CN112876585A - 一种Ag/MXene引发的自由基聚合及有机水凝胶制备方法 - Google Patents

一种Ag/MXene引发的自由基聚合及有机水凝胶制备方法 Download PDF

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CN112876585A
CN112876585A CN202110066131.XA CN202110066131A CN112876585A CN 112876585 A CN112876585 A CN 112876585A CN 202110066131 A CN202110066131 A CN 202110066131A CN 112876585 A CN112876585 A CN 112876585A
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mxene
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孙晓毅
罗嘉盛
李娟�
蒙健强
王洪杨
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Abstract

本发明具体公开了一种Ag/MXene作为引发剂的应用，Ag/MXene作为引发剂，可在无氧或有氧条件下引发烯烃类单体在有机溶剂或水溶液或混合溶剂中的聚合反应；所述的Ag/MXene是由MXene与具有氧化性的银离子发生氧化还原反应所制得，同样地，MXene与其他贵金属(如金、钯)复合后也具有优异的引发烯烃类单体聚合的作用。本发明创新地发现，Ag/MXene可在无需常规引发条件下(例如添加光引发剂或者普通自由基引发剂)，即可引发烯烃类单体聚合。并且通过此法制备的纳米复合有机水凝胶具有优良的保水性能、粘附性、抗冻抗干性能和近红外光热转换性能。

Description

一种Ag/MXene引发的自由基聚合及有机水凝胶制备方法
技术领域
本发明涉及MXene和自由基聚合领域，且特别涉及一种Ag/MXene引发的自由基聚合方法及有机水凝胶的制备及应用。
背景技术
自由基聚合是一种链式反应，主要包括链引发、链增长、链终止和链转移四个基元反应。链引发及引发方法是形成单体自由基(活性种)的反应，是聚合反应的第一步。常用产生自由基的方法是引发剂的受热分解或氧化还原分解反应，也可以用加热、紫外线辐照、高能辐照、电解和等离子体引发等方法产生自由基。
MXene是一类材料科学中的新型二维无机化合物，是由几个原子层厚度的过渡金属碳化物、氮化物或碳氮化物构成。由于MXene材料独特的表面结构以及活性终端基团(-OH、-O、-F)，使其具备优良的导电性、载流子迁移率、亲水性、弹性模量、光热转换性质等，可被广泛应用于催化、储能、海水淡化、光热治疗和电磁屏蔽等诸多领域。然而MXene自身易氧化降解，限制其进一步发展，将MXene与聚合物基材料复合能够有效提高MXene的环境稳定性，拓宽其实际应用范围。
虽然现在已经有二维MXene材料具有自引发光接枝和光聚合(self-initiatedphotografting and photopolymerization，简称SIPGP)的作用{ChemicalCommunications 2015,51(2),314-317}，该类MXene引发聚合的机理为在紫外光的辐照下，MXene表面被激发产生自由基，进一步引发单体聚合。此外，发明人研究团队报道了以超声辅助同步刻蚀剥离方法制备的二维MXene材料作为自由基引发剂引发烯烃类单体聚合及合成聚合物水凝胶{中国专利号：201910496381X，Chemical Science 2019,10(46),10765-10771}。但是，该MXene材料制备时仅收集高离心速度下(离心速度通常在10000rpm以上)的上清液产品，产率不高，且引发聚合必须在无氧条件下进行。目前未见在不除氧条件下，MXene材料引发聚合的报道。而传统方法刻蚀得到的MXene材料不具备引发单体聚合的作用，且目前尚未见无需光照条件、无需除氧直接以Ag/MXene材料作为自由基引发剂引发烯烃类单体聚合及合成聚合物凝胶的研究报道。
发明内容
本发明的目的在于提供一种Ag/MXene作为自由基引发剂的应用。
本发明第二目的在于，提供一种采用Ag/MXene作为自由基引发剂制备聚合物有机水凝胶的方法。
一种Ag/MXene作为自由基引发剂的应用，将Ag/MXene作为引发剂，引发烯烃单体在除氧/有氧条件下聚合；
所述的Ag/MXene的制备方法为：将MXene与具有氧化性的银离子(例如硝酸银)发生氧化还原反应制得；
所述的Ag可替为Au，Pd等贵金属；
所述的M为过渡金属中的至少一种；优选为Ti；
所述的A为IIIA或IVA元素中的至少一种；优选为Al；
所述的X为C和/或N；优选为C。
本发明创新地发现，所述常规方法制得的MXene，通过与贵金属阳离子(Ag+、Pd2+、Au3+)发生氧化还原反应，得到贵金属负载的MXene二维材料具有良好的引发作用，可在无需现有常规引发条件下(例如无常规的光引发或者普通自由基引发剂引发下)，即可引发烯烃单体聚合。
本发明所述Ag/MXene具有引发作用的关键是MXene与贵金属单质的复合，相较于现有的方法，本发明制备方法制得的二维复合材料可表现出良好的自由基引发作用。
本发明优选的PM/MXene(PM为贵金属)层状化合物制备过程(以Ag/MXene为例)为：通过LiF/HCl作为刻蚀剂，在35℃反应48h，用去离子水在3500rpm下离心洗涤至pH＝5～6，再用3500rpm离心得到上清液，得到的上清液即为MXene纳米片。于上清液中逐滴加入硝酸银水溶液，混合反应10min即得Ag/MXene材料。
本发明所述的应用，采用本发明创新的Ag/MXene，可以出人意料地起到引发烯烃单体聚合的作用；可无需光照辐射、或者常规自由基引发剂(例如过硫酸盐、过氧化氢、核黄素)的作用下，引发所述的烯烃单体聚合。
所述的应用，Ag/MXene作为引发剂，在水溶液或者有机溶剂体系引发烯烃单体在除氧条件下聚合得到聚合物。在多元醇水混合溶剂体系Ag/MXene引发烯烃单体在室温不需除氧也可聚合得到聚合物。
所述的烯烃单体为含双键的单体；
优选为具有式1、式2、式3、式4结构式的单体；
Figure BDA0002904192150000031
R1～R3独自为H、C1～C6的烷基、C1～C6的烷氧基或C1～C6的N-取代烷基氨基、笼型六面体倍半硅氧烷基。R4可为H、氟、氯、溴、碘等卤素原子、胺基、羟基、羧基、磺酸基、C1～C6的烷基、C1～C6的烷氧基或C1～C6的N-取代烷基氨基。n为聚乙二醇二丙烯酸酯中重复单元数，在2-200区间内。
作为优选，所述引发剂与单体的质量比为5～500。
作为优选，聚合起始溶液中，单体浓度为0.01～30wt％。
作为优选，多元醇水溶液中多元醇的含量为10％～100％。
作为优选，聚合反应的温度为室温(水溶液和多元醇水溶液)、40℃(四氢呋喃溶液、二甲基亚砜溶液)、60℃(N,N-二甲基甲酰胺溶液)。
本发明还提供了一种聚合物有机水凝胶的制备方法，由Ag/MXene、单体、交联剂组成的多元醇水溶液中在无需除氧条件下聚合得到。
现有技术中，丙烯酸类、甲基丙烯酸类和丙烯酰胺类单体通常需在光照辐射引发，或者自由基引发剂例如过硫酸盐、过氧化氢、核黄素，实现聚合和凝胶化。传统方法常规刻蚀得到的MXene不具备引发作用，而本发明创新地采用所述的Ag/MXene作为引发剂，可使单体在黑暗条件下即可实现聚合和凝胶化。不仅如此，较其它引发剂引发制备的凝胶，采用该方法制得的凝胶还具有良好的光热转换性能。
与现有技术相比，本发明的有益效果在于：
(1)本发明首次发现且通过电子顺磁共振(EPR)、核磁共振等手段证实，本发明所述的Ag/MXene具有产生自由基、引发聚合作用，可在无光照辐射、无常规自由基引发剂下，即可引发多种单体聚合。
(2)本发明制备得到的Ag/MXene，不仅能引发单体制得有机水凝胶，而且能赋予凝胶优异的保水性能、粘附性、抗冻抗干性能和近红外光热转换性能。
附图说明
【图1】为本发明实施例2中Ag/MXene纳米片水溶液和四氢呋喃溶液的电子顺磁共振谱图；
【图2】为本发明实施例3中Ag/MXene纳米片在水溶液中引发N,N-二甲基丙烯酰胺(DMAAm)单体聚合核磁图；
【图3】为本发明实施例4中Ag/MXene纳米片在有机溶剂中引发不同单体聚合核磁表征及单体结构图；
【图4】为本发明实施例5中Ag/MXene材料在不同多元醇水溶液中引发丙烯酰胺聚合示意图；
【图5】为本发明实施例6中Ag/MXene纳米片在丙三醇水溶液中引发不同单体聚合示意图；
【图6】为本发明实施例7中Ag/MXene纳米片引发丙烯酰胺单体聚合制备得到的纳米复合有机水凝胶的光热升温图；
【图7】为本发明实施例8中Ag/MXene纳米片引发丙烯酰胺单体聚合制备得到的纳米复合有机水凝胶在室温环境的质量变化图；
【图8】为本发明实施例9中Ag/MXene纳米片引发丙烯酰胺单体聚合制备得到的纳米复合有机水凝胶粘附不同物体表面的示意图；
【图9】为本发明实施例10中不同贵金属复合MXene材料引发丙烯酰胺聚合示意图。
具体实施方式
以下实施例旨在说明本发明而不是对本发明的进一步限定。
实施例1
制备Ag/Ti3C2Tx、Au/Ti3C2Tx、Pd/Ti3C2Tx二维纳米材料
Ag/Ti3C2Tx的制备：
将1g Ti3AlC2(400目)均匀分散在1.6g LiF/20mL HCl(9M)溶液中，在35℃反应48h，超声30min，用去离子水反复洗涤至pH约为5～6；然后，用3500rpm、离心10min取上清液得到Ti3C2Tx纳米片。将上清液冻干得到Ti3C2Tx粉末，取10mg重新超声分散到4g水中；再取3.94mg硝酸银溶于1g水，逐滴加入Ti3C2Tx水溶液中，再反应10min，得到Ag/Ti3C2Tx水溶液。
Au/Ti3C2Tx的制备：
将1g Ti3AlC2(400目)均匀分散在1.6g LiF/20mL HCl(9M)溶液中，在35℃反应48h，超声30min，用去离子水反复洗涤至pH约为5～6；然后，用3500rpm离心10min取上清液得到Ti3C2Tx纳米片。将上清液冻干得到Ti3C2Tx粉末，取10mg重新超声分散到4g水中；再取浓度为100mg/mL氯金酸水溶液53μL(5.3mg)溶于1g水，逐滴加入Ti3C2Tx水溶液中，再反应10min，得到Au/Ti3C2Tx水溶液。
Pd/Ti3C2Tx的制备：
将1g Ti3AlC2(400目)均匀分散在1.6g LiF/20mLHCl(9M)溶液中，在35℃反应48h，超声30min，用去离子水反复洗涤至pH约为5～6；然后，用3500rpm离心10min取上清液得到Ti3C2Tx纳米片。将上清液冻干得到Ti3C2Tx粉末，取10mg重新超声分散到4g水中；再取4.2mgPdCl2溶于0.1g乙醇和0.9g水混合溶剂，逐滴加入Ti3C2Tx水溶液中，再反应10min，得到Pd/Ti3C2Tx水溶液。
实施例2
Ag/MXene纳米片水溶液和四氢呋喃中电子顺磁共振谱图
本发明所述Ag/MXene材料通过电子顺磁共振谱图(EPR)证明Ag/MXene水溶液体系产生羟基自由基，Ag/MXene四氢呋喃溶液体系产生超氧阴离子自由基，可引发单体聚合，具体如下：
将1μL 5,5-二甲基-1-氧化吡咯啉(DMPO)溶于50μLAg/MXene溶液中，对照组为原MXene溶液，通过BrukerA300光谱仪进行自由基检测。EPR结果见图1，表明MXene水溶液中不产生羟基自由基，而Ag/MXene水溶液中可以产生羟基自由基，且Ag/MXene四氢呋喃溶液中有超氧阴离子自由基信号峰出现，因此可以引发单体聚合。
实施例3
Ag/MXene纳米片水溶液中引发N,N-二甲基丙烯酰胺单体聚合核磁表征
将实施例1得到的0.125mgAg/MXene纳米片、40μL DMAAm单体和1mL水加入反应瓶中，橡胶塞密封后，氮气鼓泡除氧5min，置于20℃环境下避光反应24h。反应结束时加入对苯醌水溶液(保持浓度1μmol/mL)终止反应。将反应原液冷冻干燥，取5mg溶于0.5mL氘代氯仿(CDCl3)中，通过核磁表征单体是否聚合。核磁结果见图2。
由图2可知，单体不饱和双键碳上的氢的特征峰主要在5.6、6.3、6.6ppm处(图2中a，b标记处)，而冻干后样品的核磁共振氢谱在1-2，2.6ppm处(图2中a＇，b＇标记处)出现了聚合后饱和碳主链上的氢的特征峰，表明有聚合物的生成，Ag/MXene纳米片具有引发作用。
实施例4
Ag/MXene纳米片在有机溶剂(N,N-二甲基甲酰胺、四氢呋喃、二甲基亚砜)中引发不同单体聚合核磁表征
将实施例1得到的0.5mgAg/MXene纳米片、100mg(固态)/100μL(液态)单体(丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸甲酯、苯乙烯、甲基丙烯酸异丁基低聚倍半硅氧烷酯)和1mL有机溶剂加入反应瓶中，橡胶塞密封后，氮气鼓泡除氧5min，置于60℃环境下避光反应24h。反应结束时，将反应原液滴入8倍反应原液体积的冰甲醇或冰石油醚中，沉淀出聚合物。将聚合物真空干燥后，取5mg溶于0.5mL氘代氯仿(CDCl3)中，通过核磁表征聚合物。核磁结果和单体结构见图3。
由图3(a)可知，六组样品的核磁共振氢谱在1-2ppm处出现聚合后饱和碳主链上的氢的特征峰，表明有聚合物的生成，Ag/MXene纳米片具有引发作用。图3(b)为对应单体结构示意图。
实施例5
Ag/MXene材料在不同多元醇水溶液中引发丙烯酰胺聚合
称量1g浓度为Ag/Ti3C2Tx，1g水和4g多元醇(乙二醇或1,2-丙二醇或丙三醇或聚乙二醇200或聚乙烯醇)于25mL反应瓶中，搅拌均匀，加入1g的丙烯酰胺单体、0.0060gN,N-亚甲基双丙烯酰胺交联剂，20℃下避光反应，即可形成聚合物有机水凝胶。不同Ag/MXene聚合得到的凝胶图见图4所示，凝胶样品倒置后不流动，说明不同Ag/MXene材料在有氧条件下可以起到引发单体聚合进一步得到凝胶。
实施例6
Ag/MXene纳米片在丙三醇水溶液中引发不同单体聚合
称量1gAg/Ti3C2Tx水溶液，1g水和4g丙三醇于25mL玻璃瓶中，搅拌均匀，分别称量1g不同单体{丙烯酰胺(AAm)、N-异丙基丙烯酰胺(NIPAAm)、2-丙烯酰胺基-2-甲基丙磺酸(AMPS)、甲基丙烯酰基乙基磺基甜菜碱(SBMA)、4-羟基丁基丙烯酸酯(4-HBA)、甲基丙烯酸(MAAc)和甲基丙烯酸羟乙酯(HEMA)}，0.0060g N,N-亚甲基双丙烯酰胺(MBA)，20℃下避光反应，即可形成聚合物有机水凝胶。不同单体聚合得到的凝胶图见图5所示，凝胶样品倒置后不流动，说明不同Ag/MXene材料可以起到引发不同单体聚合进一步得到凝胶。
实施例7
Ag/MXene纳米片引发AAm单体聚合制备得到的纳米复合有机水凝胶光热转换实验
为了评估纳米复合有机水凝胶的光热效应，对实施例5制备的Ag/Ti3C2Tx纳米复合有机水凝胶(Ag/Ti3C2Tx OHG)，在功率密度为1.0W/cm2下，利用808nm近红外激光照射5min，每隔30s用红外成像仪记录其温度变化。使用纯水作为对照(1.0W/cm2)。结果如图6所示，Ag/Ti3C2Tx纳米复合有机水凝胶在1.0W/cm2808nm激光光照5min后，温度升高达40℃，纯水同等条件下温度升高仅2℃。
实施例8
Ag/MXene纳米片引发AAm单体聚合制备得到的纳米复合有机水凝胶的环境稳定性实验
将实施例5制备的Ag/Ti3C2Tx有机水凝胶(Ag/Ti3C2Tx OHG)和水凝胶(Ag/Ti3C2TxHG)置于22℃，45％湿度环境下，记录凝胶体积和质量变化，质量变化见图7。由图7可知，Ag/Ti3C2Tx有机水凝胶在22℃，45％湿度环境下存放9天以后，质量损失在18.1％以内；而Ag/Ti3C2Tx水凝胶在22℃，45％湿度环境下存放9天以后，质量损失达到82.9％。因此Ag/Ti3C2Tx有机水凝胶相比水凝胶表现出优良的保水性能。
实施例9
Ag/MXene纳米片引发AAm单体聚合制备得到的纳米复合有机水凝胶粘附不同物体表面示意图
将实施例5制备的Ag/Ti3C2Tx有机水凝胶上表面粘附在玻璃板上，在下表面上粘附橡胶质地的洗耳球(质量37.6g)、聚四氟乙烯材质的活塞(质量47.2g)、装水的塑料盖瓶(质量48.7g)、金属盖(质量54.7g)、木头架子(质量7.1g)和手指皮肤，见图8，发现其对于不同材料表面具有广泛持久的粘附力。
实施例10
不同贵金属复合MXene材料引发丙烯酰胺聚合
称量1g浓度为Ag/Ti3C2Tx或Au/Ti3C2Tx或Pd/Ti3C2Tx水溶液，1g水和4g丙三醇于25mL玻璃瓶中，搅拌均匀，加入1g的丙烯酰胺单体、0.0060gN,N-亚甲基双丙烯酰胺交联剂，20℃下避光反应10min后，即可形成聚合物有机水凝胶。不同Ag/MXene聚合得到的凝胶图见图9所示，凝胶样品倒置后不流动，说明不同Ag/MXene材料在不除氧条件下可以起到引发单体聚合进一步得到凝胶。

Claims (7)

1.一种Ag/MXene作为自由基引发剂的应用，其特征在于，将Ag/MXene作为引发剂，引发烯烃单体在水溶液、有机溶剂及多元醇水溶液中聚合；
所述的Ag/MXene由硝酸银加入常规MXene分散液中发生氧化还原反应制得；
所述的Ag可替换为Au，Pd等贵金属；
所述的MXene为具有二维层状结构的过渡金属碳化物；
所述的M为过渡金属中的至少一种；
所述的A为IIIA或IVA元素中的至少一种；
所述的X为C和/或N。
2.如权利要求1所述的应用，其特征在于，聚合过程在无光引发条件下进行，或者，在无外加过硫酸盐化合物、过氧化物、核黄素中的至少一种的自由基引发剂下进行。
3.如权利要求1所述的应用，其特征在于，所述的有机溶剂为N,N-二甲基甲酰胺(DMF)、四氢呋喃(THF)和二甲基亚砜(DMSO)中的至少一种。
4.如权利要求1所述的应用，其特征在于，所述的多元醇为丙三醇(Gly)、乙二醇(EG)、1,2-丙二醇(1,2-PG)、聚乙二醇200(PEG200)、聚乙烯醇(PVA)中的至少一种。
5.如权利要求1所述的应用，其特征在于，所述的烯烃单体为含双键的单体；
优选为具有式1、式2、式3、式4结构式的单体；
Figure FDA0002904192140000011
R1～R3独自为H、C1～C6的烷基、C1～C6的烷氧基或C1～C6的N-取代烷基氨基、笼型六面体倍半硅氧烷基。R4可为H、氟、氯、溴、碘等卤素原子、胺基、羟基、羧基、磺酸基、C1～C6的烷基、C1～C6的烷氧基或C1～C6的N-取代烷基氨基。n为聚乙二醇二丙烯酸酯中重复单元数，在2-200区间内。
6.如权利要求1所述的应用，其特征在于，水溶剂所述的烯烃单体为丙烯酰胺(AAm)、N,N-二甲基丙烯酰胺(DMAAm)、N-异丙基丙烯酰胺(NIPAM)、2-丙烯酰胺-2-甲基丙磺酸(AMPS)、甲基丙烯酰基乙基磺基甜菜碱(SBMA)、甲基丙烯酸(MAAc)和甲基丙烯酸羟乙酯(HEMA)中的至少一种；有机溶剂所述的烯烃单体为丙烯酸甲酯(MA)、丙烯酸乙酯(EA)、丙烯酸丁酯(BA)、甲基丙烯酸甲酯(MMA)、苯乙烯(St)和甲基丙烯酸异丁基低聚倍半硅氧烷酯(POSSMA)中的至少一种；多元醇水溶液中所述的烯烃单体为丙烯酰胺(AAm)、N-异丙基丙烯酰胺(NIPAM)、2-丙烯酰胺-2-甲基丙磺酸(AMPS)、甲基丙烯酰基乙基磺基甜菜碱(SBMA)、4-羟基丁基丙烯酸酯(4-HBA)、甲基丙烯酸(MAAc)、甲基丙烯酸羟乙酯(HEMA)、聚乙二醇二丙烯酸酯(PEGDA)中的至少一种。
7.一种聚合物有机水凝胶的制备方法，其特征在于，由Ag/MXene、单体、交联剂组成的多元醇水溶液无需除氧聚合得到；优选地，所述的Ag/MXene由权利要求1应用方法制得。
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