CN117377713A - 由磺化芳基聚合物形成的新型膦酰化未氟化和部分氟化的芳基聚合物以及由聚合物型全氟磺酸形成的新型聚合物型全氟膦酸、其制备方法及在电学膜应用中的用途 - Google Patents
由磺化芳基聚合物形成的新型膦酰化未氟化和部分氟化的芳基聚合物以及由聚合物型全氟磺酸形成的新型聚合物型全氟膦酸、其制备方法及在电学膜应用中的用途 Download PDFInfo
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Abstract
本发明包括新的物质类型，即高度膦酰化和低度膦酰化的芳基聚合物以及聚合物型全氟膦酸，其原料为其磺酰化形式，还包括由磺酸形式制备膦酰化聚合物的通用方法以及它们在电学膜方法中的用途。
Description
现有技术
最常描述的膦酰化体系是基于借助于芳基卤化物和二或三烷基亚磷酸酯的亲核取代(米歇利斯-阿尔布佐夫(Michaelis-Arbusow)重排和米歇利斯-贝克(Michaelis-Becker)重排)合成的芳基聚合物。
这些膦酰化的芳基聚合物具有较高的热和化学稳定性。另外，它们即使在未润湿的状态下也显示出良好的质子导电率。[1-5]
例如从DE 102011015 212 A1中得知，这些膦酰化的芳基聚合物的缺点是它们在未水合(即干燥)状态下是非常脆的并且由此不能制备正常工作的膜。脆性行为随着温度升高和湿度降低而增加并且导致膜的机械失效。这使得无法将这些聚合物用作超过100℃温度范围的电学膜方法的膜。
在Kyoji Kimoto的专利US6680346B1中说明了直接合成膦酰化的全氟膦酸。其中的权利要求涉及以下结构(图2)，其中m为0或1，n为2或3，X、Y是H或C6H4SO3H，并且比值A/B为1.5至15。
从EP2514773A1看出，由于难以控制聚合条件，US6680346B1中的合成聚合物经受环化作用，这导致了聚合期间的链转移并且由此造成分子量降低和材料机械强度降低。随着短链含膦酰基单体与四氟乙烯单体的摩尔比增大，进一步有利于副反应，这限制了离子交换能力和材料稳定性的提升。
本文请求保护的方法没有这种限制，因为现今可以以保持不变的品质来制备聚合物型全氟磺酸，其示例可以在图1中看到。
所描述的膦酰化反应因此产生了聚合物型全氟膦酸的新型稳定的材料类别并且不具有US6680346B1中的缺点。在磺酰化的芳基聚合物中也有同样的表现，基础聚合物已经具有良好的机械特性，在其作为膦酰化聚合物的新形式中也保留了这些良好的机械特性。
发明内容
本发明的任务是基于寻找和合成新型的膦酰化聚合物，所述膦酰化聚合物即使在干燥状态下也质子导电、并且是化学和机械稳定的。这是通过以下方式实现的：首先借助于氯磺化将已经具有良好机械特性并带有磺酸基团的磺酰化聚合物用亚硫酰氯转化为-SO2Cl形式。从-SO2Cl形式触发，已经可以用三烷基亚磷酸酯例如三(三甲基硅烷基)亚磷酸酯(TTMSP)进行膦酰化或者将-SO2Cl形式用亚硫化钠转化为-SO2Na(磺酸钠)形式并且将其膦酰化，或者继续将-SO2Na形式转化为-SO2Li(磺酸锂)形式并且进而将其膦酰化。利用这种方法，可以从所有具有磺酸基团的聚合物来合成具有高机械柔性、化学稳定性和高质子导电率的膦酰化聚合物。在其磺酰化形式中已经具有良好机械和化学特性的聚合物在膦酰化之后保持了这些特性并且与含磺酸的聚合物不同在超过100℃时具有非常好的质子导电率。(图3)
这个反应应尽可能高效且简单，在此正是这样。
膦酰化聚合物应可溶于常见的溶剂中，以便能够由其制备膜。
利用本文中说明的合成方法，理论上可以由所有磺酰化聚合物来合成膦酰化聚合物。
本发明是基于向磺酰化聚合物中引入反应基团-X(-X可以是-SO2Cl、-SO2Na、-SO2Li)以及反应基团与三烷基亚磷酸酯例如三(三甲基硅烷基)亚磷酸酯(TTMSP)的反应。
根据膦酰化度，膦酰化聚合物还可以包含游离的反应基团-X。这些游离基团可以用于将膦酰化聚合物后续地共价交联或者将未反应掉的基团再次转化为-SO3H形式并且因此获得既包含磺酰化基团又包含膦酰化基团的聚合物。
膦酰化可以在溶液中进行。为此，可以将具有反应基团-X的聚合物溶解在溶剂中，例如N-甲基吡咯烷酮(NMP)、二甲基乙酰胺(DMAc)、二甲亚砜(DMSO)等。可以选择性地预先、直接在溶解过程之前或将聚合物溶解之后加入TTMSP。依据所希望的膦酰化度，相对于聚合物称入量加入0.1重量％(重量百分比)(对于较少的膦酰化度)至5000重量％(对于较高的膦酰化度)。
这个反应在高沸点溶剂如NMP、DMAc和DMSO中最好且最快地进行。在反应期间，可以观察到气体形成，这表明反应何时开始，或者不再形成气体表明反应结束。
将这个反应保持在反应温度(60-200℃)直至气体形成停止，所述反应温度与所使用的聚合物、其分子量和溶剂无关。随后将反应继续维持温度2至8小时，以便确保反应完全。
随后借助于蒸馏来移除反应副产物和过量的TTMSP，而呈其三甲基硅烷基酯形式的膦酰化聚合物留在溶剂中。
现在将聚合物溶液浇入水中并且依据膦酰化度不同作为固体沉淀(低膦酰化度)或进入溶液中(高膦酰化度)。通过加热水/聚合物混合物，将膦酰化聚合物从其三甲基硅烷基酯形式水解为游离的聚合物型膦酸。
为了完全分离出水解副产物，可以依据膦酰化度简单地用水清洗聚合物。不溶于水的部分可以用水洗出并过滤掉，或者可以通过渗析来纯化溶于水的部分。
另一个变体是，不使聚合物溶液在水中沉淀，而是在分离掉过量的TTMSP之后将聚合物溶液从[0015]直接进一步加工成膜并且随后将其在热水至沸水中水解或用热的水蒸气进行后续处理。
图4中展示了非限制性的实施例的对应的示例性反应概览。
可以将所获得的聚合物与碱性聚合物例如与聚苯并咪唑或阴离子交换聚合物共混成酸碱共混物膜、共价交联膜和共价交联酸碱共混物膜。
膦酰化聚合物与碱性聚合物之间的混合比可以为99mol％膦酰化聚合物/1mol％碱性聚合物与1mol％膦酰化聚合物/99mol％碱性聚合物之间。
另外还可以将任意的磺酰化聚合物以任意量加入到所述聚合物或共混物中。
可以将所获得的聚合物与碱性聚合物例如聚苯并咪唑或阴离子交换聚合物共混成酸碱共混物膜、共价交联膜和共价交联酸碱共混物膜。
膦酰化聚合物与碱性聚合物之间的混合比可以为99mol％膦酰化聚合物/1mol％碱性聚合物与1mol％膦酰化聚合物/99mol％碱性聚合物之间。
另外还可以将任意的磺酰化聚合物以任意量加入到所述聚合物或共混物中。
另外还可以用任意量的磷酸对共混物膜进行掺杂。作为磷酸掺杂度优选的是介于40重量％与500重量％之间的值。
所获得的聚合物可以用在电化学电池中。所获得的聚合物优选可以用在-30℃至250℃的温度范围内的低温或中温燃料电池中，或者可以用在在0℃至250℃的温度范围内的低温或中温电解池中。此外，所获得的聚合物可以用在-70至250℃的化学合成反应器中。所获得的聚合物还可以用作一次电池和二次电池中的隔膜或者用作电极、一次电池和二次电池中的粘合剂。
非限制性实施例：
将2g磺酰化聚醚酮醚酮酮(sPEKEKK)与55g亚硫酰氯混合，加热到90℃并且煮沸回流。随后向其中加入DMF(二甲基甲酰胺)并且加热直至不再能看到气体形成。随后再维持反应温度2小时，以保证反应完全。现在蒸馏掉过量的亚硫酰氯和副产物，并且用THF(四氢呋喃)将产物制浆。现在可以将溶液/悬浮液在异丙醇或水中沉淀。将产物清洗直至中性并且随后干燥。现在，先前的磺酰化聚合物以-SO2Cl形式存在。现在，将2M亚硫化钠溶液中的产物转化为-SO2Na形式。随后过滤掉聚合物并且再次用水清洗，以便洗出过量的亚硫化钠。随后将-SO2Na形式的聚合物与10重量％的LiCl溶液混合，以便将其转化为-SO2Li形式。随后将聚合物再次用水清洗，以冲洗掉过量的盐。随后将聚合物干燥。
可以以全部三种形式-SO2Cl、-SO2Na和-SO2Li用TTMSP进行膦酰化，其中-SO2Li形式是优选的。
现在，可以将具有-SO2Cl、-SO2Na或-SO2Li基团的聚合物与有机溶剂如DMAc、NMP、DMSO等和TTMSP混合并且膦酰化。
在聚合物型全氟磺酸的情况下，可以使用来自如[0019]至[0021]中说明地进行的反应的聚合物粒料、粉末等，或者可以直接使用全氟磺酸膜。为此，将全氟磺酸膜穿过热的亚硫酰氯/DMF浴(在其中进行氯磺化)，然后穿过水浴，以便进行冲洗。随后将现在具有-SO2Cl形式的膜穿过亚硫化钠浴，其中产生-SO2Na形式并且随后再次穿过水浴以便进行冲洗。随后将呈-SO2Na形式的膜穿过LiCl浴并且转化为-SO2Li形式并且随后再次在水浴中清洗。可以将膜的所有三种形式，即-SO2Cl、-SO2Na和-SO2Li，穿过经加热的TTMSP浴并且随后穿过热的/煮沸的水浴，以便通过水解来获得膦酸形式。这既可以以连续的辊对辊方法实现，但是也可以以批量法实现。现在可以将膜干燥并且直接再次使用。对于膦酰化而言优选的是-SO2Cl形式。
对实验的分析：
在此示例性地说明这些膦酰化聚合物之一、其离子交换能力、直至180℃的导电率(图3)。
离子交换能力的测定
将100mg的经处理的聚合物用饱和NaCl溶液覆盖，搅拌约2小时并且加入2滴溴百里酚蓝作为指示剂。在此，膦酰化聚合物的质子交换Na离子并且产生HCl。这种HCl可以借助于用0.1mol NaOH滴定来检测。由此可以测定IEC直接。为了测定总计的IEC总，向同一溶液加入过量的3ml的NaOH 0.1M，再次搅拌2小时并且随后用HCl反向滴定。
对于[0019]中的实验，对于膦酰化PEKEKK(pPEKEKK)获得了IEC直接＝0.95mmol/g和IEC总＝2.2mmol/g。在图3中的导电率测量中可以非常好地看到，即使在超过100℃的情况下非常好的质子导电性。另外，相比之下，看到Nafion 212及其在相同测量条件下在30℃下50％室内湿度降低到180℃下0.2％室内湿度时导电率的降低。
由此，在高温下的高导电率可以归因于SO2基团对膦酸基团的电子产生了较强的吸电子效应。
文献
[1]Vladimir Atanasov and Jochen Kerres
Highly Phosphonated Polypentafluorostyrene；Macromolecules 2011,44,16,6416-6423
[2]Vladimir Atanasov,Dietrich Gudat,Bastian Ruffmann,Jochen Kerres,
Highly phosphonated polypentafluorostyrene:Characterization andblends with polybenzimidazole,
European Polymer Journal,Volume 49,Issue 12,2013,Pages 3977-3985,
[3]Vladimir Atanasov,Matthias Bürger,Sandrine Lyonnard,Lionel Porcar,Jochen Kerres,
Sulfonated poly(pentafluorostyrene):Synthesis&characterization,
Solid State lonics,Volume 252,2013,Pages 75-83,
[4]Vladimir Atanasov,Jochen Kerres,
ETFE-g-pentafluorostyrene:Functionalization and proton conductivity,
European Polymer Journal,Volume 63,2015,Pages 168-176,
[5]Vladimir Atanasov,Andrey Oleynikov,Jiabing Xia,Sandrine Lyonnard,Jochen Kerres,
Phosphonic acid functionalized poly(pentafluorostyrene)aspolyelectrolyte membrane for fuel cell application
Journal of Power Sources,Volume 343,2017,Pages 364-372
Claims (17)
1.由包含磺酸基团的初始聚合物制备膦酰化的聚合物的方法，所述方法具有以下方法步骤：
a)借助于氯磺化将所述初始聚合物用亚硫酰氯转化为(-SO2Cl)-的形式，
b)将中间产物用三(三甲基硅烷基)亚磷酸酯转化为膦酰化的聚合物，
其中所述初始聚合物为选自由以下项组成的组的项：聚酰亚胺、聚醚酮(PEK)、聚醚醚酮(PEEK)、聚醚酮醚酮酮
(PEKEKK)、聚碳酸酯、聚砜、聚亚砜、聚硫化物、未氟化和部分氟化的聚醚砜、未氟化和部分氟化的聚醚醚砜、聚酯、聚苯乙烯、聚合物型全氟膦酸。
2.根据权利要求1所述的方法，其特征在于，在方法步骤a)之后，首先通过与亚硫化钠反应转化为含钠形式(-SO2Na)。
3.根据权利要求2所述的方法，其特征在于，在转化为钠形式之后，首先通过与氯化锂或氢氧化锂或者其他锂盐反应转化为含锂形式(-SO2Li)。
4.根据前述权利要求中任一项所述的方法，其特征在于，方法步骤b)在溶剂中、优选在高沸点溶剂中进行，其中所述溶剂为选自由以下项组成的组的至少一项：N-甲基吡咯烷酮(NMP)、二甲基乙酰胺(DMAc)、二甲亚砜(DMSO)。
5.根据权利要求4所述的方法，其特征在于，在方法步骤b)期间将所述溶剂加热直至沸腾温度。
6.根据权利要求5所述的方法，其特征在于，将所述反应混合物加热至所述溶剂的沸腾温度至少2小时、优选至少8小时。
7.根据前述权利要求中任一项所述的方法，其特征在于，在方法步骤b)之后将未反应掉的活性基团(-SO2Cl、含钠形式或含锂形式)逆反应成磺酸基团。
8.根据前述权利要求中任一项所述的方法，其特征在于，三(三甲基硅烷基)亚磷酸酯的量为所述中间产物的0.1至5000重量百分比。
9.根据前述权利要求中任一项所述的方法，其特征在于，所述初始聚合物作为膜存在，所述方法步骤a)和b)通过在相应的反应物中浸浴来进行，其中接着所述方法步骤之后分别通过在水中浸浴来冲洗所述膜。
10.根据以上权利要求中任一项所述的膦酰化的聚合物和膜，其特征在于，所述聚合物既包含磺基基团也包含膦酸基团。
11.根据以上权利要求中任一项所述的膦酰化的聚合物和膜，其特征在于，所述聚合物为膦酰化的聚醚酮醚酮酮(sPEKEKK)。
12.根据以上权利要求中任一项所述的聚合物和膜在电化学电池中的用途。
13.根据权利要求12所述的膜的用途，用在-30℃至250℃的温度范围内的低温或中温燃料电池中。
14.根据权利要求12所述的膜的用途，用在0℃至250℃的温度范围内的低温或中温电解池中。
15.根据权利要求12所述的膜的用途，用在-70至250℃的化学合成反应器中。
16.根据权利要求12所述的膜作为一次电池和二次电池中的隔膜的用途。
17.根据权利要求12所述的聚合物作为一次电池和二次电池的电极中的粘合剂的用途。
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| PCT/DE2022/100466 WO2022268265A1 (de) | 2021-06-23 | 2022-06-23 | Neuartige phosphonierte nichtfluorierte und teilfluorierte arylpolymere aus sulfonierten arylpolymeren und neuartige polymere perfluorphosphonsäuren aus polymeren perfluorsulfonsäuren, deren herstellungsverfahren und anwendung in elektromembrananwendungen |
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