CN113248733B - 一种基于纳米复合引发剂的高弹高韧纳米复合水凝胶的制备方法 - Google Patents
一种基于纳米复合引发剂的高弹高韧纳米复合水凝胶的制备方法 Download PDFInfo
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Abstract
本发明公开了一种基于纳米复合引发剂的高弹高韧纳米复合水凝胶的制备方法,通过纳米复合引发剂与纳米复合交联剂的设计,在自由基聚合反应的初始,利用配位共价作用将引发剂和交联剂均匀吸附在金属纳米材料表面,将丙烯酰胺单体加入上述体系形成前驱溶液,在紫外光激发下引发自由基聚合反应,使反应在纳米材料表面进行,得到高弹性化学交联水凝胶制品。研究结果表明,该方法制备的水凝胶具有优异的力学性能,如拉伸强度可达3.13MPa、断裂伸长率可达3036%,韧性达到25.45MJ/m3。
Description
技术领域
本发明涉及一种基于纳米复合引发剂的高弹高韧纳米复合水凝胶的制备方法,属于纳米功能材料领域。
背景技术
自由基聚合反应是指单体借助于光、热、辐射、引发剂等的作用下,单体分子活化为活性的自由基,再与其他的单体分子连锁聚合形成高聚物的化学反应。在链引发阶段,传统的小分子引发剂会先形成初始自由基,接着引发剂自由基和单体碰撞,形成单体自由基。之后在链增长基元反应中,单体反复和单体自由基发生加聚反应,形成大分子游离基,在遇到交联剂失活之前,这段预聚物也会不断变长。当整个网络中交联剂含量较少时,会有无数条这样的预聚物悬垂在网络结构中,而它们对材料的机械强度是没有任何作用的。
发明内容
单点引发的缺点是单点引发剂在引发自由基聚合过程中,不可避免地会产生无数条悬垂于网络中的预聚物链,它们对于网络能量的耗散不起任何作用。所以,本发明设计了一种新型的纳米复合引发剂,通过配位共价作用将引发剂束缚在纳米材料的表面,在聚合反应的初始阶段将预聚物固定在纳米材料的表面,参与网络结构的组成。一方面金纳米颗粒和二氧化硅纳米颗粒具有单分散特性,在充当网络交联点时可以让整个凝胶网络更加规整有序;另一方面,金纳米颗粒将单点引发剂束缚在一起,限制了拖曳聚合物链的无序运动,在抵抗外力作用时,会减少应力集中,耗散能量,达到相同资源条件下,材料的最大化利用。
为了改善自由基聚合过程中悬垂预聚物的问题,本发明提供了一种基于纳米复合引发剂的高弹高韧纳米复合水凝胶的制备方法,采用纳米复合引发剂,通过配位共价作用将小分子引发剂束缚在纳米材料的表面,之后将丙烯酰胺单体加入体系形成前驱溶液,在紫外光激发下引发自由基聚合反应,使反应在纳米材料表面进行,得到高弹性化学交联水凝胶制品。与传统水凝胶的小分子交联剂和单点引发剂不同的是,这种纳米复合的多链引发剂在网络中既起到引发剂作用,又能作为一种交联剂成分。此外纳米二氧化硅作为交联点是可控且分散的,当凝胶受到外力时,这种均匀的网络结构更有利于能量的传递与耗散,从而提高凝胶整体的力学性能。
本发明基于纳米复合引发剂的高弹高韧纳米复合水凝胶的制备方法,将乙烯基修饰后的SiO2纳米颗粒作为交联剂,在自由基聚合反应的初始,利用配位共价作用将引发剂和交联剂均匀吸附在金属纳米材料表面,将丙烯酰胺单体加入上述体系形成前驱溶液,在紫外光激发下引发自由基聚合反应,使反应在纳米材料表面进行,得到高弹性化学交联水凝胶制品。具体包括如下步骤:
步骤1:单分散金纳米颗粒的制备
采用改良的Frens法合成金纳米颗粒。在含有磁力搅拌子的100ml双口圆底烧瓶中,配制50mL浓度5-15mM的HAuCl4水溶液,搅拌下加热至强烈回流(滴速达到1滴每秒);同时,配制5ml浓度1-15wt%的柠檬酸钠水溶液,迅速添加至回流的HAuCl4溶液中,随后反应混合物在1分钟内发生黄色、无色、黑色、紫红色的颜色转变,得到金纳米颗粒溶液回流5分钟后停止加热,冷却到室温,并转移到干净的玻璃介质瓶中4℃冷藏保存。得到的金纳米粒子通过透射电子显微镜和紫外光谱表征。
步骤1中,HAuCl4和柠檬酸钠的摩尔比为1:2。
步骤1中,金纳米颗粒的浓度为250-750ppm。
步骤2:乙烯基修饰的SiO2纳米颗粒的制备
采用溶胶凝胶法,将乙烯基三乙氧基硅烷水解制得乙烯基修饰的SiO2纳米颗粒。
(Huang,Yan,et al."An intrinsically stretchable and compressiblesupercapacitor containing a polyacrylamide hydrogel electrolyte."AngewandteChemie International Edition 56.31(2017):9141-9145.)
步骤3:高弹高韧纳米复合水凝胶的制备
在空气温度和湿度下,将引发剂加入到步骤1获得的单分散金纳米颗粒溶液中,放置于超声清洗机中逐渐超声溶解,完成金纳米颗粒的第一次组装;随后加入单体丙烯酰胺、乙烯基修饰的SiO2纳米颗粒,将此混合物再一次放于超声清洗机中溶解成均相的前体溶液,然后放于紫外光固化箱中,由紫外光引发自由基聚合反应,20min后即可得到目标水凝胶。
步骤3中,所述引发剂优选为Irgacure907(2-甲基-1-(4-甲硫基苯基)-2-吗啉-1-丙酮),加入量是丙烯酰胺摩尔量的0.1-2mol%。
步骤3中,单分散金纳米颗粒溶液的添加量为5ml,单体丙烯酰胺的添加量为1g,乙烯基修饰的SiO2纳米颗粒的摩尔量为丙烯酰胺摩尔量的0.05-1mol%。
步骤3中,紫外光照射功率为5-10W,波长为365nm。
与现有技术相比,本发明的有益效果体现在:
本发明采用一锅法制备了金纳米复合的高弹性坚韧水凝胶,克服了传统水凝胶制备过程繁琐,不可调控的缺点。合成的目标水凝胶具有优异的韧性且强度也远远超出传统水凝胶。
本发明通过将乙烯基修饰后的二氧化硅纳米颗粒作为交联剂,引发剂吸附在金纳米颗粒的表面作为纳米复合引发剂,之后在紫外光引发下形成聚合物网络。这就与传统的小分子交联点和单点引发有很大的区别,单点引发剂在引发自由基聚合过程中不可避免地会产生无数条悬垂于网络中的预聚物链,它们对于网络能量的耗散不起任何作用,并且造成了凝胶网络结构的力学性能差。而这种纳米复合引发剂则可以很容易解决这个问题,一是利用金纳米颗粒和二氧化硅纳米颗粒的单分散特性,在作为交联剂时可以规整网络结构;二是引发剂可以束缚住拖曳的预聚物链,让整个网络拥有更有效的能量传递系统。在抵抗外力时,能够减少应力集中,达到相同资源条件下的材料最大化利用效率。
附图说明
图1是合成的三种水凝胶的应力应变曲线图。
图2是三种不同水凝胶的韧性和临界拉伸倍数的对比图。
图3是合成的纳米复合引发剂水凝胶以及传统小分子引发剂水凝胶的应力-应变曲线。
图4是传统小分子引发剂水凝胶和纳米复合引发剂水凝胶的拉伸光学图片,拉伸倍数,ε。
具体实施方式
下面结合具体实施例进一步说明本发明的技术方案。
实施例1:单分散金纳米颗粒的制备
1、在含有磁力搅拌子的100ml双口圆底烧瓶中,配制50毫升HAuCl4(5mM)水溶液,溶液加热到强烈回流,同时搅拌,直到达到快速滴速(约1滴每秒);同时,配制5ml柠檬酸钠(浓度为5wt%)水溶液,将此柠檬酸钠溶液迅速添加到回流的HAuCl4溶液中,加入后反应混合物在1分钟内由黄色、无色、黑色、紫红色转变,得到的金纳米颗粒溶液回流5分钟后熄火,将混合物冷却到室温,并转移到一个干净的玻璃介质瓶中冷藏(4℃)。
2、在含有磁力搅拌子的100ml双口圆底烧瓶中,配制50毫升HAuCl4(10mM)水溶液,溶液加热到强烈回流,同时搅拌,直到达到快速滴速(约1滴每秒);同时配制5ml柠檬酸钠(浓度为10wt%)水溶液,将此柠檬酸钠溶液迅速添加到回流的HAuCl4溶液中,加入后反应混合物在1分钟内由黄色、无色、黑色、紫红色转变,得到的金纳米颗粒溶液回流5分钟后熄火,将混合物冷却到室温,并转移到一个干净的玻璃介质瓶中冷藏(4℃)。
3、在含有磁力搅拌子的100ml双口圆底烧瓶中,配制50毫升HAuCl4(15mM)水溶液。溶液加热到强烈回流,同时搅拌,直到达到快速滴速(约1滴每秒);同时配制5ml柠檬酸钠(浓度为15wt%)水溶液,将此柠檬酸钠溶液迅速添加到回流的HAuCl4溶液中,加入后反应混合物在1分钟内由黄色、无色、黑色、紫红色转变,得到的金纳米颗粒溶液回流5分钟后熄火。将混合物冷却到室温,并转移到一个干净的玻璃介质瓶中冷藏(4℃)。
实施例2:
1、乙烯基修饰的SiO2纳米颗粒的制备
采用水解法制备纳米二氧化硅,取适量乙烯基三乙氧基硅烷于去离子水中,剧烈搅拌12h,可得质量分数为6.7wt%的纳米二氧化硅分散液。
2、SiO2@Ir907水凝胶的制备
在空气温度和湿度下,将引发剂2-甲基-1-(4-甲硫基苯基)-2-吗啉-1-丙酮(Ir907)加入到去离子水中,放置于超声清洗机中逐渐超声溶解,然后向溶液中加入单体丙烯酰胺、乙烯基修饰的SiO2纳米颗粒,将此混合物再一次放于超声清洗机中超声10s,溶解成均相的前体溶液,然后放于紫外光固化箱中,由紫外光引发自由基聚合反应,20min后即可得到水凝胶。本实施例中的水凝胶和实施例3中的目标水凝胶作为对照实验组,不加金纳米颗粒,只是单纯以SiO2为纳米交联剂的水凝胶网络,来证明SiO2对网络力学性能的贡献值。
实施例3:
1、乙烯基修饰的SiO2纳米颗粒的制备
采用水解法制备纳米二氧化硅,取适量乙烯基三乙氧基硅烷于去离子水中,剧烈搅拌12h,可得质量分数为6.7wt%的纳米二氧化硅分散液。
2、SiO2@Au@Ir907水凝胶的制备
在空气温度和湿度下,将引发剂2-甲基-1-(4-甲硫基苯基)-2-吗啉-1-丙酮(Ir907)加入到单分散金纳米颗粒溶液中,放置于超声清洗机中逐渐超声溶解,完成金纳米颗粒的第一次组装;然后向金纳米颗粒溶液(浓度为500ppm)中加入单体丙烯酰胺,乙烯基修饰的SiO2纳米颗粒,将此混合物再一次放于超声清洗机中超声10s,溶解成均相的前体溶液,然后放于紫外光固化箱中,由紫外光引发自由基聚合反应,20min后即可得到目标水凝胶。
实施例4:
1、乙烯基修饰的SiO2纳米颗粒的制备
采用水解法制备纳米二氧化硅,取适量乙烯基三乙氧基硅烷于去离子水中,剧烈搅拌12h,可得质量分数为6.7wt%的纳米二氧化硅分散液。
2、SiO2@Au@Ir2959水凝胶的制备
在空气温度和湿度下,将引发剂2-羟基-4-(2-羟乙氧基)-2-甲基苯丙酮(Ir2959)加入到单分散金纳米颗粒溶液中,放置于超声清洗机中逐渐超声溶解,完成金纳米颗粒的第一次组装;然后向金纳米颗粒溶液(浓度为500ppm)中加入单体丙烯酰胺,乙烯基修饰的SiO2纳米颗粒,将此混合物再一次放于超声清洗机中超声10s,溶解成均相的前体溶液,然后放于紫外光固化箱中,由紫外光引发自由基聚合反应,20min后即可得到水凝胶。本实施例的凝胶主要和实施例3中的目标水凝胶作为对照组,引发剂2-羟基-4-(2-羟乙氧基)-2-甲基苯丙酮和金纳米颗粒之间无配位作用,金纳米颗粒只是单纯物理加入,没有参与凝胶网络的形成,来证明金属配位作用对网络力学性能的贡献值。
本发明首次提出来纳米复合引发剂的设计,用来解决自由基聚合反应过程中悬垂预聚物链的问题。实验研究表明,该方法成功地制备出超弹性、坚韧的水凝胶,实现了相同资源环境条件下材料对力学性能的优化贡献率。从图2中可以得出,目标水凝胶SiO2@Au@Ir907的韧性是无金属配位相互作用水凝胶SiO2@Au@Ir2959的12.9倍,拉伸倍数是其2.5倍;目标水凝胶SiO2@Au@Ir907的韧性是单纯添加SiO2纳米颗粒的SiO2@Ir907水凝胶的1.5倍,临界拉伸应力是其3.5倍。从图3中可以得出传统小分子引发剂水凝胶的拉伸应力值为0.0536MPa,拉伸倍数为143%,韧性值为0.0375MJ/m3。而纳米复合引发剂水凝胶的拉伸应力、拉伸倍数和韧性值分别是传统小分子引发剂水凝胶的58倍、21倍和679倍。
Claims (1)
1.一种基于纳米复合引发剂的高弹高韧纳米复合水凝胶的制备方法,其特征在于包括如下步骤:
步骤1:单分散金纳米颗粒的制备
采用改良的Frens法合成金纳米颗粒;在含有磁力搅拌子的100ml双口圆底烧瓶中,配制50mL浓度5-15mM 的HAuCl4水溶液,搅拌下加热至回流;同时,配制5ml浓度1-15wt%的柠檬酸钠水溶液,迅速添加至回流的HAuCl4溶液中,随后反应混合物在1分钟内发生黄色、无色、黑色、紫红色的颜色转变,得到金纳米颗粒溶液,回流5分钟后停止加热,冷却到室温,4℃冷藏保存;
步骤2:乙烯基修饰的SiO2纳米颗粒的制备
采用溶胶凝胶法,将乙烯基三乙氧基硅烷水解制得乙烯基修饰的SiO2纳米颗粒;
步骤3:高弹高韧纳米复合水凝胶的制备
在空气温度和湿度下,将引发剂加入到步骤1获得的单分散金纳米颗粒溶液中,放置于超声清洗机中逐渐超声溶解,完成金纳米颗粒的第一次组装;随后加入单体丙烯酰胺、乙烯基修饰的SiO2纳米颗粒,将此混合物再一次放于超声清洗机中溶解成均相的前体溶液,然后放于紫外光固化箱中,由紫外光引发自由基聚合反应,得到目标水凝胶;
步骤1中,HAuCl4和柠檬酸钠的摩尔比为1:2;
步骤1中,金纳米颗粒的浓度为250-750ppm;
步骤3中,所述引发剂为Irgacure907,加入量是丙烯酰胺摩尔量的0.1-2mol%;
步骤3中,单分散金纳米颗粒溶液的添加量为5ml,单体丙烯酰胺的添加量为1g,乙烯基修饰的SiO2纳米颗粒的摩尔量为丙烯酰胺摩尔量的0.05-1mol%;
步骤3中,紫外光照射功率为5-10W,波长为365nm。
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