【作者】 郭军红；

【导师】 杨保平； 崔锦峰；

【作者基本信息】 兰州理工大学 ， 化学工艺， 2008， 硕士

【摘要】 本论文通过将阻燃元素溴的高分子化,合成了低分子量高溴含量溴碳环氧树脂,将溴碳环氧树脂应用于防火涂料中,使得含溴本体阻燃高分子材料在防火涂料中既是基体树脂,又是高分子阻燃剂,双重功效不仅提高了防火涂料的阻燃时效性,而且增强了树脂与阻燃材料的相容性。以溴化钠-溴酸钠为溴化试剂,在乙醇溶液中,酸性条件下合成了四溴双酚A;以四溴双酚A与环氧氯丙烷在碱性条件下通过逐步聚合得到低分子量高溴含量四溴双酚A环氧树脂;对合成条件进行了探索,确定了原料配比与反应温度,并对影响产物性能与产率的因素进行了分析;确定合成四溴双酚A反应温度为室温,反应温度控制在25～30℃,NaBr以饱和水溶液形式加入,物料配比为BPA∶NaBr∶NaBrO₃/（mol）=3.0∶8.8∶4.35,回流反应温度控制在70～80℃之间;通过正交试验设计,以反应温度、四溴双酚A与环氧氯丙烷及加碱量之比设计四因素三水平正交试验,确定了当反应温度为60℃、TBA/环氧氯丙烷（mol）=1/8、TBA/NaOH（mol）=1/3时,合成的四溴双酚A环氧树脂环氧值为0.158,环氧当量约为623,平均分子量为1266,聚合度约为2,且产率最大。并对合成四溴双酚A和四溴双酚A环氧树脂的官能团进行了红外光谱表征。用高氯化聚乙烯树脂对四溴双酚A环氧树脂进行冷拼改性,当mTBA环氧树脂/mHCPE（重量比）=1/3、树脂占涂层干膜重量为1/3、聚磷酸铵的含量为16%～18%、三聚氰胺的含量为10%～11.5%、季戊四醇的含量为5%～6.5%时防火涂料耐火阻燃时间达150min。采用自制模拟燃烧试验装置对防火涂料的阻燃性能进行了测试,确定了防火涂料的最优配方;运用热重分析法和扫描电镜对防火涂料中P-C-N体系、氯化石蜡、三氧化二锑、硼酸锌、三氧化钼等的多元协效阻燃机理进行较深入的研究,为防火涂料的研究及工业生产提供有效的理论依据。通过对溴碳环氧树脂水性化的研究,选用苯基缩水甘油醚对三乙烯四胺封端,然后再与四溴双酚A环氧树脂加成得到自乳化型四溴双酚A环氧树脂固化剂。实验发现当苯基缩水甘油醚∶三乙烯四胺=2～2.2∶1时,表干时间30min,实干时间15h,耐碱时间360h,抗冲击强度45Kg·cm,涂层性能达最佳;当用四溴双酚A环氧树脂作为封端剂时所得涂层氧指数达35.4。通过对防火涂料基料、阻燃助剂、功能性添加剂等因素的分析,以正交试验确定了水性钢结构防火涂料的最佳配方,并对水性钢结构防火涂料进行了性能检测,开发出了环境友好型涂料,拓展了溴碳环氧树脂的应用领域。更多还原

【Abstract】 In this paper,the flame-retardant element bromine of polymeric was achieved using synthesis of low molecular weight high bromic bromine-carbon epoxy resin.The bromine-carbon epoxy resin was applied in flame-retardant coatings.The bromic intrinsical flame-retardant polymers used as binder of fire retardant coatings as well as macromolecule flame-retardant not only improved timeliness of fire retardant,but also reinforced comlatibility of resin and flame-retardant.Tetrabromobisphenol A was prepared using sodium bromide and sodium bromate as brominating agent,under acidic condition and in ethanol solution.Low molecular weight high bromic tetrabromobisphenol A epoxy resin was prepared using tetrabromobisphenol A and epoxy chloropropane under alkaline conditions by stepwise polymerization.Synthesis condition was explored,synthetical temperature was under room temperature and controlled within the range of 25～30℃,sodium bromide was joined in the form of saturation aqueous solution,mol ratio of material BPA:NaBr:NaBrO₃ was 3.0:8.8:4.35,the temperature of refluence reaction was controlled between 70～80℃,and then the influence factor of performance and percentage of production was analyzed.The orthogonal experiments was adopted,designing four factors and three level orthogonal test using reaction temperature,ratio of tetrabromobisphenol A,epoxy chloropropane and dosage of base as main influence factor.When reaction temperature was 60℃,the mol ratio of TBA/ECH was 1/8,TBA/NaOH was 1/3,the epoxy value of synthetical tetrabromobisphenol A epoxy resin was 0.158,epoxy equivalent weight was about 623,average molecular weight was 1266 and degree of polymerization was 2.The functional group of tetrabromobisphenol A and tetrabromobisphenol A epoxy resin has been characterized by Fourier Transform Infrared Ray（FT-IR）.When tetrabromobisphenol A epoxy resin was modified by hichloridize polyethylene under room temperature using as binder of super-thin intumescent flame-retardant coatings for steel structure and the ratio of TBA/HCPE was 1/3,the resin content in the film was 1/3,ammonium polyphosphate content between 16%～18%,melamine content between 10%～11.5%,pentaerythritol content between 5%～6.5%,the flame-retardant timeliness of the coatings was 150 min.The best formula of flame-retardant coatings was ascertained using a self-regulating simulative burning tester which tested the performance of fire-retardant for coatings.The mechanism of multi-synergetic fire retardant by system of P-C-N,chloroparaffin,antimonous oxide,zinc borate and molybdic oxide which provided effective academic sustain for research and industrial production that has been studied in-depth by Themrogrvaimertie Analysis（TGA）and Scanning Electron Microscope（SEM）.Self-emulsification tetrabromobisphenol A epoxy resin curing-agent was prepared that used for waterborne bromine-carbon epoxy resin.It was found when the ratio of phenyl glycidyl ether and triethylene-tetraamine was 2～2.2:1,the best performance of film achieved.For example surface drying time was 30 min,solid drying time was 15h,alkali resistant time was 360h,resisted impact strength was 45 Kg·cm.The oxygen-index reached 35.4 when using tetrabromobisphenol A epoxy resin as end capping agent.The best formula of waterborne fire-retardant coatings for steel structure was ascertained using orthogonal test which binder,fire-retartant auxiliary and functional additive was analyzed. The performance of waterborne fire-retardant coatings for steel structure reached requirement of national standard.The applied field of bromine-carbon epoxy resin was expanded that amicable environment type coatings and waterborne textile fire-retardant has been prepared.更多还原