CN112125928A - 一种(3,5-二氟苯基)二苯基氧膦的制备方法 - Google Patents
一种(3,5-二氟苯基)二苯基氧膦的制备方法 Download PDFInfo
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Abstract
Description
技术领域
本发明属于有机合成技术领域,涉及一种(3,5-二氟苯基)二苯基氧膦的制备方法。
背景技术
质子交换膜燃料电池是一种清洁高效的新能源发电装置,受到广泛的关注。质子交换膜是燃料电池的核心部件之一。目前,杜邦公司生产的Nafion膜是广泛使用的商业膜。但Nafion膜由于价格高、耐甲醇性差、高温低湿环境下电导率急剧下降等缺点,限制了其进一步发展。因此,磺化芳香类聚合物质子交换膜成为目前的研究热点。其中,选择合适的有机单体成为首要的研究方向。磺化聚芳(硫)醚氧膦类聚合物单体中所含的氧膦基团还具有较强的吸水保湿性、以及与无机粒子或有机物的粘结性,表现出了优异的综合性能,在燃料电池领域显示了潜在的应用前景。
经对现有技术的检索发现,X.H.Ma等在《Journal of Power Sources》(2009,188,57-63)上发表“Synthesis and properties of sulfonated poly(arylene etherphosphine oxide)s for proton exchange membranes”。该文报道了磺化聚芳醚氧膦质子交换膜的制备及性能,所述膜表现了较好的热稳定性、化学稳定性及较高的质子电导率,表明氧膦基团的引入有利于提高膜的综合性能。
但是该现有技术涵盖的聚合物种类相对较少,结构也较为单一。针对一些新型的聚合物的合成,本发明提供了一种新的氧膦单体的合成路线,拓展了该技术的应用范畴。
发明内容
本发明的目的就是提供一种(3,5-二氟苯基)二苯基氧膦的制备方法。
本发明的目的可以通过以下技术方案来实现:
一种(3,5-二氟苯基)二苯基氧膦的制备方法,其中(3,5-二氟苯基)二苯基氧膦的结构式如下所示:
制备反应方程式如下:
制备方法包括:将1-溴-3,5-二氟苯溶液加入至含镁粉的反应溶剂中,并在惰性气体氛围中于0℃至室温下进行格氏反应2-6h,之后再加入二苯基氯化磷溶液并在0℃至室温下反应,经0.5-1.5mol/L稀酸淬灭反应后,通过第一纯化处理得到浅棕色油状产物;最后将浅棕色油状产物经双氧水或叔丁基过氧化氢氧化,并通过第二纯化处理后,即得到所述的(3,5-二氟苯基)二苯基氧膦。
进一步地,所述的惰性气体包括氮气或氩气,所述的1-溴-3,5-二氟苯溶液及含镁粉的反应溶剂中,溶剂均包括乙醚或四氢呋喃。
进一步地,所述的稀酸包括稀硫酸、稀盐酸或稀磷酸中的一种。
进一步地,所述的第一纯化处理依次包括稀释、洗涤、脱水、过滤、蒸干溶剂过程;所述的第二纯化处理依次包括稀释、洗涤、脱水、过滤、蒸干溶剂、重结晶过程。其中,洗涤过程所用洗涤剂均包括碳酸氢钠溶液、碳酸钠溶液或水中的至少一种,脱水过程所用脱水剂均包括无水硫酸镁、无水氯化钙或无水碳酸钠中的至少一种。
进一步地,所述的第二纯化处理中,重结晶过程所用溶剂包括环己烷、正己烷或四氯化碳中的至少一种。
与现有技术相比,本发明所得的化合物含二卤素官能团,可与双官能团的羟基或类羟基单体(如含有二羟基/巯基官能团或类羟基/巯基官能团化合物)在碱性条件下发生芳香亲核取代反应,得到含氧膦结构单元的聚合物。另外,本发明所得化合物的氧膦基团具有良好的吸水保湿性与耐氧化稳定性,并且制备方法操作简单,不需加热,原料易得,安全性高,得到的可与双官能团的羟基或类羟基单体在碱性条件下发生芳香亲核取代反应,得到含氧膦结构单元的聚合物,制备成质子交换膜并进一步应用于燃料电池、离子交换树脂、膜分离、传感器等多种功能材料领域,与商业化的Nafion膜相比,该类膜具有优异的耐氧化、耐水解、耐热等性能,同时具有机械强度高,易改性,成本低、电导率高等优点。
附图说明
图1为实施例中制备得到的(3,5-二氟苯基)二苯基氧膦的红外谱图;
图2为实施例中制备得到的(3,5-二氟苯基)二苯基氧膦的1H-NMR谱图。
具体实施方式
下面结合附图和具体实施例对本发明进行详细说明。
一种(3,5-二氟苯基)二苯基氧膦的制备方法,包括:
制备方法包括:将1-溴-3,5-二氟苯溶液加入至含镁粉的反应溶剂中,并在氮气或氩气氛围中于0℃至室温下进行格氏反应2-6h,得到3,5-二氟苯基溴化镁(II);之后将3,5-二氟苯基溴化镁(II)与二苯基氯化膦溶液混合,并在0℃至室温下反应8-16h,采用0.5-1.5mol/L的稀硫酸、稀盐酸或稀磷酸淬灭反应后,通过第一纯化处理得到浅棕色油状产物;最后将浅棕色油状产物经双氧水或叔丁基过氧化氢氧化,并通过第二纯化处理后,即得到(3,5-二氟苯基)二苯基氧膦。
其中,1-溴-3,5-二氟苯溶液、含镁粉的反应溶剂以及二苯基氯化膦溶液中的溶剂均包括乙醚或四氢呋喃;第一纯化处理依次包括稀释、洗涤、脱水、过滤、蒸干溶剂过程;第二纯化处理依次包括稀释、洗涤、脱水、过滤、蒸干溶剂、重结晶过程。并且,洗涤过程所用洗涤剂均包括碳酸氢钠溶液、碳酸钠溶液或水中的至少一种,脱水过程所用脱水剂均包括无水硫酸镁、无水氯化钙或无水碳酸钠中的至少一种。此外,第二纯化处理中,重结晶过程所用溶剂包括环己烷、正己烷或四氯化碳中的至少一种。
以下实施例以本发明技术方案为前提进行实施,给出了详细的实施方式和具体的操作过程,但本发明的保护范围不限于下述的实施例。
实施例:
一种(3,5-二氟苯基)二苯基氧膦的制备方法,包括:
1)在装配有搅拌棒、加料漏斗、冷凝器以及气体入口的250mL圆底烧瓶中,持续通入氮气,并加入Mg屑1.2715g与20mL四氢呋喃,使Mg屑充分浸没于四氢呋喃中,之后加入100mL含10.6743g 1-溴-3,5-二氟苯的四氢呋喃溶液中,并在室温下持续搅拌4h,得到3,5-二氟苯基溴化镁溶液;
2)在0℃下通过加料漏斗将3,5-二氟苯基溴化镁溶液滴加至50mL含11.2953g二苯基氯化磷的四氢呋喃溶液中,所得反应混合物经彻夜(12h)搅拌后,加入至100mL 1M盐酸中淬灭;
3)采用300mL乙酸乙酯将所得反应产物混合液稀释,并转移至分液漏斗中,分层后取有机层,并依次采用蒸馏水、稀NaHCO3溶液、蒸馏水进行洗涤,之后加入无水MgSO4干燥,过滤并蒸发至干,得到浅棕色油状物;
4)将浅棕色油状物溶于150mL乙醚/丙酮(体积比1:1)中,并缓慢加入12mL30%H2O2,搅拌20min,并采用薄层色谱跟踪反应,直至反应结束;
5)将反应混合物用125mL 10%Na2S2O3溶液处理除去反应混合物中过量的氧化剂H2O2,分层后取有机层,并用300mL乙酸乙酯稀释,再依次采用蒸馏水、稀NaHCO3溶液、蒸馏水洗涤有机层;最后经MgSO4干燥、真空除去溶剂后,得到灰白色固体;
6)将灰白色固体产物在环己烷中重结晶两次,即得到9.75g的白色结晶固体产物,(3,5-二氟苯基)二苯基氧膦,反应产率为62%。
如图1及图2所示分别为(3,5-二氟苯基)二苯基氧膦的红外谱图及1H-NMR谱图,其特征峰为:1169(O=P),1606,1595,1491,1436,1422(苯环),证明本实施例成功合成了(3,5-二氟苯基)二苯基氧膦。
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改,并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此,本发明不限于上述实施例,本领域技术人员根据本发明的揭示,不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。
Claims (10)
2.根据权利要求1所述的(3,5-二氟苯基)二苯基氧膦的制备方法,其特征在于,所述的格氏反应在惰性气体保护下进行,反应温度为0℃至室温,反应时间为2-6h。
3.根据权利要求2所述的(3,5-二氟苯基)二苯基氧膦的制备方法,其特征在于,所述的惰性气体包括氮气或氩气。
4.根据权利要求1所述的(3,5-二氟苯基)二苯基氧膦的制备方法,其特征在于,所述的1-溴-3,5-二氟苯溶液及含镁粉的反应溶剂中,溶剂均包括乙醚或四氢呋喃。
5.根据权利要求1所述的(3,5-二氟苯基)二苯基氧膦的制备方法,其特征在于,所述的稀酸包括浓度为0.5-1.5mol/L的稀硫酸、稀盐酸或稀磷酸中的一种。
6.根据权利要求1所述的(3,5-二氟苯基)二苯基氧膦的制备方法,其特征在于,所述的第一纯化处理依次包括稀释、洗涤、脱水、过滤、蒸干溶剂过程;所述的第二纯化处理依次包括稀释、洗涤、脱水、过滤、蒸干溶剂、重结晶过程。
7.根据权利要求6所述的(3,5-二氟苯基)二苯基氧膦的制备方法,其特征在于,所述的第一纯化处理及第二纯化处理中,洗涤过程所用洗涤剂均包括碳酸氢钠溶液、碳酸钠溶液或水中的至少一种。
8.根据权利要求6所述的(3,5-二氟苯基)二苯基氧膦的制备方法,其特征在于,所述的第一纯化处理及第二纯化处理中,脱水过程所用脱水剂均包括无水硫酸镁、无水氯化钙或无水碳酸钠中的至少一种。
9.根据权利要求6所述的(3,5-二氟苯基)二苯基氧膦的制备方法,其特征在于,所述的第二纯化处理中,重结晶过程所用溶剂包括环己烷、正己烷或四氯化碳中的至少一种。
10.根据权利要求1所述的(3,5-二氟苯基)二苯基氧膦的制备方法,其特征在于,浅棕色油状产物氧化过程中,所用氧化剂包括双氧水或叔丁基过氧化氢中的至少一种。
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