硕士学位论文新型磷氮系膨胀型阻燃剂的合成及其阻燃性能研究作 者：卞小闯指导教师：朱广军教授南京理工大学2013年3月MDDissertationStudy on the Synthesis and Flame Resistance ofNovel Intumescent Flame RetardantsContaining Phosphorus and NitrogenByBian Xiao Ch uangSupervised by ProjZh u GuangjunNanj ing University of Science&TechnologyMarch，2013声 明本学位论文是我在导师的指导下取得的研究成果，尽我所知，在本学位论文中，除了加以标注和致谢的部分外，不包含其他人已经发表或公布过的研究成果，也不包含我为获得任何教育机构的学位或学历而使用过的材料。与我一同工作的同事对本学位论文做出的贡献均已在论文中作了明确的说明。B年弓只移B学位论文使用授权声明南京理工大学有权保存本学位论文的电子和纸质文档，可以借阅或上网公布本学位论文的部分或全部内容，可以向有关部门或机构送交并授权其保存、借阅或上网公布本学位论文的部分或全部内容。对于保密论文，按保密的有关规定和程序处理。研究生签名： 了：!鱼2 20|亏年；R巧日硕士论文 新型磷氮系膨胀型阻燃剂的合成及其阻燃性能研究摘 要膨胀型阻燃齐U(IFR)是一种以氮、磷为主要组成的复合阻燃剂，广泛应用于日常用品、电子电器、国防工业、交通运输、宇航事业和建筑等诸多领域。本文以POCl3和新戊二醇、季戊四醇等为主要原料合成了系列新型膨胀型阻燃剂，并对其性能及其在聚丙烯中应用进行了研究。本论文主要包含以下几点内容：1、本文制备了以新戊二醇磷酰氯为中间体的系列膨胀型阻燃剂，在合成中间体新戊二醇磷酰氯时采用超声波技术，探讨了超声波条件下对反应产率的影响。在合成新戊二醇磷酰氯为中间体的系列膨胀型阻燃剂时以新戊二醇乙撑磷酰胺为例通过单因素实验探讨了反应温度、溶剂的选择、缚酸剂对反应产率的影响。本文以中间体与苯并咪唑及苯并三氮唑合成了两种未见文献报道的新型膨胀型阻燃剂，并对其反应机理进行了探讨。2、本文制备了以季戊四醇双磷酰氯为中间体的系列膨胀型阻燃剂，在合成中间体季戊四醇双磷酰氯时采用超声波技术，探讨了超声波对反应时间、反应温度的影响。在合成季戊四醇双磷酸酯二乙胺时，设计了正交实验，确定了最优工艺条件为：n伸间体1：m二乙胺1=1：4，反应温度80，反应时间3h。3、通过热重分析(TGDSC)对制得的八种阻燃剂的热稳定性进行测试，得出各种阻燃剂的初始分解温度及残炭量，并通过高温马弗炉煅烧实验，确定膨胀型阻燃剂受热后膨胀成炭的能力，筛选出性能优良的膨胀型阻燃剂，并初步探讨磷、氮、碳三者协同作用对其膨胀成炭的能力的影响。4、在所制得的八种阻燃剂中挑选具有代表性的三种阻燃剂，通过不同配比与聚丙烯进行混炼，测定它们的氧指数、阻燃效率、冲击强度、拉伸强度，分析力学性能降低原因，总结规律，得出最佳阻燃剂的添加量。本课题的实验工作对今后膨胀型阻燃剂的实际生产及应用具有重要的指导意义。关键词：膨胀型阻燃剂，新戊二醇，季戊四醇，超声波，合成工艺条件，性能测试硕士论文 新型磷氮系膨胀型阻燃剂的合成及其阻燃性能研究AbstractIntumescent flame retardant(IFR)is a kind of composite flame retardant with nitrogenand phosphorus as the main component which is widely used in commodity,electronicappliances，defense industry,transportation，aerospace industry and construction,etcIn thispaper a series of novel IFR were synthesized with POCl3，neopentyl glycol andpentaerythritol as the main reagents，and aferwards their properties and application werestudiedThe main research contents are as follows：1In this paper,series Intumescent flame retardant were prepared by using neopentylglycol chlorophosphate as intermediate，ultrasonic technology was used to synthesiseneopentyl glycol chlorophosphate，and the effect of ultrasonic on yield Was studied，thee伍：ct of ultrasonic on yield of products Was studiedTaking the synthesis of neopentylglycol ethylene phosphoramide as an examplethe effect factors on yield such as reactiontemperature，solvent，acid-binding agent were studied through single factor experimentTwo kinds of novel IFR were prepared by reacting intermediate、ith benzimidazole andbenzotriazole respectively in this paper,and they havent been reported previously,then theirreaction mechanism Was studied2In this paper,another series intumescent flame retardant were prepared by using pentaerythritol phosphonyl dichloride as intermediate，ultrasonic technology Was also usedto synthesise pentaerythritol phosphonyl dichloride，and effects of ultrasonic on reactiontime and reaction temperature were studiedThe optimal reaction conditions of preparrationof pentaerythritol double phosphate diethylamine were obtained through orthogonalexperiment and as fellows：n(intermediate)：n(diethylamine)=1：4reaction temperature is80reaction time is 3 h3T11ermai stability of eight kinds of IFR Was tested through TGDSC，their initialdecomposition temperature were obtained as well as the amount of residual carbonTheability of intumescing into carbon after heated of IFR Was obtained through hi曲temperature muffle furnace calcination experimentThe optimal IFR Was selected and usedto study the effect of synergy of phosphorus，nitrogen and carbon on the ability ofintumescing into carbon4Three kinds of representative IFR were selected and mixed with polypropylene indifferent ratioTheir oxygen index，flame retardant efficiency，impact strength，tensilestrength were tested and the reason of decreasing in mechanical properties were analysedIIIAbstract 硕士论文Finally the optimal additive amount of flame retardant was obtained after summarizing theabove rulesThe experiments in this paper have an important guiding significance on theproduction and application of IFR in futureKey words：intumescent flame retardant，neopentyl glycol，pentaerythritol，ultrasonic，synthesis conditions，property testing硕士论文 新型磷氮系膨胀型阻燃剂的合成及其阻燃性能研究目 录摘iIjIAbstractIII目 录、l，1绪论111课题概述112阻燃剂的分类1121无机阻燃剂一2122卤系阻燃剂一3123有机磷系阻燃剂一3124有机硅系阻燃剂一413未来阻燃剂的研究方向414膨胀型阻燃剂概述5141膨胀型阻燃剂的分类5142膨胀型阻燃剂的组成及阻燃机制615本课题研究的主要内容及意义7151课题研究的主要内容一715