【作者】 宦双燕；

【导师】 杨兴钰；

【作者基本信息】 华中师范大学 ， 有机化学， 2001， 硕士

【摘要】 火灾每年给世界各国造成大量的人员伤亡和巨大的财产损失，对易燃和可燃材料进行阻燃处理是防止和减少火灾的战略性措施之一，阻燃剂及阻燃材料的研究、生产和应用是关系到“环境和人类”的重大举措。 有机阻燃剂主要是卤系和磷系，卤系由于dioxin（裂解和燃烧产物毒性）问题，引起社会关注。磷系阻燃剂近年来受到重视，特别是其中的膨胀型阻燃剂，由于具有低烟、低毒的优点，不含卤素和锑，是阻燃剂无卤化的途径之一，前景看好。在含磷阻燃剂的研究开发中，这种集碳源、酸源和气源于一体的膨胀型阻燃剂日益引起重视。我们采用Pudovik加成和成盐反应等方法引入集碳源和酸源于一体的1，3，2-二氧磷杂环己烷结构，合成了三个系列共二十六个未见文献报导的化合物：（1）N，N’-对苯二胺基-二苄基-α-氨基-5，5-二甲基-4-杂芳基-2-氧代-1，3，2-二氧磷杂环己烷膦酸酯；（2）5，5-二甲基-4-杂芳基-2-酰胺乙基-2-氧代-1，3，2-二氧磷杂环己烷膦酸酯（及其N-羟甲基化产物）；（3）5，5-二甲基-4-杂芳基-2-氧代-1，3，2-二氧磷杂环己环磷酸三聚氰胺盐。我们对反应条件和后处理过程进行了探索和改进。采用IR，¹HNMR，¹³CNMR，³¹PNMR，MS和元素分析等方法对目标化合物进行了结构表征，并对其波谱性质进行了系统分析，结果表明合成化合物的结构和预期目标化合物结构一致。 对部分具有代表性化合物进行了热重（TG）和差热（DTA）分析，这些化合物多数在220℃以上开始分解，具有一定的热稳定性，在220～400℃降解迅速，与大部分高分子材料的热氧降解温区重叠，具有较好的阻燃配伍性能。600℃时，残炭量均较高，在30％左右，具有较好的成炭作用。 将这三个系列化合物分别应用于醇酸清漆，环氧树脂（E-44）和棉布中进行初步阻燃性能测试。其中用于环氧树脂（E-44）的水平燃烧试验（GB2408-80）和用于棉布的垂直燃烧实验（GB5455-97）是标准实验方法。结果表明，题称 一 化合物具有较好的阻燃效果。其中，化合物二＿且添加量为 1％时可以达到 1秒钟 内自熄的效果，含一OH基的化合物酯溶性好，添加量较大时，阻燃漆膜仍然透 明光亮，含卤素的化合物，添加量小时O．5％)就能达到1秒内自熄的效果，可见＿＿－这类化合物中磷一卤之间存在协同效应。化合物1－＿。作为反应型阻燃剂应用到 棉布中，经过阻燃整理的棉布手感较好，可以达到离火自熄的效果，且具有一定 的耐洗性能，垂直燃侥实验中，化合物！e阻燃效果最好，初始燃烧长度为9． Zcm，洗后燃侥长度为12．scm；化合物巨＿f在环氧树脂（E—44）中阻燃效果较前 两个系列好，水平燃烧试验中，添加量在10％左右时，燃烧长度小于Zcm，燃浇 过程中有发泡膨胀现象，样品离火后迅速炭化自熄，无熔融、滴落现象，发烟量 小，是一类较好的膨胀型阻燃剂。 通过热分析和初步阻燃应用实验可见，合成的目标化合物都具有较好的阻 燃性能，是一类具有应用开发价值的膨胀型阻燃剂。更多还原

【Abstract】 Fire disasters make great number of deaths and heavy property loss every year all over the world. Treating inflammable materials with flame retardants is one of the strategic measures to prevent and decrease fire disasters. The study, produce and use of flame retardants and fireproofing materials are significant behaves that concerning " ENVIRONMENT AND HUMAN " problem.Organic flame retardant includes halogenated and phosphated flame retardant. Halogenated flame retardant set off attention because of dioxin (toxicity of splitting decomposition and combustion products) problem. People attach importance to phosphated flame retardant especially intumescent flame retardant which containing no halogen and antimony. Being an effective way to produce nonhalogen flame retardant and with merits of low smoking and low toxicity, Intumescent flame retardant has a positive prospect. Intumescent flame retardant which containing carbon source,acid source and gas source as a whole has received increasing interest in the investigate and develop fields of phosphorus-containing flame retardant. To get further information, we introduced the structure of 1,3, 2-dioxaphosphorinane through Pudovik addition and salt forming reaction and have synthesized 26 novel compounds : (1) N, N ’ -phenylenediamino-Dibenzyl-a-amino-5, 5-dimethyl-4-heteroaryl-2-oxy-1,3, 2-dioxaphosphorinane phosphonate; (2)5, 5-dimethyl-4-heteroaryl-2-amide-ethyl-2-oxy-l, 3, 2-dioxaphosphorinane phosphonate (and it’s N-hydroxymethyl product); (3) 5, 5-dimethyl-4-heteroaryl-2-oxy-l, 3, 2-dioxaphosphorinane phosphate melamine salt. The reaction conditions and aftertreatment process were studied and improved. The structures of the title compounds were confirmed by IR^HNMR, 13 CNMR, 31 PNMR, MS and elementary analysis. The spectroscopy properties were investigatedsystemetically. Result shows that the structures of the synthesized compounds are identical with the expected ones.TG and DTA analysis of some of the compounds were discussed. Most of the compounds begin to decompose at 220 and have certain thermal stability. They decompose rapidly during 220~400癈 and overlapping many high polymer materials’ decomposition temperature range and show good fireproofing compatibility with materials. The high carbon residue of about 30% at 600癈 shows that the compounds have good carbonization function.We applied the Compounds to alkyd resin varnish, epoxy resin (E ?44) and cotton cloth to test their flame resistance. Among the methods,the Level combustion method (GB2408-80) used in epoxy resin (E-44) and perpendicular combustion method (GB5455-97) used in cotten cloth are standard methods. Result indicates that the title compounds have good flame resistance. The compounds I ,~i give effect of self-extinguish in Is with 1% addition in alkyd resin varnish. Compounds with-OH have good dissolvability and give transparent and bright varnish coat with high addition. Compounds with-Cl give effect of self-extinguish in Is with 0. 5% addition, phosphorus and halogen in these compounds show cooperate fireproofing effect. Compounds I e~h can be used in cotton cloth as reactive flame retardant. The treated cloth gives good feel and can give self-extinguish effect after deviate from fire and has certain washing fastness. Compound I a~f have better flame resistance than others in epoxy resin (E-44). In the level combustion test, combustion length is less than 2 cm with a 10% addition. The samples foamed and expand during combustion process. They carbonize and extinguish after deviate from fire,without melting and dropping and with low smoking.Thermal analysis and initial fireproofing test show that the title compounds are promising intumescent flame retardants.更多还原