CN112646089A - 一种复合水凝胶及其制备方法和应用 - Google Patents
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Abstract
本发明公开了一种复合水凝胶及其制备方法和应用。这种复合水凝胶包括第一网络和第二网络;其中,第二网络半互穿第一网络;第一网络包括异丙基丙烯酰胺基单体和纳米颗粒形成的水凝胶;第二网络包括高分子聚合物。这种复合水凝胶可以应用在生物和/或医药领域。本发明提供的复合水凝胶具有双重网络结构,具有温度响应性和超高机械性能。这种高弹性水凝胶的制备采用廉价易得的原料和温和的制备工艺,使得水凝胶的制备容易放大生产,拓展了其应用范围。
Description
技术领域
本发明涉及水凝胶技术领域,特别涉及一种复合水凝胶及其制备方法和应用。
背景技术
水凝胶含有大量水分,具有三维网络结构,因此其在生物医用领域的应用价值越来越明显,可以用作生物传感器、组织工程支架、生物分离、药物释放载体等。这些应用领域对水凝胶的生物相容性和机械性能特别是拉伸强度都有一定的要求,而传统的化学交联水凝胶有着不规则的交联点,并且聚合物分子链的长度分布也不均一,这导致其力学性能较差无法满足对力学性能要求较高的应用需求。传统的化学交联水凝胶往往需要添加小分子化学交联剂,对水凝胶的生物相容性有着很大的负面影响。
专利文献CN107840926A公开了一种快速响应的高强度水凝胶,该发明公开的凝胶制备方法首先制备双键功能化的N-异丙基丙烯酰胺微凝胶作为交联剂制备水凝胶,该技术方案的反应步骤较多,制备方法繁琐,增加了制备过程的操作难度和制备结果的控制难度。
现有技术水凝胶的制备方法繁琐、中间的反应步骤较多,反应结果不易控制,具有温度响应性的超高强度水凝胶已有报道较少,且普遍存在力学强度差的技术难题,需要进一步改进。
发明内容
本发明旨在至少解决现有技术中水凝胶存在的上述技术问题之一。为此,本发明的目的之一在于提供一种具有温度响应性的高弹性复合水凝胶,本发明的目的之二在于提供这种复合水凝胶的制备方法,本发明的目的之三在于提供这种复合水凝胶的应用。
本发明的发明构思如下:本发明通过设计一种具有双重网络结构的复合水凝胶,可以提高水凝胶的机械性能,使其具有超高的弹性。具体来说,本发明复合水凝胶的制备选用异丙基丙烯酰胺及其衍生物为基础单体,采用无机纳米颗粒作为凝胶增强剂,同时起到交联剂的作用,避免了体系额外添加小分子交联剂提高水凝胶的生物相容性,采用自由基溶液聚合的方法制备第一层凝胶网络结构,然后通过添加增强剂形成半互穿网络形成凝胶体系的第二重网络结构。
为了实现上述目的,本发明所采取的技术方案是:
本发明的第一方面提供了一种复合水凝胶,所述复合水凝胶包括第一网络和第二网络;
所述第二网络半互穿所述第一网络;
所述第一网络包括异丙基丙烯酰胺基单体和纳米颗粒形成的水凝胶;
所述第二网络包括高分子聚合物。
优选的,所述复合水凝胶中,所述异丙基丙烯酰胺基单体包括N-异丙基丙烯酰胺、丙烯基-N-异丙基丙烯酰胺、葡萄糖基-N-异丙基丙烯酰胺、壳聚糖基-N-异丙基丙烯酰胺中的至少一种。在本发明的一些实施例中,异丙基丙烯酰胺基单体选用N-异丙基丙烯酰胺。
优选的,所述复合水凝胶中,所述纳米颗粒包括纳米氧化石墨烯、纳米粘土、碳纳米管中的至少一种。
优选的,所述复合水凝胶中,所述高分子聚合物包括聚乙二醇、聚乙烯醇、聚乙二醇甲基丙烯酸酯、聚乙烯吡咯烷酮、羟乙基纤维素、羟丙基甲基纤维素、羧甲基纤维素、甲基纤维素中的至少一种;进一步优选的,所述高分子聚合物包括聚乙二醇、聚乙二醇甲基丙烯酸酯、羟乙基纤维素中的至少一种。
优选的,所述复合水凝胶的相转变温度为34℃~40℃;进一步优选的,所述复合水凝胶的相转变温度为35℃~39℃。
优选的,所述复合水凝胶的拉伸断裂伸长率为900%~1200%。
本发明的第二方面提供了一种复合水凝胶的制备方法,包括以下步骤:
1)将高分子聚合物溶于溶剂中,得到高分子聚合物溶液;
2)将所述高分子聚合物溶液、异丙基丙烯酰胺基单体与纳米颗粒混合,得到混合溶液;
3)将所述混合溶液与引发剂混合,反应,得到复合水凝胶。
本发明第二方面提供制备得到的复合水凝胶结构和/或组成如本发明第一方面所述的复合水凝胶。
优选的,所述制备方法的步骤1)中,高分子聚合物溶液的质量浓度为1%~10%;进一步优选的,高分子聚合物溶液的质量浓度为2%~8%。
优选的,所述制备方法的步骤1)中,溶剂为水。
优选的,所述制备方法的步骤2)中,高分子聚合物、异丙基丙烯酰胺基单体与纳米颗粒的质量比为(3~80):100:(0.3~40);进一步优选的,高分子聚合物、异丙基丙烯酰胺基单体与纳米颗粒的质量比为(5~50):100:(0.5~4);再进一步优选的,高分子聚合物、异丙基丙烯酰胺基单体与纳米颗粒的质量比为(10~40):100:(1~2.5)。
优选的,所述制备方法的步骤2)中,混合的方式包括搅拌;进一步优选的,混合的方式包括磁力搅拌。
优选的,所述制备方法的步骤2)中,混合的方式还包括超声波混合。
优选的,所述制备方法的步骤3)中,引发剂选自偶氮类化合物、过氧化物、过硫酸盐中的至少一种;进一步优选的,引发剂选自偶氮二异丁腈、偶氮二异庚腈、过氧化氢、叔丁基过氧化氢、过硫酸钠、过硫酸钾、过硫酸铵中的至少一种;再进一步优选的,引发剂选自过硫酸钠、过硫酸钾、过硫酸铵中的至少一种。
优选的,所述制备方法的步骤3)中,引发剂的用量为异丙基丙烯酰胺基单体质量的1%~30%;进一步优选的,引发剂的用量为异丙基丙烯酰胺基单体质量的5%~28%;再进一步优选的,引发剂的用量为异丙基丙烯酰胺基单体质量的12.5%~25%。
优选的,所述制备方法的步骤3)中,混合溶液与引发剂混合得到的反应混合液是在模具中进行反应。
优选的,所述制备方法的步骤3)中,反应的温度为50℃~80℃;反应的时间为2小时~10小时。
优选的,所述制备方法的步骤3)中,反应为水浴反应。
本发明的第三方面提供了一种复合水凝胶在生物和/或医药领域中的应用,所述复合水凝胶为本发明第一方面所述的复合水凝胶,或者是由本发明第二方面所述的制备方法制得。
优选的,所述复合水凝胶在生物传感器、组织工程支架、生物分离、凝胶绷带或药物释放载体中的应用。
本发明的有益效果是:
本发明提供的复合水凝胶具有双重网络结构,具有温度响应性和超高机械性能。这种高弹性水凝胶的制备采用廉价易得的原料和温和的制备工艺,使得水凝胶的制备容易放大生产,拓展了其应用范围。
具体来说,与现有技术相比,本发明具有如下优点:
本发明的水凝胶体系引入能够增强水凝胶力学性能的无机纳米颗粒作为交联剂分子,避免了额外添加小分子化学交联剂影响水凝胶的生物相容性,同时,体系引入生物相容性好的高分子聚合物作为复合水凝胶的第二网络提高水凝胶的力学强度。
本发明制备的双网络高强度水凝胶具有温度响应性,通过调整温敏单体和增强剂的用量可以调整凝胶的相转变温度,拓展了该复合水凝胶的功能性和应用范围。
本发明的复合水凝胶具有超高拉伸断裂伸长率,应用前景广阔,如应用在生物医药领域,可用作生物传感器、组织工程支架、生物分离、药物释放载体等。
具体实施方式
以下通过具体的实施例对本发明的内容作进一步详细的说明。实施例中所用的原料、试剂或装置如无特殊说明,均可从常规商业途径得到,或者可以通过现有技术方法得到。除非特别说明,试验或测试方法均为本领域的常规方法。
实施例1
本例具有双网络结构的复合水凝胶制备方法包括如下步骤:
称取0.2g聚乙二醇甲基丙烯酸酯溶于10mL纯水中配成水溶液,然后分别称取2gN-异丙基丙烯酰胺、0.02g氧化石墨烯加入上述溶液中,磁力搅拌4小时,超声波混合均匀形成均匀的混合溶液,再向该混合溶液中添加0.3g过硫酸铵,磁力搅拌形成均匀的反应混合液,最后将反应混合液倒入模具中,置于50℃的水浴中反应3小时,得到具有温度响应性的高弹性水凝胶。
经检测发现,本例制备得到的水凝胶中,聚乙二醇甲基丙烯酸酯半互穿聚N-异丙基丙烯酰胺水凝胶,形成双重网络结构。
经测试,本例水凝胶的相转变温度为35℃,拉伸断裂伸长率达1200%。
实施例2
本例具有双网络结构的复合水凝胶制备方法包括如下步骤:
称取0.5g羟乙基纤维素溶于10mL纯水中配成水溶液,然后分别称取2g N-异丙基丙烯酰胺、0.02g氧化石墨烯加入上述溶液中,磁力搅拌4小时,超声波混合均匀形成均匀的混合溶液,再向该混合溶液中添加0.5g过硫酸铵,磁力搅拌形成均匀的反应混合液,最后将反应混合液倒入模具中,置于50℃的水浴中反应3小时,得到具有温度响应性的高弹性水凝胶。
经检测发现,本例制备得到的水凝胶中,羟乙基纤维素半互穿聚N-异丙基丙烯酰胺水凝胶,形成双重网络结构。
经测试,本例水凝胶的相转变温度为37℃,拉伸断裂伸长率达1160%。
实施例3
本例具有双网络结构的复合水凝胶制备方法包括如下步骤:
称取0.8g羟乙基纤维素溶于10mL纯水中配成水溶液,然后分别称取2g N-异丙基丙烯酰胺、0.05g纳米粘土加入上述溶液中,磁力搅拌2小时,超声波混合均匀形成均匀的混合溶液,再向该混合溶液中添加0.25g过硫酸铵,磁力搅拌形成均匀的反应混合液,最后将反应混合液倒入模具中,置于50℃的水浴中反应3小时,得到具有温度响应性的高弹性水凝胶。
经检测发现,本例制备得到的水凝胶中,羟乙基纤维素半互穿聚N-异丙基丙烯酰胺水凝胶,形成双重网络结构。
经测试,本例水凝胶的相转变温度为39℃,拉伸断裂伸长率达900%。
本发明实施例制得的复合水凝胶微观结构为双重网络结构,其具有温度响应性和超高机械性能。
本发明提供的这种复合水凝胶可以广泛应用在生物、医药领域,如可用作生物传感器、组织工程支架、生物分离、凝胶绷带或药物释放载体等等,应用前景广阔。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (10)
1.一种复合水凝胶,其特征在于:所述复合水凝胶包括第一网络和第二网络;
所述第二网络半互穿所述第一网络;
所述第一网络包括异丙基丙烯酰胺基单体和纳米颗粒形成的水凝胶;
所述第二网络包括高分子聚合物。
2.根据权利要求1所述的一种复合水凝胶,其特征在于:所述异丙基丙烯酰胺基单体包括N-异丙基丙烯酰胺、丙烯基-N-异丙基丙烯酰胺、葡萄糖基-N-异丙基丙烯酰胺、壳聚糖基-N-异丙基丙烯酰胺中的至少一种。
3.根据权利要求1所述的一种复合水凝胶,其特征在于:所述纳米颗粒包括纳米氧化石墨烯、纳米粘土、碳纳米管中的至少一种。
4.根据权利要求1所述的一种复合水凝胶,其特征在于:所述高分子聚合物包括聚乙二醇、聚乙烯醇、聚乙二醇甲基丙烯酸酯、聚乙烯吡咯烷酮、羟乙基纤维素、羟丙基甲基纤维素、羧甲基纤维素、甲基纤维素中的至少一种。
5.根据权利要求1至4任一项所述的一种复合水凝胶,其特征在于:所述复合水凝胶的相转变温度为34℃~40℃。
6.根据权利要求1至4任一项所述的一种复合水凝胶,其特征在于:所述复合水凝胶的拉伸断裂伸长率为900%~1200%。
7.一种复合水凝胶的制备方法,其特征在于:包括以下步骤:
1)将高分子聚合物溶于溶剂中,得到高分子聚合物溶液;
2)将所述高分子聚合物溶液、异丙基丙烯酰胺基单体与纳米颗粒混合,得到混合溶液;
3)将所述混合溶液与引发剂混合,反应,得到如权利要求1至6任一项所述的复合水凝胶。
8.根据权利要求7所述的制备方法,其特征在于:所述步骤2)中,高分子聚合物、异丙基丙烯酰胺基单体与纳米颗粒的质量比为(3~80):100:(0.3~40)。
9.根据权利要求7所述的制备方法,其特征在于:所述步骤3)中,反应的温度为50℃~80℃;反应的时间为2小时~10小时。
10.一种复合水凝胶在生物和/或医药领域中的应用,其特征在于:所述复合水凝胶为权利要求1至6任一项所述的复合水凝胶,或者是由权利要求7至9任一项所述的制备方法制得。
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