CN111410742B - 一种改性聚芳醚砜膜及其制备方法 - Google Patents

一种改性聚芳醚砜膜及其制备方法 Download PDF

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CN111410742B
CN111410742B CN202010256566.6A CN202010256566A CN111410742B CN 111410742 B CN111410742 B CN 111410742B CN 202010256566 A CN202010256566 A CN 202010256566A CN 111410742 B CN111410742 B CN 111410742B
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张东宝
于冉
张奇
张建民
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Nanjing Qingyan Polymer New Materials Co ltd
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Abstract

本发明公开了一种改性聚芳醚砜膜及其制备方法，通过优选其片段的占比，获得了一种稳定性好，IEC和吸水率高、结构简单的改性聚芳醚砜膜。

Description

一种改性聚芳醚砜膜及其制备方法
技术领域
本发明属于高分子材料领域，具体涉及一种改性聚芳醚砜膜及其制备方法。
背景技术
聚芳醚砜(PAES)是一类含有芳基、砜、醚结构的聚合材料，其通常具有优秀的机械性能、耐热性能以及较好的抗水解性能。经质子化修饰后在质子交换膜材料中用途广泛，如可用于燃料电池领域的质子交换。
PAES的常见质子化改性有羧基化和磺酸化，如专利CN201610497149公开了一系列含羧基侧链聚芳醚砜，其亲水性、水通量等均获得了显著提高。另一种较常用的质子化改性方式为磺酸化，即制备成磺化聚芳醚砜(SPAES)。目前制备磺化聚芳醚砜的工艺已经较为成熟，所制备的磺化聚芳醚砜也结构多种多样，但是通常由磺化聚芳醚砜制备的膜其在IEC、吸水率和机械性能之间难以得到良好的平衡。故本领域依旧需要探寻综合性能更优，结构更简单的改性磺化聚芳醚砜。。
发明内容
本发明提供了一种改性磺化聚芳醚砜，一种改性聚芳醚砜膜，其结构式为
Figure BDA0002437565900000011
其中，
0<x<1，且y＝1-x。
优选地，x的取值范围为0.1-0.9，更优选地，取值范围为0.1-0.7，更优选地，取值范围为0.3-0.5。
本发明还提供所述改性聚芳醚砜膜的制备方法，包括如下步骤：
1)4,4'-二氯二苯砜和发烟硫酸反应，得到4,4'-二氯二苯砜-3,3'-二磺酸二钠；
2)4,4'-二氯二苯砜-3,3'-二磺酸二钠和4,4'-二羟基联苯、4,4'-二羟基二苯甲烷反应，得到中间产品；
3)将中间产品质子化制备薄膜，得到所述改性聚芳醚砜膜。
优选地，步骤1)的反应条件为4,4'-二氯二苯砜和发烟硫酸的摩尔比为2-6:1，其中发烟硫酸以SO3计算；反应温度为120-130℃，反应时间为15-24h。
优选地，步骤1)还包括反应完毕后用NaOH调节pH，并进行盐析的操作。
优选地，步骤2)的反应条件为4,4'-二氯二苯砜-3,3'-二磺酸二钠、4,4'-二羟基联苯、4,4'-二羟基二苯甲烷的摩尔比为2:1:1。
有益效果：
本发明的改性聚芳醚砜具有结构简单、制备工艺简单，吸水性好，IEC高，水解稳定性高，且机械性能还较好的优势，具有较高的使用价值。
具体实施方式
以下对本发明的具体实施方式进行详细说明，应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不构成对本发明的限制。
实施例1：
1)合成4,4'-二氯二苯砜-3,3'-二磺酸二钠
参照文献方法，向250mL反应瓶中加入发烟硫酸和4,4'-二氯二苯砜，控制其摩尔比(发烟硫酸以SO3计算)为3:1，然后升温至120℃下反应20h，反应结束后，将反应瓶中反应液倾入冰水中，并搅拌至冰块消融，随后盐析，过滤，产物复溶于纯水后调节pH至7左右，二次盐析，过滤，滤饼真空干燥得粗品，粗品采用乙醇和水混合溶液重结晶得到纯品。
2)中间产物的制备
选用带有氮气置换装置、分水器的干燥三口瓶，在氮气保护下将制备的10mmol的4,4'-二氯二苯砜-3,3'-二磺酸二钠溶入30mL的DMSO和30mL甲苯的混合液中，然后加入5mmol的4,4'-二羟基联苯，5mmol的4,4'-二羟基二苯甲烷，12.5mmol的碳酸钾，然后升温至140℃反应4h，其中缩聚产生的水以甲苯-水共沸物的形式除去，然后升温至160℃继续反应6h，反应完毕后，将反应液倾入冰水中析出目标产物，过滤，用去离子水反复洗涤，干燥得到中间产物。
3)制备改性聚芳醚砜质子交换膜
将中间产物溶于有机溶剂中，过滤，平铺在玻璃上，干燥成型；成型后的膜剥离后在乙醇中洗涤，然后水浴下在硫酸中充分浸泡，最后用去离子水洗涤并烘干，得到改性聚芳醚砜质子交换膜。
其中，所得膜的结构式如下：
Figure BDA0002437565900000021
实施例2-9：
具体制备工艺和实施例1完全相同，唯一的区别是在步骤2)中所采用的4,4'-二羟基联苯的物质的量分别为：1mmol、2mmol、3mmol、4mmol、6mmol、7mmol、8mmol、9mmol；而对应采用的4,4'-二羟基二苯甲烷的物质的量则分别为：9mmol、8mmol、7mmol、6mmol、4mmol、3mmol、2mmol、1mmol。
实验例1：离子交换容量(IEC)测试
IEC测定采用本领域常用的NaOH滴定法进行，过程简述如下：真空高温干燥膜样品，测其重量，然后再用NaCl溶液中充分置换氢离子，采用酚酞为指示剂，进行滴定。各个实施例所得结果参见表1：
表1
序号 x/y 理论IEC 测定IEC
实施例2 1/9 3.49 3.45±0.02
实施例3 2/8 3.50 3.47±0.02
实施例4 3/7 3.51 3.46±0.03
实施例5 4/6 3.51 3.47±0.02
实施例1 5/5 3.52 3.47±0.04
实施例6 6/4 3.53 3.48±0.02
实施例7 7/3 3.54 3.51±0.03
实施例8 8/2 3.55 3.50±0.02
实施例9 9/1 3.56 3.55±0.04
结果显示，实测IEC值和理论IEC值有所差距，整体测定值偏小，且由于测试误差原因，导致其数据有所波动，整体上IEC值并没有明显差别。
实验例2：吸水率测试
通过测量特定温度下充分吸水后的膜质量和吸水前干燥膜的质量来测试吸水率，具体测试方法为选择一定大小的膜在70℃下烘干10h，测得到其质量W0，然后将其置于纯水中自然溶胀24h，测试其质量W1，吸水率＝(W1-W0)/W0×100％。理论上对于用于燃料电池中用于质子交换的膜，其吸水性越好，代表其质子导电率越高。其吸水率见表2。
表2
序号 x/y 吸水率
实施例2 1/9 51.1±0.6
实施例3 2/8 51.1±0.5
实施例4 3/7 51.2±0.5
实施例5 4/6 52.4±0.4
实施例1 5/5 52.6±0.6
实施例6 6/4 52.5±0.7
实施例7 7/3 52.9±0.5
实施例8 8/2 53.1±0.3
实施例9 9/1 55.4±0.6
通常情况下，吸水率主要跟可与水形成强氢键的基团数量有关，而xy片段中均含有相同数量的SO3H，考虑到分子量因素，故x占比越高时其吸水率应当越高。结果显示，x占比越高时其吸水率确实越高，整体区别较为显著。
实验例3：水解稳定性测试
水解稳定性可代表膜在极端情况下的稳定性，测试方法为，将一定大小的膜在放入温度为80℃的水中，对折，测试其从对折至开始到对折外表面出现裂痕的时间，每个样品品行测试三次，结果记录在表3中。
表3
序号 x/y 时间/h
实施例2 1/9 36.6±0.1
实施例3 2/8 35.2±0.1
实施例4 3/7 32.8±0.2
实施例5 4/6 32.2±0.1
实施例1 5/5 30.3±0.2
实施例6 6/4 20.5±0.3
实施例7 7/3 15.5±0.3
实施例8 8/2 14.1±0.3
实施例9 9/1 14.4±0.2
由此可知，x/y比值对水解稳定性的影响较大，其中y占比越高，其机械性能越好，但是其在y占比增大的同时性能变好的变化幅度越来越小，基本上在5:5-3:7的比例调整中性能变化不大。考虑到机械性能往往和膜分子内聚力相关，而内聚力和分子间的相互作用力相关，和分子本身的柔性、是否形成网格等有一定关系，故推测y占比较高时分子柔性更大，在高温合成时其更容易形成网格结构，故机械性能好。

Claims (5)

1.一种改性聚芳醚砜膜，其结构式为
Figure FDA0003705613380000011
其中，
0<x<1，且y＝1-x其中，x的取值范围为0.3-0.5。
2.根据权利要求1所述改性聚芳醚砜膜的制备方法，其特征在于，包括如下步骤：
1)4,4'-二氯二苯砜和发烟硫酸反应，得到4,4'-二氯二苯砜-3,3'-二磺酸二钠；
2)4,4'-二氯二苯砜-3,3'-二磺酸二钠和4,4'-二羟基联苯、4,4'-二羟基二苯甲烷反应，得到中间产品；
3)将中间产品质子化制备薄膜，得到所述改性聚芳醚砜膜。
3.根据权利要求2所述的制备方法，其特征在于，步骤1)的反应条件为4,4'-二氯二苯砜和发烟硫酸的摩尔比为2-6:1，其中发烟硫酸以SO3计算；反应温度为120-130℃，反应时间为15-24h。
4.根据权利要求3所述的制备方法，其特征在于，步骤1)还包括反应完毕后用NaOH调节pH，并进行盐析的操作。
5.根据权利要求2所述的制备方法，其特征在于，步骤2)的反应条件为4,4'-二氯二苯砜-3,3'-二磺酸二钠、4,4'-二羟基联苯、4,4'-二羟基二苯甲烷的摩尔比为2:1:1。
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