resins (EPs) in different ratios with thermal curing technology. The structure of CLEP–DOPO–POSS was confirmed by Fourier transform infrared spectroscopy, NMR spectroscopy (¹H-NMR and ²⁹Si-NMR), matrix-assisted laser desorption ionization time-of-flight, and X-ray diffraction. The thermal stability, mechanical properties and flame retardancy effect of CLEP–DOPO–POSS on EP were comprehensively evaluated via thermogravimetric analysis (TGA), dynamic mechanical analysis, universal tensile testing, limiting oxygen index (LOI) measurement, UL-94 testing, and cone calorimetry. The flame-retardant mechanism of the EP modified with CLEP–DOPO–POSS was investigated by TGA–IR, TGA–mass spectrometry, and scanning electron microscopy. The experimental results show that CLEP–DOPO–POSS was homogeneously dispersed in the EP matrix. The LOI value reached 31.9, and the UL-94 grade passed V-0 with the presence of only 0.28% P (2.91 phr CLEP–DOPO–POSS). In addition, the EP composite containing CLEP–DOPO–POSS exhibited a better thermal stability and mechanical properties. The flame-retardant mechanism was attributed to the quenching effect of the phosphorus-containing free radicals and the formation of phosphorus- and silicon-containing char layers in the condensed phase. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47607.