CN112094297A - 一种含恶二唑环反应型阻燃剂及其制备方法 - Google Patents
一种含恶二唑环反应型阻燃剂及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种含恶二唑环反应型阻燃剂及其制备方法,包括:5‑(氨基甲基)‑1,3,4‑噁二唑‑2‑羧酸乙酯与磷试剂(含磷酰氯基化合物)反应产物经水解制备含恶二唑环反应型阻燃剂;该反应型阻燃剂含双官能度羧酸,可用作橡胶、塑料、纤维、涂料等高分子材料的反应型阻燃剂;该反应型阻燃剂工艺生产条件简单、产率较高、后处理过程简便,适合工业化生产。
Description
技术领域
本发明属于阻燃剂技术领域,具体涉及一种含恶二唑环反应型阻燃剂及其制备方法。
背景技术
大部分高分子材料因其氧指数较小而易燃烧,因高分子材料燃烧引起的火灾已成为现代社会的重大灾害之一,火灾给人民的生命、财产安全带来极大的威胁,因此如何降低高分子材料的燃烧性能已成为目前的研究焦点。传统的卤系阻燃剂由于在燃烧过程中存在的环境安全隐患问题导致其应用不断受到限制,随着一系列法律法规的实施,寻找其合适的替代品已迫在眉睫。磷氮阻燃剂由于其用量少、高效且无毒等优点而成为阻燃家族的新宠,被认为是最有潜力的无卤阻燃剂。磷氮阻燃剂主要有添加型和反应型两大类。“添加型”阻燃剂适用于大部分的高分子材料,但是该类阻燃剂要想满足材料的防火等级要求往往需要较高的添加量。上述阻燃剂往往导致材料的加工性能、力学性能、电学性能或机械性能受到较大的破坏,更糟糕的是该类阻燃剂经常会发生从材料基体内部迁移出来并且在材料表面起霜,从而影响材料的使用寿命及其阻燃性能。而“反应型”阻燃剂可与高分子材料之间通过牢固的共价键作用,能有效的解决添加型阻燃剂的缺点,保持材料的各种性能,防止阻燃剂的迁移失效。因此,开发反应型磷氮阻燃剂具有重要的意义。
发明内容
本发明的目的是针对卤系阻燃剂的环境安全问题和添加型磷氮阻燃剂用量大等缺点而提供一种反应型磷氮阻燃剂及其制备方法。
为达到上述目的,本发明通过下述技术方案来实现:
一种含恶二唑环反应型阻燃剂,其分子结构式为:
其中,R为烷基或苯基。
上述的含恶二唑环反应型阻燃剂的制备方法,包括如下步骤:
(1)在装有溶剂的反应器中加入5-(氨基甲基)-1,3,4-噁二唑-2-羧酸乙酯和缚酸剂,随后滴入磷试剂,搅拌均匀,将温度控制在40℃~70℃,恒温反应4~12h,反应完毕后,过滤,取滤液减压蒸发回收溶剂,得白色固体。
(2)将步骤(1)白色固体溶于无水乙醇中,冰浴下滴加3mol/L甲醇钠的甲醇溶液,于10℃~50℃反应2~5h。缓慢滴加乙醇稀释的质量分数为15%~20%的硫酸溶液,调节反应液pH值为7.0~7.5,出现大量白色固体,过滤,取滤液减压蒸馏得到白色固体,用丙酮重结晶,得到含恶二唑环反应型阻燃剂。
按上述方案,每摩尔5-(氨基甲基)-1,3,4-噁二唑-2-羧酸乙酯需要溶剂为1000mL~2000mL。
按上述方案,所述5-(氨基甲基)-1,3,4-噁二唑-2-羧酸乙酯与磷试剂的摩尔比为2:1~1.2,磷试剂与缚酸剂的摩尔比为1:1。
按上述方案,所述溶剂为氯仿、乙醚、二氯甲烷、四氢呋喃、1,4-二氧六环或二氯乙烷中的一种。
按上述方案,所述缚酸剂为三乙胺、吡啶、氢氧化钠或者碳酸钠中的一种。
按上述方案,所述磷试剂为苯膦酰二氯、异丙基二氯磷酸中的一种。
本发明的优点与效果是:
(1)本发明所述的阻燃剂不含卤素、有效减少了高分子燃烧时有毒有害气体的排放,减少了对环境的污染和对人体的伤害。本发明提供的阻燃剂可与聚合物单体或低聚物反应,生成阻燃高分子材料,避免了阻燃剂的迁移、析出,使得阻燃作用更持久,且对材料的加工性能及其物理机械性能影响较小。
(2)本发明所述的阻燃剂分子链含有恶二唑环,能够提高所应用的高分子材料的热稳定性,能够发挥磷氮协同阻燃增效。
(3)本发明工艺生产条件简单、产率较高、后处理过程简便,适合工业化。
附图说明
图1为含恶二唑环反应型阻燃剂的13C-NMR。
具体实施方式
为使本发明实现的技术手段、创作特征、达成目的与功效易于明白了解,下面结合具体实施方式,进一步阐述本发明本发明测试:
实施例1
第一步:在装有500mL干燥氯仿的反应瓶中加入50.02g 5-(氨基甲基)-1,3,4-噁二唑-2-羧酸乙酯和15.53g三乙胺,混合均匀后,移至0℃冰水浴,称量29.92g苯膦酰二氯放入恒压滴液漏斗中,在冰浴下开始滴加,于1h滴完后将温度升至60℃,恒温反应6h,反应完毕后,过滤,取滤液减压蒸发回收溶剂,得白色固体。
第二步:往第一步得到的白色固体中加入200mL无水乙醇,冰浴下滴加500mL3mol/L甲醇钠的甲醇溶液,于30℃反应3h后缓慢滴加乙醇稀释的质量分数为15%的硫酸溶液,调节反应液pH值至7.3,出现大量白色固体,过滤,取滤液减压蒸馏得到白色固体,用丙酮重结晶,得到含恶二唑环反应型阻燃剂,产率为68.5%。
实施例1合成的含恶二唑环反应型阻燃剂的13C-NMR谱图采用BrukerAV-400核磁共振仪测定,溶剂为CDCl3(TMS内标),结果参阅附图1。
实施例2
第一步:在装有400mL干燥氯仿的反应瓶中加入35.1g 5-(氨基甲基)-1,3,4-噁二唑-2-羧酸乙酯和10.88g三乙胺,混合均匀后,移至0℃冰水浴,称量18.16g异丙基二氯磷酸溶于30mL干燥氯仿中,并放入恒压滴液漏斗,在冰浴下开始滴加,于1h滴完后将温度升至50℃,恒温反应6h,反应完毕后,过滤,取滤液减压蒸发回收溶剂,得白色固体。
第二步:往第一步得到的白色固体中加入100mL无水乙醇,冰浴下滴加340mL3mol/L甲醇钠的甲醇溶液,于15℃反应4h后缓慢滴加乙醇稀释的质量分数为20%的硫酸溶液,调节反应液pH值至7.1,出现大量白色固体,过滤,取滤液减压蒸馏得到白色固体,用丙酮重结晶,得到含恶二唑环反应型阻燃剂,产率为74.8%。
本发明产品可用于橡胶、塑料、纤维、涂料等高分子材料的反应型阻燃剂。
本发明的含恶二唑环反应型阻燃剂在天然橡胶中的应用:
实施例3
天然橡胶的配方,按重量份数计算:天然橡胶100份、氧化锌6份、硬脂酸2份、防老剂4010NA 1份、石蜡3份、硫磺3份、促进剂CZ0.5份、促进剂DM 1份、炭黑(N330)20份、可膨胀石墨10份、反应型阻燃剂40份。经过塑练、混炼、压延及压出、硫化,得到阻燃天然橡胶。
实施例4
无阻燃天然橡胶配方:按重量份数计算,天然橡胶100份、氧化锌4份、硬脂酸2份、防老剂4010NA 2份、石蜡4份、硫磺3份、促进剂CZ 1份、促进剂DM 1份、炭黑(N330)20份、可膨胀石墨5份、反应型阻燃剂20份。经过塑练、混炼、压延及压出、硫化,得到阻燃天然橡胶。
对比例1
无阻燃天然橡胶配方:按重量份数计算,天然橡胶100份、氧化锌6份、硬脂酸2份、防老剂4010NA0.5份、石蜡3份、硫磺3份、促进剂CZ 0.5份、促进剂DM 0.8份、炭黑(N330)20份。经过塑练、混炼、压延及压出、硫化,得到天然橡胶。
实施例3、4和对比例1制备的橡胶的极限氧指数(LOI)按照GB/T 2406.2-2009进行测试;垂直燃烧测试按GB/T 2408-2008进行测试;拉伸强度和断裂伸长率参照GB/T 528-2009进行。测试结果参见表1所示。
样品 | LOI,% | 拉伸强度,MPa | 断裂伸长率,% | UL-94rate |
实施例3 | 29.6 | 7.84 | 654.56 | V-0 |
实施例4 | 25.1 | 7.45 | 686.71 | V-0 |
对比例1 | 19.3 | 6.54 | 621.37 | N.R. |
以上结果显示,相对于对比例,加入反应型阻燃剂后,实施例的力学性能和阻燃性能都有提高;不同的磷试剂对橡胶的性能有影响,苯膦酰二氯相比于异丙基二氯磷酸有更好的应用效果。上述结果表明实施例3、4制备的橡胶兼具良好的拉伸强度、断裂伸长率和阻燃性。
以上显示和描述了本发明的基本原理和主要特征和本发明的优点。本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明精神和范围的前提下,本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。
Claims (6)
2.一种含恶二唑环反应型阻燃剂及其制备方法,其特征在于,包括以下步骤:
(1)在装有溶剂的反应器中加入5-(氨基甲基)-1,3,4-噁二唑-2-羧酸乙酯和缚酸剂,随后滴入磷试剂,搅拌均匀,将温度控制在40℃~70℃,恒温反应4~12h,反应完毕后,过滤,取滤液减压蒸发回收溶剂,得白色固体;
(2)将步骤(1)白色固体溶于无水乙醇中,冰浴下滴加3mol/L甲醇钠的甲醇溶液,于10℃~50℃反应2~5h。缓慢滴加乙醇稀释的质量分数为15%~20%的硫酸溶液,调节反应液pH值为7.0~7.5,出现大量白色固体,过滤,取滤液减压蒸馏得到白色固体,用丙酮重结晶,得到含恶二唑环反应型阻燃剂。
3.根据权利要求2所述的一种含恶二唑环反应型阻燃剂及其制备方法,其特征在于,步骤(1)中所述的溶剂为氯仿、乙醚、二氯甲烷、四氢呋喃、1,4-二氧六环或二氯乙烷中的一种。
4.根据权利要求2所述的一种含恶二唑环反应型阻燃剂及其制备方法,其特征在于,步骤(1)中所述的缚酸剂为三乙胺、吡啶、氢氧化钠或者碳酸钠中的一种。
5.根据权利要求2所述的一种含恶二唑环反应型阻燃剂及其制备方法,其特征在于,步骤(1)中所述的磷试剂为苯膦酰二氯、异丙基二氯磷酸中的一种。
6.根据权利要求2所述的一种含恶二唑环反应型阻燃剂及其制备方法,其特征在于,步骤(1)中所述的5-(氨基甲基)-1,3,4-噁二唑-2-羧酸乙酯与磷试剂的摩尔比为2:1~1.2,磷试剂与缚酸剂的摩尔比为1:1。
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