有机聚合磷酸酯阻燃剂的合成及应用研究

【作者】 曹阳；

【导师】 杨锦飞；

【作者基本信息】 南京师范大学 ， 有机化学， 2014， 硕士

【摘要】 随着塑料、橡胶和纤维等高分子材料的迅猛发展,阻燃剂的需求成迅猛的增长趋势。自20世纪90年代以来,随着阻燃剂研究的深入,磷酸酯类阻燃剂从单磷酸酯向聚合磷酸酯类阻燃剂过渡。磷酸酯阻燃剂具有蒸汽压低、迁移性小、耐久性好、毒性低、等优点,因而被广泛用于多种合成高分子材料中。本文研究并采用绿色的工艺合成了单磷酸酯阻燃剂磷酸三苯酯(TPP),并以TPP为原料,合成聚合磷酸酯RDP、BDP,采用正交实验法和单因素法分别对催化剂的种类、反应时间、反应温度、物料比等因素进行了讨论,确定了最佳工艺条件:磷酸三苯酯(TPP):反应温度15～20 ℃,反应时间2.5 h,n(PhOH):n(NaOH)=1:1.15,n(PhOH):n(POC13)=1:0.36,产率可达94.7%。对废水成分进行分析,苯酚含量和磷酸根含量均符合国家化学合成类废水排放标准。溶剂水重复利用2次仍能达到理想的效果。在小试工艺基础上进行中试,反应平稳,实验结果良好。间苯二酚双(二苯基)磷酸酯(RDP):采用TPP和间苯二酚按2.1:1.0的摩尔比,添加1.00%‰用量的碱性离子液体作为催化剂,在120～130℃下进行酯交换反应,反应时间为4h,得到无色透明的产品,其中RDP单体收率可达到90.7%;双酚A双(二苯基)磷酸酯(BDP):采用TPP和双酚A按2.2:1.0的摩尔比,添加1.3%‰用量的碱性离子液体作为催化剂催,在130～140 ℃下进行酯交换反应,反应时间为4 h,得到无色透明的产品,其中BDP单体收率可达到89.7%;在小试工艺基础上对RDP、BDP进行中试,反应平稳,实验结果良好。对中试产品进行表征,与目标产物相符。利用HPLC对RDP和BDP中TPP含量进行检测,达到市场产品标准。采用IR、1HNMR等方法对产品结构进行表征,结果与目标分子相符,并测试酸值、粘度和热稳定性等物理性质,符合市场产品要求。在参考国内外相关文献之后,将合成产品RDP、BDP、TPP用于聚碳酸酯/丙烯腈-丁二烯-苯乙烯三元共聚物(PC/ABS)共混物,对材料的阻燃性能和力学性能进行了相关的测试分析,实验结果表明RDP、BDP是性能优良的阻燃剂。更多还原

【Abstract】 With the rapid development of polymer materials such as plastic,rubber and fiber,the demand of flame retardants have been showing a tendence of increaseing in recent years.With the deep research of the flame retardants,phosphate flame retardants make the transition from single phosphate to polymer phosphate.phosphate flame retatdants have advantages on low vapour pressure,poor mobility and low toxicity.Therefore they are widely used in a variety of synthetic polymeric materials.In this paper,we study and synthesis triphenyl phosphate(TPP)in a green process,and use TPP as raw material to synthesis low polymeric phosphate RDP、BDP.The effect of the kinds of catalyst,the reaction time,reaction temperature and ratio of raw materials are investigated by orthogonal experiment and single factor.The optimum technological conditions are determined.Triphenyl phosphate(TPP):the reaction temperature is 20～25 ℃,the reaction time is 2.5 hour,n(PhOH):n(NaOH)mole ratio is 1:1.15,n(PhOH):n(POCl3)mole ratio is 1:0.36,the yield of TPP can be up to 94.7%.The composition of waste water is analyzied.The result shows that phenol content and phosphate content meet the national industrial wastewater discharge standards.When the solvent of water is reused in 2 times,it can still achieve the ideal effect.Take process for pilot on the basis of underbrush,the reaction is smooth and steady;the result of test is good.Resorcinol(diphenyl)phosphate ester(RDP):n(TPP):n(resorcinol)mole ratio is 2.1:1.0,the alkaline ionic liquids catalyst dosage is 1 ‰.The reaction temperature is 120～130 ℃,the reaction time is 4 hour.At the end of reaction,the colourless and transparent product is got.The yield of RDP can be up to 90.7%.Bisphenol A dis(diphenyl)phosphate ester(BDP):n(TPP):n(bisphenol A)mole ratio is 2.2:1.0.the alkaline ionic liquids catalyst dosage is 1.3‰,The reaction temperature is 130～140 ℃,the reaction time is 4 hour,At the end of reaction,the colourless and transparent product is got.The yield of BDP can be up to 89.7%.Take large process for RDP and BDP on the basis of underbrush,the reaction is smooth and steady;the result of test is good.The products are characterized,matching their target molecules.RDP and BDP are teted by HPLC,meeting the standards.IR and 1H NMR are used to characterize their chemical structures,matching with their target molecules.The results show the four oligomeric phosphate flame retardants have better tests the acid value,viscosity and thermal stability.On the base of literatures at home and abroad,the RDP,BDP and TPP is respectively tesed PC/ABS.The flame retardant properties and mechanical properities of the materials are studied.The results show that RDP and BDP are a kind of high performance flame retardants.更多还原