【作者】 张丽萍；

【导师】 杨兴钰；

【作者基本信息】 华中师范大学 ， 有机化学， 2004， 硕士

【摘要】 高分子材料的应用领域日益扩大，已遍及国民经济的各个领域和人民生活的各个方面，由其可燃性所带来的火灾危险已受到各国政府和人民的密切关注，也是有关人类和环境的重大社会问题。因此，推广使用阻燃材料，对易燃和可燃材料进行阻燃处理，制订合理的阻燃法规和阻燃标准，以提高全社会防止火灾的能力，尽量减少火灾损失，具有重大的现实意义。 由于对材料的抑烟、减毒要求日益严格，使当今许多传统的阻燃剂面临困境，而膨胀型阻燃剂低烟、低毒的特点正给它的发展提供了良好的机遇，成为20世纪90年代以来阻燃剂最为活跃的研究领域之一，也被认为是实现阻燃无卤化的很有希望的途径之一。 因此，我们设计并合成了集酸源、炭源、气源于一体的三个系列二十四个未见文献报导的化合物：①N，N′-双（5，5-二甲基-4-芳基-2-氧（硫）代-1，3，2-二氧磷杂环己基-2-）哌嗪；②N，N′-双（5，5-二甲基-4-芳基-2-氧（硫）代-1，3，2-二氧磷杂环己基-2-）乙（丙、己）二胺；③N，N′-双（5，5-二甲基-4-芳基-2-氧（硫）代-1，3，2-二氧磷杂环己基-2-）脲（硫脲、胍）。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、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。 对部分具有代表性的化合物进行了热重（TG）和差示扫描量热（DSC）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，残炭量较高，具有较好的成炭作用。前两个系列的化合物在相应失重温区内都出现了吸热峰，这对阻燃体系是非常有利的。 将这三个系列化合物分别应用于醇酸清漆、环氧树脂（E-44）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）是标准实验方法。结果表明，题称化合物具有较好的阻燃效果。阻燃醇酸清漆时，添加量为1％可以达到1～2秒钟内的自熄效果；当添加量为10％时，环氧树脂样条燃烧长度在10～20mm左右，均能达到自熄效果。前两个系列的化合物在环氧树脂（E－44）中的阻燃效果明显优于第三系列。燃烧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。本论文阐述了膨胀型阻燃剂的阻燃机理，依据阻燃效果的不同，初步探讨了磷、硫、芳构型碳含量对阻燃性能的影响。 通过热分析和初步阻燃实验结果表明，我们所合成的目标化合物都具有较好的阻燃性能，与高分子材料具有较好的配伍性，是一类具有应用开发价值的膨胀型阻燃剂。更多还原

【Abstract】 With the development of science technology, the application of polymeric materials has been on the rise and has involved almost every aspect of people’s daily life. Accordingly, the fire disasters caused by then- combustion, which is a social problem that concerns all human beings and then- environment, have attracted more and more attention from people all over the world. Thus, it is of great significance to carry research on the treatment of inflammable materials with flame retardants, and to lay out reasonable flame retardant regulation and standard so as to improve people capability of preventing fire disasters and to reduce the loss caused by those disasters.Many traditional flame retardants are in a dilemma due to the more and more strict requirement of less smoke and less poisonous, which, however, offers a good opportunity for the development of the inrumescent flame retardant(IFR) owing to its low smoke and low poison characteristics,and IFR has becoming one of the most active research fields and one of the most promising approach to realizing the accomplishment of research on non-halogen flame retardant.Therefore, we design and synthesize 24 novel compounds that have never been Reported in any literature:(1)N,N-bis(5,5-dimethyl-4-aiyl-2-oxo(sul)-l,3,2-dioxaph osphacyclohexyl-2-)piperazine;(2)N,N’-bis(5,5-dunethyl-4-aryl-2-oxo(sul)-1,3,2-di oxaphosphacyclohexyl-2-)ethylene(promethylene,hexmethylene)diamine;(3)N,N’-bis(5,5-dimethyl-4-aryl-2-oxo(sul)-l,3,2-dioxaphosphacyclohexyl-2-)urea(thiourea ,imino-urea).The reaction conditions and after-treatment process are studied and improved. The structure of the target compounds are confirmed by IR, 1HNMR, 31NMR, MS and elementary analysis. The spectroscopy properties are analyzed systematically. Result shows that the structures of the synthesized compounds are identical with the expected ones.TG and DSC analysis of some of the typical compounds are discussed. Most of the compounds begin to decompose at 220℃ and have certain thermal stability.They decompose rapidly during 220-400℃ and overlap many high polymer materials decomposition temperature range and show good fireproofing performance with materials.The high carbon residues at 600℃, which shows that the compounds have good carbonization function.We apply the compounds to alkyd resin varnish, epoxy resin(E-44) to test their flame resistanc. Among the methods the level combustion method (GB2408-80) used in epoxy resin are standard methods. Result indicates that the title compounds have better flame resistance capability. The compounds I have the effect of self-extinguish within Is or 2s with 1% addition in alkyd resin varnish. All title compounds have the effect of self-extinguish with 10% addition in epoxy resin(E-44), and the combustion length is about 10~20mm in the level combustion test. Compounds I and II have better flame retardance than compounds III in epoxy resin(E-44). The samples foam and expand during the combustion process, and they carbonize and extinguish right after being deviated from fire, without melting and dropping and with low smoking. The thesis also gives a brief description of flame-retarding mechanisms and discusses the influence of the factor, such as P%,S% and the existence of aromatization carbon on flame retardance.The above thermal analysis and initial fireproofing test show that the target compounds do have better flame retardance and are promising m flame retardants.更多还原