CN109021185B - pH刺激响应型星形石墨烯分散剂的合成方法 - Google Patents
pH刺激响应型星形石墨烯分散剂的合成方法 Download PDFInfo
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Abstract
本发明公开了一种pH刺激响应型星形石墨烯分散剂的合成方法,包括以下步骤:a、采用ARGET‑ATRP法以α‑溴代异丁酸乙酯为引发剂引发苯乙烯聚合得到第一大分子引发剂,标记为PS‑Br;b、采用α‑溴代异丁酸乙酯为引发剂引发甲基丙烯酸二甲氨基乙酯聚合得到第二大分子引发剂,标记为PDMAEMA‑Br;c、采用先臂后核、ARGET‑ATRP法合成,以步骤a和步骤b中大分子引发剂PS‑Br和PDMAEMA‑Br为臂,以二乙烯基苯(DVB)为核,合成星形聚合物,即为石墨烯分散剂。通过本发明的合成方法能够得到一种分散性能好、存储稳定的石墨烯分散剂。
Description
技术领域
本发明涉及一种石墨烯分散剂的合成方法,特别是涉及一种pH刺激响应型星形石墨烯分散剂的合成方法。
背景技术
石墨烯是一种由sp2杂化碳原子组成的二维晶体材料,被认为是世界上最薄的材料。由于具有比表面积高、突出的拉伸强度、导热、导电性能,在很多科技领域引起了广泛的关注,但是这些应用极大的受到了它的溶解性的限制。为了解决这一问题,可溶性的分散剂逐渐被研发来改性石墨烯表面,使得石墨烯的溶解性提高。目前,主要改善石墨烯表面是通过共价键和非共价键的方法,非共价键的方法优先被选择,因为它避免破坏石墨烯的特有的性能。另外,石墨烯还存在一些潜在的应用,传感器、药物输送等。因此,不同种类的响应性的分散剂被开发出来,包括pH、温度、光、氧化还原响应的分散剂。一旦石墨烯的表面被分散剂改性,这些响应就能控制石墨烯的团聚和分散。但这些分散剂或因自身性能或因制备不易控制或因成本高等因素尚有不足,需要本领域技术人员研发出一种分散性能好、存储稳定的石墨烯分散剂。
发明内容
为了解决现有技术存在的问题,本发明提供了一种pH刺激响应型星形石墨烯分散剂的合成方法,以提高石墨烯在水中的溶解性。
为实现上述目的,本发明采取的技术方案是一种pH刺激响应型星形石墨烯分散剂的合成方法,包括以下步骤:
a、采用电子转移再生催化剂原子转移自由基聚合(ARGET-ATRP)法,采用α-溴代异丁酸乙酯为引发剂引发苯乙烯聚合得到第一大分子引发剂,标记为PS-Br;
b、采用电子转移再生催化剂原子转移自由基聚合(ARGET-ATRP)法,采用α-溴代异丁酸乙酯为引发剂引发甲基丙烯酸二甲氨基乙酯聚合得到第二大分子引发剂,标记为PDMAEMA-Br;
c、采用先臂后核、ARGET-ATRP法合成,以步骤a和步骤b中大分子引发剂PS-Br和PDMAEMA-Br为臂,以二乙烯基苯(DVB)为核,合成星形聚合物,即为石墨烯分散剂。
于本发明一实施例中,第一大分子引发剂的合成为:将苯乙烯、引发剂α-溴代异丁酸乙酯(EBIB)、催化剂、配体、还原剂、溶剂依次加入装有温度计的三口烧瓶中,鼓泡除氧气,在氩气或者氮气的保护下,温度90-120℃反应5-24h,然后对反应产物进行后处理即得到第一大分子引发剂PS-Br,数均分子量范围8000-12000。
于本发明一实施例中,所述第一大分子引发剂的后处理为:将反应完毕得到的产物用溶剂稀释,过中性氧化铝柱子,减压蒸馏除去大部分溶剂得到产物,然后真空烘箱干燥,得到淡黄色的固体。
于本发明一实施例中,其中所述催化剂为过渡金属卤化物CuCl2、CuBr2;所述配体为五甲基二乙烯三胺或三-(N,N-二甲基氨基乙基)胺;所述还原剂为辛酸亚锡或抗坏血酸;所述溶剂为甲苯、苯甲醚、N,N-二甲基甲酰胺、乙酸乙酯或四氢呋喃中的任一种。
于本发明一实施例中,所述催化剂:单体=(0.01:100)~(0.05:100),所述催化剂:配体=(1:10)~(1:20),所述催化剂:还原剂=(1:10)~(1:20),以上均为摩尔比;同时,所述溶剂占反应体系总质量的20%~100%。
于本发明一实施例中,第二大分子引发剂的合成为:将甲基丙烯酸二甲氨基乙酯、引发剂α-溴代异丁酸乙酯(EBIB)催化剂、配体、还原剂、溶剂依次加入装有温度计的三口烧瓶中,鼓泡除氧气,在氩气或者氮气保护下,温度60-90℃反应8-24h,然后对反应产物进行后处理即得到第二大分子引发剂PDMAEMA-Br,数均分子量在5000-7000。在当PDMAEMA聚合物溶液呈现酸性时,聚合物结构中的叔胺基高度质子化形成季铵盐,以离子形态稳定存在,从而提高了聚合物在水中的溶解性。
于本发明一实施例中,所述第二大分子引发剂的后处理为:将反应完毕得到的产物用溶剂稀释,过中性氧化铝柱子,减压蒸馏除去大部分溶剂得到产物,然后真空烘箱干燥,得到接近无色的固体。
于本发明一实施例中,所述催化剂为过渡金属卤化物CuCl2、CuBr2;所述配体为五甲基二乙烯三胺或三-(N,N-二甲基氨基乙基)胺;所述还原剂为辛酸亚锡或抗坏血酸;所述溶剂为甲苯、苯甲醚、N,N-二甲基甲酰胺、乙酸乙酯或四氢呋喃中的一种;
所述催化剂:单体=(0.03:100)~(0.06:100),所述催化剂:配体=(1:10)~(1:20),所述催化剂:还原剂=(1:15)~(1:25),以上均为摩尔比;同时,所述溶剂占反应体系总质量的30%~100%。
于本发明一实施例中,所述石墨烯分散剂的合成方法为:将第一大分子引发剂、第二大分子引发剂和溶剂放入三口烧瓶中,待将第一大分子引发剂和第二大分子引发剂完全溶解后,加入催化剂、配体、还原剂、交联剂二乙烯基苯,磁力搅拌均匀,鼓泡20-50min,在温度70-110℃下反应12-72h,得到产物,即为石墨烯分散剂。
于本发明一实施例中,所述催化剂为过渡金属卤化物CuCl2、CuBr2;所述配体为五甲基二乙烯三胺或三-(N,N-二甲基氨基乙基)胺;所述还原剂为辛酸亚锡或抗坏血酸;
所述催化剂:配体=(1:10)~(1:20),所述催化剂:还原剂=(1:15)~(1:25);所述第一大分子引发剂:第二大分子引发剂=(1:9)~(4:6),所述第一大分子引发剂和第二大分子引发剂之和:交联剂=(1:1)-(1:15),以上均为摩尔比;同时,所述溶剂占反应体系总质量的75~100%。所述溶剂为甲苯和苯甲醚。
本技术方案具有以下有益效果:
本发明采用电子转移再生催化剂原子转移自由基聚合(ARGET-ATRP)、先臂后核的合成方法得到一种异臂星形聚合物,即为石墨烯分散剂。通过以聚苯乙烯(PS)、聚甲基丙烯酸二甲氨基乙酯(PDMAEMA)为臂,以二乙烯基苯(DVB)为核,使得PS分子链上苯环结构的π电子能够和石墨烯的π电子相互作用;同时制备出的分散剂具有pH刺激响应,分散剂在水溶液中pH响应明显,并且分散剂分散石墨烯的效果佳,存储稳定。
本发明采用电子转移再生催化剂原子转移自由基聚合(ARGET-ATRP),在体系中只加入少量的(占单体摩尔数的几到几百ppm)高价过渡金属化合物/配体络合物(Mt n+1X/L)的情况下,引入一种还原剂,将Mt n+1X/L持续地还原为低价过渡金属卤化物/配体络合物(Mt nX/L),保证可较大的[Mt nX/L]/[Mt n+1X/L]值,从而保证可体系的聚合速率。
附图说明
图1是实施例1中第一大分子引发剂的GPC曲线;
图2是实施例1中第二大分子引发剂的GPC曲线;
图3是实施例1中星形石墨烯分散剂的GPC曲线;
图4是实施例2中星形石墨烯分散剂的GPC曲线;
图5是实施例3中星形石墨烯分散剂的GPC曲线;
图6是实施例4中星形石墨烯分散剂的GPC曲线;
图7是实施例5中星形石墨烯分散剂的GPC曲线;
图8是星形石墨烯分散剂合成路线示意图;
图9星形石墨烯分散剂的CO2刺激响应示意图;
图10是星形石墨烯分散剂在不同pH下分散石墨烯水溶液。
具体实施方式
下面结合实施例及附图1至10对本发明作进一步描述。
实施例1
用ARGET-ATRP法合成数均分子量约为10000大分子引发剂PS-Br
苯乙烯32g,引发剂α-溴代异丁酸乙酯(EBIB)0.693g,催化剂CuBr2 0.511g、配体PMDETA 0.1386g、还原剂Sn(EH)2 0.2448g,溶剂苯甲醚6.4g依次加入装有温度计的三口烧瓶中,鼓泡30min除氧气。在氩气的保护下90℃反应5小时,采用气相色谱测单体转化率。结束后,磁力搅拌使其溶解在四氢呋喃中,过中性氧化铝柱子,减压蒸馏除去大部分溶剂得到产物,40℃真空烘箱干燥,得到淡黄色的固体,即为第一大分子引发剂PS-Br。通过凝胶渗透色谱(GPC)进行分子量的测定,如图1所示。
采用ARGET-ATRP法合成数均分子量约为6000大分子引发剂PDMAEMA-Br
甲基丙烯酸二甲氨基乙酯31.4g,引发剂α-溴代异丁酸乙酯(EBIB)1.0207g,催化剂CuBr2 0.255g、配体PMDETA 0.0693g、还原剂Sn(EH)2 0.1224g,溶剂甲苯50g、苯甲醚5.12g依次加入装有温度计的三口烧瓶中,鼓泡30min除氧气。在氩气的保护下90℃反应24h,采用气相色谱测单体转化率。结束后,使其溶解在乙酸乙酯中,过中性氧化铝柱子,减压蒸馏除去大部分溶剂得到产物,40℃真空烘箱干燥,得到橘黄色的固体,即为第二大分子引发剂PDMAEMA-Br。通过凝胶渗透色谱(GPC)进行分子量的测定,如图2所示。
星形石墨烯分散剂的合成
第一大分子引发剂:第二大分子引发剂=1:4,大分子引发剂:交联剂=1:1。
取分子量为9600大分子引发剂PS-Br 2g,分子量为6600的大分子引发剂PDMAEMA-Br 5.5g,甲苯19g,苯甲醚3g放入装有温度的三口烧瓶中,待其完全溶解后,加入催化剂CuBr2 0.2326g、配体PMDETA 1.8052g、还原剂Sn(EH)2、二乙烯基苯0.1354g,磁力搅拌均匀,鼓泡30min,在温度90℃下反应72h,四氢呋喃溶解,过中性氧化铝柱,减压蒸馏除去大部分溶剂,40℃真空烘箱干燥后得到黄色固体产物,即为星形石墨烯分散剂。星形分散剂的分子量由图3所示,星形分散剂的合成路线示意图如图8所示。
实施例2
与实施例1不同之处是,本实施例的星形石墨烯分散剂的合成采用的配比是:第一大分子引发剂:第二大分子引发剂=1:4,大分子引发剂:交联剂=1:5。
取分子量为9600大分子引发剂PS-Br 2g,分子量为6600的大分子引发剂PDMAEMA-Br 5.5g,甲苯19g,苯甲醚3g放入装有温度的三口烧瓶中,待其完全溶解后,加入催化剂CuBr2 0.2326g、配体PMDETA 1.8052g、还原剂Sn(EH)2、二乙烯基苯0.6771g,磁力搅拌均匀,鼓泡30min,在温度90℃下反应72h,四氢呋喃溶解,过中性氧化铝柱,减压蒸馏除去大部分溶剂,40℃真空烘箱干燥后得到黄色固体产物,即为星形石墨烯分散剂。星形分散剂的分子量由图4所示,星形分散剂的合成路线示意图如图8所示。
实施例3
与实施例1不同之处是,本实施例的星形石墨烯分散剂的合成采用的配比是:第一大分子引发剂:第二大分子引发剂=1:4,大分子引发剂:交联剂=1:15。
取分子量为9600大分子引发剂PS-Br 2g,分子量为6600的大分子引发剂PDMAEMA-Br 5.5g,甲苯19g,苯甲醚3g放入装有温度的三口烧瓶中,待其完全溶解后,加入催化剂CuBr2 0.2326g、配体PMDETA 1.8052g、还原剂Sn(EH)2、二乙烯基苯2.0312g,磁力搅拌均匀,鼓泡30min,在温度90℃下反应72h,四氢呋喃溶解,过中性氧化铝柱,减压蒸馏除去大部分溶剂,40℃真空烘箱干燥后得到黄色固体产物,即为星形石墨烯分散剂。星形分散剂的分子量由图5所示,星形分散剂的合成路线示意图如图8所示。
实施例4
与实施例1不同之处是,本实施例的星形石墨烯分散剂的合成采用的配比是:第一大分子引发剂:第二大分子引发剂=1:9,大分子引发剂:交联剂=1:1。
取分子量为9600大分子引发剂PS-Br 2g,分子量为6600的大分子引发剂PDMAEMA-Br 12.375g,甲苯49.6590g,苯甲醚7.8409g放入装有温度的三口烧瓶中,待其完全溶解后,加入催化剂CuBr2 0.2326g、配体PMDETA 1.8052g、还原剂Sn(EH)2、二乙烯基苯0.2708g,磁力搅拌均匀,鼓泡30min,在温度90℃下反应72h,四氢呋喃溶解,过中性氧化铝柱,减压蒸馏除去大部分溶剂,40℃真空烘箱干燥后得到黄色固体产物,即为星形石墨烯分散剂。星形分散剂的分子量由图6所示,星形分散剂的合成路线示意图如图8所示。
实施例5
与实施例1不同之处是,本实施例的星形石墨烯分散剂的合成采用的配比是:第一大分子引发剂:第二大分子引发剂=4:6,大分子引发剂:交联剂=1:1。
取分子量为9600大分子引发剂PS-Br 2g,分子量为6600的大分子引发剂PDMAEMA-Br 2.0625g,甲苯19g,苯甲醚3g放入装有温度的三口烧瓶中,待其完全溶解后,加入催化剂CuBr2 0.2326g、配体PMDETA 1.8052g、还原剂Sn(EH)2、二乙烯基苯0.2708g,磁力搅拌均匀,鼓泡30min,在温度90℃下反应72h,四氢呋喃溶解,过中性氧化铝柱,减压蒸馏除去大部分溶剂,40℃真空烘箱干燥后得到黄色固体产物,即为星形石墨烯分散剂。星形分散剂的分子量由图7所示,星形分散剂的合成路线示意图如图8所示。
实施例6
对上述实施例1制备得到石墨烯分散剂进行石墨烯分散液的制备
将10mg星形分散剂溶于5mL的蒸馏水,待其完全溶解,称取10mg石墨烯放入,超声30min使其分散均匀。将含有石墨烯的溶液进行离心(转速4500rpm),取上清液,即为石墨烯分散液。
星形石墨烯分散剂的CO2刺激响应测试
将石墨烯分散液通入CO2 30min,通入CO2后,原本几乎不溶于水的星形石墨烯分散剂很好的溶于了水。这是由于CO2的通入,使得体系变成了酸性,PDMAEMA由非离子态转化为离子态,如图9所示。
其原理如下:
星形石墨烯分散剂在不同pH下分散石墨烯水溶液对比
分别配置3%NaOH溶液、以及3%HCl溶液,将实施例1中星形石墨烯分散剂在不同酸碱度下分散石墨烯。制备出石墨烯分散液,经过7天后,酸性条件下(3%HCl)的分散液依然分散均匀,而碱性条件下,分散剂和石墨烯均沉在底部,如图10所示。
上述具体实施例只是用来解释说明本发明,而非是对本发明进行限制,在本发明的宗旨和权利要求的保护范围内,对本发明做出的任何不付出创造性劳动的替换和改变,皆落入本发明专利的保护范围。
Claims (10)
1.一种pH刺激响应型星形石墨烯分散剂的合成方法,其特征在于,包括以下步骤:
a、采用电子转移再生催化剂原子转移自由基聚合(ARGET-ATRP)法,采用α-溴代异丁酸乙酯为引发剂引发苯乙烯聚合得到第一大分子引发剂,标记为PS-Br;
b、采用电子转移再生催化剂原子转移自由基聚合(ARGET-ATRP)法,采用α-溴代异丁酸乙酯为引发剂引发甲基丙烯酸二甲氨基乙酯聚合得到第二大分子引发剂,标记为PDMAEMA-Br;
c、采用先臂后核法合成,以步骤a和步骤b中大分子引发剂PS-Br和PDMAEMA-Br为臂,以二乙烯基苯(DVB)为核,合成星形聚合物,即为石墨烯分散剂。
2.根据权利要求1所述的pH刺激响应型星形石墨烯分散剂的合成方法,其特征在于,第一大分子引发剂的合成为:将苯乙烯、引发剂α-溴代异丁酸乙酯(EBIB)、催化剂、配体、还原剂、溶剂依次加入装有温度计的三口烧瓶中,鼓泡除氧气,在氩气或者氮气的保护下,温度90-120℃反应5-24h,然后对反应产物进行后处理即得到第一大分子引发剂PS-Br。
3.根据权利要求1所述的pH刺激响应型星形石墨烯分散剂的合成方法,其特征在于,所述第一大分子引发剂的后处理为:将反应完毕得到的产物用溶剂稀释,过中性氧化铝柱子,减压蒸馏除去大部分溶剂得到产物,然后真空烘箱干燥,得到淡黄色的固体。
4.根据权利要求2或3所述的pH刺激响应型星形石墨烯分散剂的合成方法,其特征在于,其中所述催化剂为过渡金属卤化物CuCl2、CuBr2;所述配体为五甲基二乙烯三胺或三-(N,N-二甲基氨基乙基)胺;所述还原剂为辛酸亚锡或抗坏血酸;所述溶剂为甲苯、苯甲醚、N,N-二甲基甲酰胺、乙酸乙酯或四氢呋喃中的任一种。
5.根据权利要求4所述的pH刺激响应型星形石墨烯分散剂的合成方法,其特征在于,所述催化剂:单体=(0.01:100)~(0.05:100),所述催化剂:配体=(1:10)~(1:20),所述催化剂:还原剂=(1:10)~(1:20),以上均为摩尔比;同时,所述溶剂占反应体系总质量的20%~100%。
6.根据权利要求1所述的pH刺激响应型星形石墨烯分散剂的合成方法,其特征在于,第二大分子引发剂的合成为:将甲基丙烯酸二甲氨基乙酯、引发剂α-溴代异丁酸乙酯(EBIB)催化剂、配体、还原剂、溶剂依次加入装有温度计的三口烧瓶中,鼓泡除氧气,在氩气或者氮气保护下,温度60-90℃反应8-24h,然后对反应产物进行后处理即得到第二大分子引发剂PDMAEMA-Br。
7.根据权利要求6所述的pH刺激响应型星形石墨烯分散剂的合成方法,其特征在于,所述第二大分子引发剂的后处理为:将反应完毕得到的产物用溶剂稀释,过中性氧化铝柱子,减压蒸馏除去大部分溶剂得到产物,然后真空烘箱干燥,得到无色的固体。
8.根据权利要求6或7所述的pH刺激响应型星形石墨烯分散剂的合成方法,其特征在于,所述催化剂为过渡金属卤化物CuCl2、CuBr2;所述配体为五甲基二乙烯三胺或三-(N,N-二甲基氨基乙基)胺;所述还原剂为辛酸亚锡或抗坏血酸;所述溶剂为甲苯、苯甲醚、N,N-二甲基甲酰胺、乙酸乙酯或四氢呋喃中的一种;所述催化剂:单体=(0.03:100)~(0.06:100),所述催化剂:配体=(1:10)~(1:20),所述催化剂:还原剂=(1:15)~(1:25),以上均为摩尔比;同时,所述溶剂占反应体系总质量的30%~100%。
9.根据权利要求1所述的pH刺激响应型星形石墨烯分散剂的合成方法,其特征在于,石墨烯分散剂的合成方法为:将第一大分子引发剂、第二大分子引发剂和溶剂放入三口烧瓶中,待将第一大分子引发剂和第二大分子引发剂完全溶解后,加入催化剂、配体、还原剂、交联剂二乙烯基苯,磁力搅拌均匀,鼓泡20-50min,在温度70-110℃下反应12-72h,得到产物,即为石墨烯分散剂。
10.根据权利要求9所述的pH刺激响应型星形石墨烯分散剂的合成方法,其特征在于,所述催化剂为过渡金属卤化物CuCl2、CuBr2;所述配体为五甲基二乙烯三胺或三-(N,N-二甲基氨基乙基)胺;所述还原剂为辛酸亚锡或抗坏血酸;所述溶剂为甲苯和苯甲醚;
所述催化剂:配体=(1:10)~(1:20),所述催化剂:还原剂=(1:15)~(1:25);所述第一大分子引发剂:第二大分子引发剂=(1:9)~(4:6),所述第一大分子引发剂和第二大分子引发剂之和:交联剂=(1:1)-(1:15),以上均为摩尔比;同时,所述溶剂占反应体系总质量的75~100%。
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