CN1312833A - 用侧链上碱性氮基团和离子交换基团对工程聚合物进行改性 - Google Patents
用侧链上碱性氮基团和离子交换基团对工程聚合物进行改性 Download PDFInfo
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- CN1312833A CN1312833A CN99809540A CN99809540A CN1312833A CN 1312833 A CN1312833 A CN 1312833A CN 99809540 A CN99809540 A CN 99809540A CN 99809540 A CN99809540 A CN 99809540A CN 1312833 A CN1312833 A CN 1312833A
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Classifications
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Abstract
本发明涉及有机金属化合物,由此有机锂化合物具有芳香基主链并具有含碱性叔氮基的去质子工程聚合物于各种芳香羧基化合物的反应和反应产物。本发明实质上涉及:a)金属化聚合物P-Me于芳香醛和酮的反应并潜在导致反应(Ⅰ)(在为酮的情况下:R1和/或R2表示带有碱性叔氮基的芳香残基,而在醛的情况下,R1是表示带有碱性叔氮基的芳香残基且R2表示H);b)金属化聚合物P-Me与芳香羧酸酯(X=OR)或与羧酸卤化物(X=Hal)的反应并潜在导致反应(Ⅱ),其中如果Ar是带有碱性叔氮基的芳香基,用卤代烷对叔氮进行季铵化是可能的(当使用双卤代烷烃时,同时进行共价交联),且如果Ar是可被磺化的芳香基,则发生反应(Ⅲ);c)由酸性一碱性聚合物混合物制得的酸性-碱性聚合物混合物和膜,其中所述混合物是通过:将反应式a)和b)中所述的酸性和碱性反应产物混合;将本发明的碱性聚合物与任意酸性聚合物混合物而得到。
Description
1.本发明的目的
本发明的目的在于:
(1)一种通过向金属化聚合物中加入含有碱性叔氮基团(例如叔胺、吡啶、嘧啶、三嗪…)的芳族酮及醛,用包含亚芳基的碱性氮基团对以芳基为主链的工程聚合物进行侧链改性的方法。
(2)通过方法(1)制备的侧链改性聚合物,其中侧链包含至少一个带有碱性叔氮的芳族基团。
(3)一种为了使阴离子交换基团与侧链改性的聚合物相结合,而用卤代烷烃对改性聚合物(2)的叔氮进行季铵化的方法。
(4)在侧链上带有阴离子交换官能团并且可以通过方法(3)制备的以芳基为主链的工程聚合物。
(6)用方法(5)制备的侧链改性聚合物,其中侧链包含至少一个带有碱性叔氮的芳族基团。
(7)一种为了使阴离子交换基团与侧链改性聚合物相结合,而用卤代烷烃对改性聚合物(6)中的叔氮进行季铵化的方法。
(8)侧链上带有阴离子交换官能团并且可以通过方法(7)制备的以芳基为主链的工程聚合物。
(9)一种通过下述顺序反应,用包含磺酸基的芳族基团对以芳基为主链的工程聚合物进行侧链改性的方法:
(9b)用硫酸,SO3/P(O)(OR)3,CISO3H等对侧基进行受控的亲电磺化反应。在这种情况下,对侧基进行选择使其较之聚合物主链进行磺化反应的反应活性更高。
(10)侧链上只带有磺酸官能团,并且可以通过方法(9)制备的以芳基为主链的工程聚合物。
(11)聚合物(2),(4),(6),(8)或(10)的膜,其中该聚合物膜可以不被硫化或以共价键交联。
(12)用碱性聚合物(2),(4),(6),(8)与含有磺酸基,膦酸基或羧基的聚合物制备酸性-碱性混合物/酸性-碱性混合物膜的方法。
(13)用碱性聚合物(2),(4),(6),(8)与含有磺酸基的聚合物(10)制备酸性-碱性混合物/酸性-碱性混合物膜的方法。
(14)可以通过方法(12)和(13)制备的酸性-碱性混合物/酸性-碱性混合物膜,其中混合物/混合物膜可进一步通过共价键交联。
(15)离子交换聚合物(4),(8),(10),(14)作为膜应用于,例如聚合物电解膜燃料电池,直接甲醇燃料电池和电渗析的膜工艺中。
(16)在侧链中含有碱性氮的亲水性聚合物(2),(6)作为膜用于渗析和反渗析,毫微过滤,扩散透析,气体渗透,渗透蒸发。
2.本发明要解决的技术问题
对于膜技术的许多应用(反渗透,毫微过滤,微量过滤和超滤,电渗析,扩散渗析,膜电解,膜燃料电池),需要含有离子交换基团的亲水或具有化学稳定性的聚合物,然而这些聚合物在工业上可利用的量有限一甚至今天,在一些情况下,具有有限化学稳定性的乙烯聚合物在上述应用中仍在被使用。而且,这些工业化聚合物的特性带宽不是很大。3.现有技术及其缺点a)用碱性氮改性的聚合物
市场上碱性氮改性的聚合物仍相当少,下面提到的是最重要的:●聚(4-乙烯基吡啶),聚(2-乙烯基吡啶)及共聚物
这两种聚合物已工业化,但也是作为与聚苯乙烯的嵌段共聚物。它们被用于,例如,制备阴离子交换膜(Reiner,Ledjeff,Gudernatsch,Krumbholz2)的前期物质或用含有钴的席夫碱络合用于选择性氧气渗透3。该类聚合物的缺点在于聚合物主链上存在叔C-H键,容易被氧化。●聚苯并咪唑
聚苯并咪唑是一类具有相当化学和机械稳定性的聚合物。许多类型的聚苯并咪唑(部分或全部为芳香族)已经被合成出来并予以检验4。但是,工业化生产的只有少数类型,其中最为重要的是聚合物PBI(聚[(2,2’-间亚苯基)-(5,5’-二苯并咪唑)]),该产品由赛拉尼斯公司(Celanese)生产,商品名为CELAZOLE。特别地,该聚合物作为低可燃性织物5用于消防队。该聚合物的缺点是其难溶于有机溶剂,并且其工作性能差,而且价格非常贵。●聚乙烯亚胺
聚乙烯亚胺作为蛋白质6的沉淀剂用于有机和生物化学。该聚合物的优点在于,由于其高亲水性(在2C上有1N),可溶于水,而且纯品不会形成任何阻抗膜,另外,由于其完全为脂肪族结构,因此其在化学上不很稳定。b)阴离子交换聚合物和膜
工业化阴离子交换聚合物和膜可以分为两大类:●通过氯代7或溴甲基化8聚合物与叔胺反应生产的阴离子交换聚合物。该反应的缺点是卤甲基化反应的致癌性以及“芳香族-CH2-NR3+原子团”结构缺乏化学稳定性。●通过叔氮的烷基化生产的阴离子交换聚合物,例如聚乙烯基吡啶 1,2,9与卤代烷烃1,2。该反应的缺点在于只有少量叔氮聚合物工业化(见上),因此获得的膜的特性带宽有限。聚乙烯基吡啶的缺点在于其化学稳定性有限(见上)。c)侧链上磺化的阳离子交换聚合物
该类聚合物和膜工业化的产品非常少。该类聚合物和膜最重要的代表有:●高氟化离子交换树脂10
该聚合物具有一全氟烷烃主链和一全氟醚侧链,在该全氟醚侧链的末端有一磺酸基。该聚合物用于需要具备强化学膜稳定性的各种用途,例如膜燃料电池11。该聚合物的缺点是价格高($800 US/sq.m),生产工艺复杂10。●Poly X 200012
该聚合物包含一聚亚苯基主链和一芳基侧链,准确的名称为聚(氧化-1,4-亚苯基-羰基-1,4-亚苯基)。该聚合物只在侧链的末端进行磺化。据文献12,该磺化聚合物甚至在温度超过100℃时仍具有良好质子导电性,在该温度下磺化聚醚醚酮(PEEK)的质子导电性已经明显下降。对于Poly X 2000而言,磺酸基位于侧链;而对于聚醚醚酮而言,磺酸基位于主链,由于聚醚醚酮主链的刚性,磺酸基不易缔合,因此具有良好质子导电性可以通过Poly X 2000中磺酸基的更好的缔合而产生出来。该聚合物的缺点在于,与磺化聚醚醚酮12相比,其热稳定性差并且尚未工业化。
4.本发明的目的
本发明的结果在于,可得到在侧链上经碱性氮改性从而使其具有亲水性的以芳基为主链的聚合物和膜,其具有良好的热和机械稳定性。另外,本发明开拓了一条通向具有化学稳定性的阳离子和阴离子交换膜的途径,此外,由于在侧链上存在离子交换基团,与离子交换基团存在于聚合物主链上相比,其在形成离子交换基团缔合物上显示出具有更高的自由度。5.本发明解决的问题(本发明的描述)
为清楚起见,本发明的说明书进一步被分为五部分:
a.通过锂化聚合物进行加成反应而生成的碱性氮改性聚合物;
b.通过锂化聚合物进行取代反应而生成的碱性氮改性聚合物;
c.阴离子交换聚合物及其膜;
d.侧链磺化的阳离子交换聚合物;
e.聚合物a或b与任何理想的磺化聚合物或与阳离子交换聚合物
d制备的酸性-碱性混合物及酸性-碱性混合物膜。a).锂化聚合物进行加成反应生成的碱性氮改性聚合物
Guiver报道了在侧链上进行了亲水改性的PSU,其过程为:首先进行金属化反应,随后加入选择的醛或酮,生成侧链上用OH基团改性的PSU13(图1)。获得了下述取代度:苯甲醛为1.9,苯酮为1.0,丙酮为0.5。
令人惊奇的是,现已发现,根据图1所示的反应,含有叔氮的芳族酮和醛能与锂化PSU发生加成反应。能够发生加成反应的这些碱性芳族酮的例子有(图2):●2,2’-二吡啶酮●4,4’-双(二甲基氨基)-苯酮(米蚩酮)●4,4’-双(二乙基氨基)-苯酮
能发生加成反应的碱性芳族醛的例子有(图2):●4-二甲基氨基苯甲醛●4-二乙基氨基苯甲醛●2-吡啶醛,3-吡啶醛,4-吡啶醛
就该反应而言,取代度取决于碱性芳族化合物的大小。因此,具有空间位阻的2,2’-二吡啶酮,4,4’-双(二甲基氨基)-苯酮(米蚩酮)和4,4’-双(二乙基氨基)-苯酮,获得的取代度为1左右,而上述空间位阻较小的醛获得的取代度能够达到2。
令人惊奇发现,在合成4,4’-双(二乙基氨基)-苯酮与锂化PSU的加成产物时,生成的聚合物由于暴露于空气中,而变成了有色物质,颜色随时间由淡绿色加深至非常深的绿色。这可能是由于发生了图3所示的反应,即因大气中存在着氧气而发生了PSU加成产物的氧化反应。据推测,生成了一种三苯甲烷染料14。该反应指出了一条生成能够键合于锂化聚合物上的有色基团的途径。这些有色基团是带正电的,由于补偿离子,例如Cl-,是能相互交换的,这意味着这些有色基团构成了进行阴离子交换的基团。由于补偿离子是能相互交换的,因此被氧化的碱性聚合物显示出具有离子导电性,其可以通过实验予以证明。由于正电荷在体系中以中介态分布:(P=聚合物主链)与正常的阴离子交换基团相比,这些阴离子交换基团是非常稳定的。
如果有意阻止PSU加成产物发生氧化反应,可以用烷基卤化物Alk-Hal捕获在加成反应过程中形成的Li-烃氧基中间体,生成醚PSU-C(C1R2)-OAlK。因此,与带有自由OH基的加成化合物相比,该加成化合物更具氧化稳定性。b).通过与锂化聚合物进行取代反应而生成的碱性氮改性聚合物
如果用低分子芳族羧酸酯与锂-有机化合物反应,那么在绝大多数情况下可以制得叔醇的锂盐(图4)16。令人感到惊奇的是,现已发现,在选择性条件下(低温,锂化PSU溶液中低的聚合物浓度,过量的碱性化合物),碱性化合物,例如异烟酸乙酯和N,N-二甲基氨基苯甲酸乙酯,与锂化PSU的反应可以控制在生成酮的阶段(图5)。
用这种方法,从锂化聚合物生产芳族侧链上用碱性氮基团(碱性氮,例如吡啶基或二烃基氨基基团)改性的聚合物是可能的。由于其具有芳香性,同时由于通过羰基官能团与主链键合,侧链具有非常好的氧化稳定性。合成出来的含有叔氮的聚合物进一步通过N-季铵化转化成具有氧化稳定性的阴离子交换聚合物(见c)。c).阴离子交换聚合物及其膜
上述用芳族侧链中碱性叔氮改性的聚合物,目前可以通过传统的方法15反应生成阴离子交换聚合物和膜,其中阴离子交换膜甚至可以通过下述方法得到:用侧链叔氮改性的锂化聚合物溶液在偶极非质子溶液(NMP,DMAc,DMF,DMSO等)中制备,卤代烷烃和卤代二烷烃以合适的摩尔比加入到溶液中以产生合适的交联度,并且升高温度将溶剂蒸出。在膜的形成过程中,叔氮季铵化于阴离子交换基团,同时二卤代烷烃在膜中形成共价键相连的网络。d).侧链磺化的阳离子交换聚合物
以b)中描述的反应(通过用羰基使芳族侧链与芳族主链聚合物键合而使芳族羧酸酯与锂化芳烃聚合物发生反应)为基础,依赖于比聚合物主链更易发生亲电磺化的芳族侧基,可以得到侧基磺化的芳族主链聚合物。为了达到这一目标,侧基上芳烃在该聚合物所有芳环中必须具有最大的电子密度。用以制备芳族侧链被磺化的芳烃为主链的聚合物的反应见图6。对于芳族侧链被磺化的PSU Udel,芳族侧链末端的芳烃是整个分子中电子密度最大的部位。因此,该芳烃被磺化并且由于从电子上看也有被磺化可能的醚桥的邻位具有空间位阻,因而实际上磺化发生在醚桥的对位。e).聚合物a或b、任何理想的磺化聚合物与阳离子交换聚合物d制备的酸性-碱性混合物及酸性-碱性混合物膜
a,b和d中新制备的聚合物以及其任何磺化聚合物能够结合用来生产新的酸性-碱性混合物及酸性-碱性混合物膜。由于与位于聚合物主链的酸性、碱性基团相比,侧基末端的酸性、碱性基团空间位阻小,因此酸性、碱性基团存在于芳族侧链的末端为混合物中离子交换基团更好地缔合提供了途径。酸性、碱性基团更好的缔合能够在聚合物基体中导致离子交换基团局部浓度的增加,从而与在主链上用酸性、碱性基团改性主链为刚性芳烃的聚合物的情况相比,甚至在离子交换基团浓度低的情况下,能产生更高的质子导电性。因此,由于存在有极度疏水的全氟主链,从而使磺酸基强烈缔合(成束)10的全氟离子交换聚合物Nafion,其相态能够用该新型酸-碱混合物“复制”替代。除通过聚盐的形成而产生的离子交联外:
6.实施例6.1 N,N-二甲基氨基苯甲醛与锂化PSU的反应配方:11.05克干燥PSF Udel P 1800(0.025摩尔)500毫升无水THF5毫升n-BuLi 10 N(0.05摩尔)10克4-二甲基氨基苯甲醛(0.13摩尔),溶于20毫升THF步骤:
在保护气中,将THF加入到反应容器里。随后,将干燥的聚合物连同氩气一起加到反应容器中,同时搅拌和彻底的冲洗。聚合物一旦溶解,在强氩气流中将其冷却至-65℃。然后,用n-BuLi对聚合物溶液进行滴定,直至出现淡黄/橙色,表明此时反应混合物已不含水。随后,在10分钟内注入10N的n-BuLi。搅拌30分钟。随后,注入4-二甲基氨基苯甲醛的THF溶液。搅拌至反应混合物失去颜色。-65℃下最长的停留时间为1小时。随后,移走丙酮冷浴,代之以冰浴。允许加热至0℃,并且在0℃搅拌1小时。随后,将反应混合物在2升的异丙醇中进行沉淀。于50℃下,首先在隔膜泵真空中,然后在油泵真空中干燥。随后,将聚合物研磨,悬浮于500毫升的甲醇中,然后再次于50℃下,在真空中干燥。所形成的改性PSU的化学结构式见图7。
对聚合物进行的元素分析及其1H-NMR光谱分析表明,其取代度为大约每个PSU重复单元有2个基团。6.2双(N,N-二乙基氨基)苯酮与锂化PSU的反应配方:11.05克干燥PSU Udel P 1800(0.025摩尔)600毫升无水THF3毫升n-BuLi 10 N(0.03摩尔)25克4,4’-双-二乙基氨基苯甲醛(0.13摩尔),溶于50毫升THF(0.077摩尔)步骤:
在保护气中,将THF加入到反应容器中。随后,将干燥的聚合物连同氩气一起加到反应容器中,同时搅拌和彻底的冲洗。聚合物一旦溶解,在强氩气流中将其冷却至-30℃。然后,用n-BuLi对聚合物溶液进行滴定,只至出现淡黄/橙色,表明此时反应混合物已不含水。随后,在10分钟内注入10N的n-BuLi。搅拌50分钟。随后,注入4,4’-二乙基氨基苯甲醛溶液。搅拌至反应混合物失去颜色,不超过24小时。随后,将20毫升异丙醇和2毫升水的混合物注入反应溶液中,然后加热至室温。将聚合物在2升的异丙醇中进行沉淀,过滤并用异丙醇冲洗。然后,将聚合物搅拌注入300毫升的i-PrOH中。随后,再次过滤并再次悬浮于i-PrOH中,搅拌并过滤。随后,将聚合物加入到5升水中并搅拌。过滤后,再次将其加入到5升水中并再次搅拌。其后,再次搅拌并冲洗至pH为7,然后,在80℃下干燥。所形成的改性PSU的化学结构式见图8。
对聚合物进行的元素分析及其1H-NMR光谱分析表明,其取代度为大约每个PSU重复单元有1个基团。聚合物为绿色,是伴随OH基团的断裂,由于氧化部分形成的结果(见图3)。如果将聚合物在更高的温度下放入稀酸中,颜色加深至黑绿色。通过1H和13C-NMR可以看到,实际上图3所示的生成反应产物6.2的反应发生了:在空气过量的情况下,反应产物6.2于60℃下存放于稀酸中以后,OH质子的1H和13C信号几乎完全消失了,其中OH质子的1H和13C信号可以通过H/D交换确定,形状扁平,化学位移为5.8ppm(1H-NMR)或85ppm(13C-NMR)。可以通过,例如PSU-Li-醇盐与碘代甲烷反应(图9),即通过将OH基团进行醚化,从而阻止发色基团的形成。氧化反应产物6.2具有离子电导率,其原因在5a)中说明。最后,分别用和不用盐酸进行二次处理,在0.5N HCl中用阻抗光谱法对氧化聚合物膜进行测定。结果:
6.3 2,2’-二吡啶酮与锂化PSU的反应配方:6.88克干燥PSU Udel P 1800(0.01556摩尔)400毫升无水THF1.7毫升n-BuLi 10 N(0.017摩尔)3.89克二(2-吡啶基)酮(0.021摩尔),溶于20毫升THF步骤:
聚合物膜 | 膜厚[μm] | Rn[Ω*sq.cm] | Rsp[Ω.cm] |
6.2+二次处理6.2不进行二次处理 | 55155 | 7.64.6 | 500840 |
在保护气中,将THF加入到反应容器中。随后,将干燥的聚合物连同氩气一起加到反应容器中,同时搅拌和彻底的冲洗。聚合物一旦溶解,在强氩气流中将其冷却至-30℃。然后,用n-BuLi对聚合物溶液进行滴定,只至出现淡黄/橙色,表明此时反应混合物已不含水。随后,在10分钟内注入10N的n-BuLi。随后搅拌30分钟。随后,将二(2-吡啶基)酮注入THF溶液。
于-30℃下,搅拌至反应混合物失去颜色,不超过48小时。随后,将10毫升异丙醇和1毫升水的混合物注入反应溶液中,然后加热至室温。将聚合物在2升的异丙醇中进行沉淀,过滤并用异丙醇和甲醇冲洗。
将沉淀聚合物再次过滤,干燥并在100毫升甲醇中搅拌。随后,再次过滤并再次悬浮于甲醇中,搅拌、过滤并在80℃下干燥。反应产物的结构式见图10。
对聚合物进行的元素分析表明,以二吡啶基计,改性PSU的取代度为大约每个PSU重复单元有0.85个基团。6.4异烟酸乙酯与锂化PSU的反应配方:8.84克干燥PSU Udel P 1800(0.02摩尔)300毫升无水THF4毫升n-BuLi 10 N(0.04摩尔)10.5毫升异烟酸乙酯(0.07摩尔)步骤:
在保护气中,将THF加入到反应容器中。随后,将干燥的聚合物连同氩气一起加到反应容器中,同时搅拌和彻底的冲洗。聚合物一旦溶解,在强氩气流中将其冷却至-30℃。然后,用n-BuLi对聚合物溶液进行滴定,只至出现淡黄/橙色,表明此时反应混合物已不含水。随后,注入10N n-BuLi。随后搅拌50分钟。随后,注入异烟酸乙酯,于-30℃下,搅拌至反应混合物失去颜色,不超过24小时。随后,将20毫升异丙醇和2毫升水的混合物注入反应溶液中,然后让温度升高到室温。将聚合物在2升的异丙醇中进行沉淀,过滤并用异丙醇冲洗。随后,在300毫升的i-PrOH中对聚合物进行搅拌。随后,再次过滤并再次悬浮于i-PrOH中,搅拌并过滤。过滤后,再次将聚合物加入到5升水中并再次搅拌。随后,再次过滤而后在80℃下干燥。反应产物见图11。
对聚合物进行的元素分析及其1H-NMR光谱分析表明,以4-比啶基羰基计,改性PSU的取代度达到1.65。6.5 N,N-二甲基氨基苯甲酸乙酯与锂化PSU的反应配方:11.05克干燥PSU Udel P 1800(0.025摩尔)600毫升无水THF5毫升n-BuLi 10 N(0.05摩尔)48.32克N,N-二甲基氨基苯甲酸乙酯,溶于100毫升THF(0.25摩尔)步骤:
在保护气中,将THF加入到反应容器中。随后,将干燥的聚合物连同氩气一起加到反应容器中,同时搅拌和彻底的冲洗。聚合物一旦溶解,在强氩气流中将其冷却至-60℃。然后,用n-BuLi对聚合物溶液进行滴定,只至出现淡黄/橙色,表明此时反应混合物已不含水。随后,在10分钟内注入10N n-BuLi。然后搅拌50分钟。随后,将N,N-二甲基氨基苯甲酸乙酯溶液注入THF。搅拌10分钟。随后,将20毫升异丙醇和2毫升水的混合物注入反应溶液中,然后让温度升高到室温。将聚合物在2升的异丙醇中进行沉淀,过滤并用异丙醇和甲醇冲洗。将沉淀聚合物再次过滤,干燥并在100毫升甲醇中搅拌。随后,再次过滤并再次悬浮于甲醇中,搅拌、过滤并在80℃下干燥。对聚合物进行的元素分析表明,取代度为每个PSU重复单元有0.75个对-N,N-二甲基氨基苯基羰基。进一步测试表明,取代度可以通过延长锂化PSU与N,N-二甲基氨基苯甲酸乙酯的反应时间来提高。本反应的产物(每个PSU重复单元带有一个对-二甲基氨基苯基羰基)见图12。6.6反应产物6.2与磺化PSU形成的酸-碱混合膜
将4克SO3Li型磺化PSU Udel溶解于25克N-甲基吡咯烷酮中。随后,将1克反应6.2的产物(每个PSU重复单元有1.1个基团)加入到上述溶液中并且搅拌至溶解。然后,将绿色非常深的溶液滤出,脱气后在玻璃板上涂成薄膜。然后于120℃将溶液蒸发掉。随后,将玻璃板放入装满淡水的水浴中,其上面的聚合物膜从玻璃板上脱离。随后,于70℃将膜在10%的硫酸中进行初次处理,然后在淡水中进行二次处理。随后,对膜的性能进行表征。表征结果:离子交换量: 1.35meq SO3H/g溶胀(H+-form,RT) : 33.14%比电阻(H+-form,RT): 27.6Ω.cm6.7由反应产物6.4和磺化PSU组成的酸-碱混合膜
将4克SO3Li型磺化PSU Udel溶解于25克N-甲基吡咯烷酮中。随后,将1克反应6.2的产物(每个PSU重复单元有1.65个基团)加入到上述溶液中并且搅拌至溶解。然后,将溶液过滤,脱气后在玻璃板上涂成薄膜。然后于120℃将溶液蒸发掉。随后,将玻璃板放入装满淡水的水浴中,其上面的聚合物膜从玻璃板上脱离。随后,于70℃将膜在10%的硫酸中进行初次处理,然后在淡水中进行二次处理。随后,对膜的性能进行表征。表征结果:离子交换量: 1.09meq SO3H/g溶胀长(H+-form,RT):24.6%比电阻(H+-form,RT):21.2 Ω.cm6.8由反应产物6.5和磺化PSU组成的酸-碱混合物膜
将4克SO3Li型磺化PSU Udel溶解于25克N-甲基吡咯烷酮中。随后,将1克反应6.2的产物(每个PSU重复单元有0.75个基团)加入到上述溶液中并且搅拌至溶解。然后,将溶液过滤,脱气后在玻璃板上涂成薄膜。然后于120℃将溶液蒸发掉。随后,将玻璃板放入装满淡水的水浴中,其上面的聚合物膜从玻璃板上脱离。随后,于70℃将膜在10%的硫酸中进行初次处理,然后在淡水中进行二次处理。随后,对膜的性能进行表征。表征结果:离子交换量: 1.11meq SO3H/g溶胀(H+-form,RT): 23.5%比电阻(H+-form,RT):17.6Ω.cm
7.本发明的新颍性上述新制备的聚合物和膜以及制备它们的方法到目前为止在文献中尚未予以报道。8.本发明的优点本发明所涉及的新制备的聚合物和膜由于具有芳族侧链,因此具有化学稳定性,并且能够在控制下进一步被改性:●通过用卤代烃使碱性氮季铵化,可以制备新的阴离子交换聚合物和膜,由于碱性氮与芳族侧链直接键合,因此变得比工业化的阴离子交换聚合物和膜更具化学稳定性。由于存在使用二卤代烃的可能 性,因此阴离子交换聚合物膜同时能够进一步通过共价键交联。●具有芳烃侧基,同时芳烃侧基发生磺化的聚合物的合成能够改善聚合物基体磺酸基的缔合,从而即使在离子交换基团浓度相对低的情况下,能够产生更高的质子导电性。●由于侧基比聚合物主链更容易移动,因此与酸性和碱性基团存在于聚合物主链的酸性-碱性混合物和酸性-碱性混合膜相比,本发明所涉及的酸性-碱性混合物和酸性-碱性混合膜可以显示出更好的离子交换基团的缔合性。除了由于聚盐形成产生的离子交联外,由于存在共价键交联从而使得这些混合物和混合物膜在溶胀和机械稳定性方面进一步提高。9.关键词芳基主链聚合物用含有碱性叔氮的侧基进行改性阴离子交换聚合物阴离子交换聚合物膜阳离子交换聚合物阳离子交换聚合物膜含有碱性叔氮的芳香族羧酸酯羧酸卤化物含有碱性叔氮的芳香酮和醛酸-碱聚合物混合物酸-碱聚合物混合物膜芳烃为主链的金属化聚合物膜燃料电池膜膜法
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Claims (26)
1.一种用含有亚芳基的碱性氮基团对以芳基为主链的工程聚合物进行侧链改性的方法,该聚合物用金属有机化合物进行去质子化处理并且由图13所列基团组成,该方法的特点在于,通过图13所示的反应,含有碱性叔氮基团(例如叔胺或碱性氮基团)的芳酮和醛(例如杂环芳香化合物,如吡啶、嘧啶、三嗪、咪唑、吡唑、三唑、噻唑、恶唑等)加入到金属化聚合物P-Me中,其中该金属化聚合物含有基团R1和/或R2,并通过桥基R4、R5或R6彼此相连,在这方面,作为中间化合物而形成的金属醇化物进一步可以用水进行质子化或用卤代烷烃进行醚化反应。
2.根据权利要求1所使用的方法制备的聚合物,其侧链用碱性叔氮基团改性。
3.一种对根据权利要求1和2制备的改性聚合物的叔氮进行季铵化的方法,其特征在于改性聚合物与卤代单烷烃反应。
4.一种同时对根据权利要求1和2制备的改性聚合物的叔氮基团进行季铵化和共价交联的方法,其特征在于改性聚合物与卤代单烷烃和卤代双烷烃的混合物反应。
5.根据权利要求3和4的方法制备的以芳基为主链的工程聚合物,其侧链上含有阴离子交换官能团,并且可同时通过共价键交联。
7.根据权利要求6所述方法制备的侧链改性聚合物。
8.一种对根据权利要求6和7制备的改性聚合物的叔氮基团进行季铵化的方法,其特征在于,为使阴离子交换基团与侧链改性聚合物结合,将改性聚合物溶液与卤代烷烃反应。
9.一种制备通过共价键交联的阴离子交换聚合物和膜的方法,其特征在于,将如权利要求6和7所述的聚合物的溶液与卤代单烷烃和卤代双烷烃的混合物反应。
10.根据权利要求8和9所述方法制备的侧链含有阴离子交换官能团的以芳基为主链的工程聚合物及其膜。
11.一种用含有磺酸基的芳基对以芳基为主链的工程聚合物进行侧链改性的方法,其特征在于,金属化聚合物经历了下述过程的反应:
11a)芳族羧酸衍生物Ar-COX,例如羧酸酯Ar-COOR′或芳族羧酸卤化物Ar-COHal,与金属化聚合物P-Me的反应:
11b)用硫酸,SO3/P(O)(OR)3,CISO3H或另一种亲电磺化剂对侧基进行的控制亲电磺化反应,在这种情况下,对侧基进行选择使其较之聚合物主链进行的磺化反应的反应活性更高。
12.只在侧链含有磺酸官能团的以芳基为主链的工程聚合物,该聚合物根据权利要求11所述方法制备。
13.由根据权利要求2,5,7,10,12所述的聚合物制备膜的方法,其特征在于,聚合物溶解于偶极非质子溶剂中,然后将聚合物溶液在载体(玻璃板、织物、带羊毛的生羊皮)上涂成薄膜,随后将溶剂蒸发掉。
14.根据权利要求13所述的方法制备的聚合物膜。
15.一种制备酸性-碱性混合物/酸性-碱性混合物膜的方法,其特征在于,根据权利要求2,5,7,10所述的侧基含有碱性基团的聚合物与含有磺酸基、膦酸基或羧基的聚合物(酸或盐的形式)在偶极非质子溶剂中混合,然后将含有两种聚合物的溶液在载体(玻璃板、织物、带羊毛的生羊皮)上涂成薄膜,溶剂在载体上蒸发掉。
16.一种制备酸性-碱性混合物/酸性-碱性混合物膜的方法,其特征在于,根据权利要求2,3,7,10所述的侧基含有碱性基团的聚合物与权利要求12所述的聚合物在偶极非质子溶剂中混合,然后将含有两种聚合物的溶液在载体(玻璃板、织物、带羊毛的生羊皮)上涂成薄膜,随后溶剂被蒸发掉。
17.根据权利要求15和16所述的方法制备的酸性-碱性混合物/酸性-碱性混合物膜,其中混合物/混合物膜可进一步通过共价键进行交联。
18.根据权利要求1至17的聚合物和膜,其特征在于,用于本发明的改性反应的优选碱性聚合物为从聚醚砜物质组中选取的聚合物,本发明的工业化聚醚砜的实例为:
●聚醚砜(PSU Udel):R2(R3=CH3)-R4-R1(R3=H)-R5-R1-R4
●聚醚砜(PES Victrex):R1-R5-R1-R4
●聚苯砜(PPhSU Radel R):R1(R3=H)-R1(R3=H)-R4-R1(R3=H)-R5-R1-R4
●聚醚醚砜(PEES Radel A):[R4-R1(R3=H)-R4-R1(R3=H)-R5-R1(R3=H)]n-[R4-R1(R3=H)-R5-R1(R3=H)]m,n/m=0.18
19.根据权利要求18的聚合物和膜,其特征在于,用于本发明的改性反应的碱性聚合物为聚醚砜PSU Udel。
21.根据权利要求20所述方法制备的阴离子交换聚合物。
22.根据权利要求13和14所述方法,由权利要求20和21所述阴离子交换聚合物得到的膜的制备方法。
23.一种制备酸性-碱性混合物/酸性-碱性混合物膜的方法,其特征在于,权利要求20至23所述阴离子交换聚合物与权利要求15,16,17所述酸性聚合物反应,生成酸性-碱性混合物/酸性-碱性混合物膜。
24.根据权利要求23所述方法制备的酸性-碱性混合物/酸性-碱性混合物膜。
25.根据权利要求5,9,10,12,17,18,19,20,21,22,23,24所述的阴离子交换聚合物作为膜应用于膜工艺中,例如用于聚合物电解膜燃料电池(PEDC),直接甲醇燃料电池(DMFC),扩散渗透和电渗透。
26.根据权利要求2,5,7,9,10,12,14,17,18,19,20,21,22,23,24所述的亲水性聚合物作为膜应用于渗析,反渗透,毫微过滤,气体渗透,蒸发渗透或perstraction。
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US11826746B2 (en) | 2017-07-06 | 2023-11-28 | Rensselaer Polytechnic Institute | Ionic functionalization of aromatic polymers for ion exchange membranes |
US12027731B2 (en) | 2018-11-26 | 2024-07-02 | Rensselaer Polytechnic Institute | Phosphate anion-quaternary ammonium ion pair coordinated polymer membranes |
CN109810254A (zh) * | 2019-01-18 | 2019-05-28 | 北京赛特超润界面科技有限公司 | 离子交联型聚醚醚酮-聚醚砜聚合物及其合成方法和薄膜及该薄膜在盐差发电中的应用 |
CN109860701A (zh) * | 2019-02-15 | 2019-06-07 | 云南大学 | 一种用于锂离子电池的全固态电解质及其制备方法 |
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CA2338606A1 (en) | 2000-02-24 |
AU771230B2 (en) | 2004-03-18 |
DE19836514A1 (de) | 2000-02-17 |
KR20010072431A (ko) | 2001-07-31 |
IL141972A (en) | 2008-06-05 |
JP2002522607A (ja) | 2002-07-23 |
DK1105433T3 (da) | 2005-01-10 |
EP1105433A1 (de) | 2001-06-13 |
KR100649370B1 (ko) | 2006-12-21 |
AU2004200396A1 (en) | 2004-02-26 |
ES2237145T3 (es) | 2005-07-16 |
CN1293123C (zh) | 2007-01-03 |
DE59910949D1 (de) | 2004-12-02 |
US20020045729A1 (en) | 2002-04-18 |
ATE280795T1 (de) | 2004-11-15 |
BR9912935B1 (pt) | 2010-09-08 |
AU5621299A (en) | 2000-03-06 |
BR9912935A (pt) | 2001-09-25 |
WO2000009588A1 (de) | 2000-02-24 |
US6590067B2 (en) | 2003-07-08 |
IL141972A0 (en) | 2002-03-10 |
ZA200102025B (en) | 2002-02-13 |
EP1105433B1 (de) | 2004-10-27 |
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