CN117659257A - 一种具有高力致变色灵敏性的纳米填料及其制备方法 - Google Patents
一种具有高力致变色灵敏性的纳米填料及其制备方法 Download PDFInfo
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Abstract
本发明公开一种具有高力致变色灵敏性的纳米填料及其制备方法,通过细乳液聚合技术,将不同力致变色基团加载于纳米填料内部,通过对组分与表面修饰的调控,优化了纳米填料的力致变色敏感性,通过填料的力敏变色,实现对高分子材料内部拉伸应力高灵敏的原位、可视自感知与自检测。其优势在于对拉伸应变的荧光显色无临界变色应变,并且对不同高分子材料及其成型工艺具有广泛的适用性,合成简单,易于加工,添加量少,可以为高分子材料失效预警、应力分布分析以及结构损伤检测提供了一种简单、可靠且低成本的技术途径。
Description
技术领域
本发明涉及智能材料技术领域,尤其涉及一种高力致变色灵敏性的纳米填料及其制备方法。
背景技术
智能材料指能够对材料内外状态及环境的变化进行自感知与自适应的新型材料,是现代先进材料发展的重要趋势,具有广阔的市场前景,目前已经发展出诸如力敏变色、湿敏变色、温敏变色、光敏变色等一系列的新型材料与产品。作为智能材料的重要组成部分,力致变色智能填料能够通过自身的颜色/荧光变化,将材料内部应力实时可视化,具有不需要复杂的外部电路元件,并且可实时、原位、全面地反映材料在受力状态下的应力/应变大小的优点。特别是在高分子材料领域,通过自身颜色变化,力致变色高分子材料不仅能够作为直观的受力分析工具,测绘高分子部件内部的应力集中情况,为更合理的部件结构设计提供指导,同时可以对材料的力学失效提供及时的预警,大幅提高系统整体的稳定性与安全性,并且在人造皮肤、仿生材料等领域也获得了广泛的应用。
现有技术中的力致变色高分子材料主要通过两种技术途径制备:一种是在高分子材料内部构造周期性结构的光子晶体(例如CN 110228153 B,CN 111925723B,CN113896925 B),从而获得对应力高度灵敏的结构色,但这种方式技术难度高、对基体与纳米填料的匹配性要求高、并且往往只能获得具有力致变色效果的薄膜材料,对不同高分子材料及其制备工艺不具有普适性;另一种是通过在高分子基体内部加载具有力致变色功能的基团,如受力后因化学键断裂而变色的力致变色分子(例如CN 112375194 B,CN 113354789B,CN 113929928B),聚集诱导发光分子(例如CN 109575910 B,CN 112608217 B)以及稀土元素掺杂的荧光粉材料(例如CN 107298977 A,CN 111944275 A)等,可以实现对不同高分子材料内部应力水平的自感知,但该方法存在力致变色灵敏度低的缺点,并且力致变色基团的添加往往会降低高分子材料的力学性能。其中发明专利CN 112608217 B公开了一种组装调控荧光增强聚集诱导发光材料、微纳米球及制备方法与应用,所获得的微纳米球具有荧光量子产率高,研磨后会发生颜色与荧光变化的优点,但没有涉及其作为填料在聚合物材料内部的应用,并且通过自组装获得的完全由力致变色基团组成的微纳米球存在粒径分布广、成本高、难以进行表面修饰的问题,进一步限制了其在聚合物材料内部的应用。
目前,为了解决力致变色基团在聚合物基体内变色灵敏性低的问题,学术界进行了广泛而深入的研究,目前主要通过在聚合物内部构造微纳结构,利用微纳结构的应力集中效应,在材料宏观应力不变的前提下,提高力致变色基团所处的微观环境的应力水平,从而起到提高其力致变色灵敏性的效果,如(Adv.Mater.2018,1800291),在加载了力致变色基团的聚合物中引入SiO2纳米粒子,通过后者的应力集中效果,提高了基体的力致变色敏感性;(Adv.Mater.2019,31,1808148)报道了一种力致变色聚合物,通过在加载了力致变色基团的聚合物基体中引入内壁吸附了SiO2纳米粒子的微米孔,起到了提高力致变色敏感性的效果,将临界变色应变降低到了75%~80%;(Adv.Mater.Technol.2022,2200566)报道了一种内部加载了力敏变色基团的微米球,将临界变色应变降低到了50%,但没有研究内部组分以及表面修饰对微球力致变色敏感性的影响。综上所述,目前尚无将力致变色基团加载于纳米填料中,利用纳米填料的高应力集中效应与广泛的工艺适应性,将不同高分子材料转化为力致变色智能材料的技术手段。并且目前的技术仍然存在临界变色应变,力致变色灵敏性仍然不足。
发明内容
本发明的目的就在于为了解决上述问题而提供一种具有高力致变色灵敏性的纳米填料及其制备方法。本发明将力致变色基团加载于纳米粒子中,获得具有广泛适用性的力致变色纳米填料。进一步地,利用纳米填料在聚合物基体内部的应力集中效应,提高在相同宏观应力水平下力致变色基团周围的微观应力水平,并进一步通过对纳米填料组分与表面修饰的优化,从而达到提高力致变色分子的显色灵敏性的效果。同时这种高力致变色灵敏性的纳米填料具有可以提高高分子力学性能的优点。
本发明通过以下技术方案来实现上述目的:
一种具有高力致变色灵敏性的纳米填料,包括力致变色基团、聚合物单体、表面活性剂、引发剂,表面修饰剂,各组分的质量百分比如下:
力致变色基团:0.01~90%;
聚合物单体:10~99.98%;
表面活性剂:0.01~50%;
引发剂:0.01~10%;
表面修饰剂:0.1~80%。
进一步方案为,所述力致变色基团包括罗丹明或其衍生物、螺吡喃或其衍生物、聚集诱导发光分子、稀土掺杂荧光材料中的一种或多种。
进一步方案为,所述聚合物单体为含有一个或多个双键的聚合物单体,包括丙烯酸酯类、苯乙烯类中的一种或多种。
进一步方案为,所述表面活性剂包括阴离子表面活性剂、阳离子表面活性剂、非离子型表面活性剂等水包油表面活性剂中的一种或多种。
进一步方案为,所述引发剂包括光激活或热激活的自由基引发剂中的一种或多种。
进一步方案为,所述表面修饰剂包括丙烯酸、甲基丙烯酸2-氨基乙基酯盐酸盐、N-(3-氨基丙基)甲基丙烯盐酸盐、烯丙基胺盐酸盐中的一种或多种。
本发明另一方面还提供了一种具有高力致变色灵敏性的纳米填料的制备方法,包括以下步骤:
步骤1,将力致变色基团、引发剂溶解于聚合物单体中,得到油相;
步骤2,将表面活性剂、表面修饰剂溶解于水中,得到水相;
步骤3,将水相与油相混合后,对混合体系进行高剪切处理,得到水包油纳米乳液;
步骤4,通过升温或紫外光照射的方式,激活引发剂,经过聚合反应,得到内部加载力致变色基团的纳米填料分散液;
步骤5,通过离心或过滤的方式去除水分,并烘干,得到内部加载力致变色基团的纳米填料粉末。
进一步方案为,高剪切处理通过超声破碎仪、高速搅拌或微射流高压均质机等设备获得。
本发明又一方面还提供了上述的纳米填料或上述的制备方法得到的纳米填料在高分子材料内部应力感知领域的用途。
本发明再一方面还提供了一种力致变色树脂,为膜状或纤维状,其含有上述的纳米填料。
本发明的有益效果在于:
本发明的一种具有高力致变色灵敏性的纳米填料及其制备方法,将纳米粒子作为力致变色基团的载体,实现其纳米封装,利用纳米填料在聚合物基体内部的应力集中效应,提高在相同宏观应力水平下力致变色基团周围的微观应力水平,并进一步通过对纳米填料组分与表面修饰的优化,从而达到提高力致变色分子的显色灵敏性的效果。将其添加到高分子材料中后,可以赋予高分子材料力致变色的功能,为原位、实时、可视的检测高分子材料内部应力分布与大小提供了技术途径。
本发明的纳米填料对高分子材料具有增韧效果。
本发明的纳米填料,可以通过对其组分、结构、表面修饰的调控,方便地调控其力敏变色效果以及增韧效果,以适应不同应用场景。
本发明的纳米填料合成简单、易于加工、适用性广,可以通过喷涂、刮涂、发泡、注塑、捏合、密炼、双螺杆挤出等工艺方式添加到不同高分子材料中。
本发明的技术路线新颖,材料实用性强,将极大地推动其在智能高分子材料,力学传感器领域的应用。
附图说明
为了更清楚地说明本发明实施例中的技术方案,下面将对实施例或现有技术描述中所需要实用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1是实施例一制备得到的具有高力致变色灵敏性的纳米填料的电子扫描电镜照片;
图2是实施例一制备得到的具有高力致变色灵敏性的纳米填料研磨前后的荧光光谱;
图3是实施例四制备得到的添加了力致变色纳米填料的聚脲涂层,随应变增加荧光光谱的变化;
图4是实施例四制备得到的添加了力致变色纳米填料的聚脲涂层,在555nm波长处的荧光强度与应力随应变变化规律的曲线。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚,下面将对本发明的技术方案进行详细的描述。显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动的前提下所得到的所有其它实施方式,都属于本发明所保护的范围。
实施例一
一种所述的具有高力致变色灵敏性的纳米填料的制备方法,包括以下步骤:
在20g纯水中,溶解100mg表面活性剂SDS,50mg甲基丙烯酸2-氨基乙基酯盐酸盐得到水相。在1g甲基丙烯酸甲酯单体中,溶解50mg热敏引发剂AIBN,30mg罗丹明衍生物(((2-(2-(丙烯酰氧基)乙基)-2',7'-二甲基-3-氧代吡咯[异吲哚-1,9'-黄烯]-3',6'-二基)双(乙基氮炔基)二丙烯酸酯)),得到油相。将水相与油相混合后,使用超声破碎仪对混合体系进行高剪切处理,获得水包油纳米乳液。升温至70℃,经过72h聚合反应,过滤并烘干,最终得到内部加载了罗丹明力致变色分子的纳米填料。所获得的纳米填料直径在100nm到200纳米之间,如附图1,并且在研磨后能产生明显的荧光,如附图2。
实施例二
一种所述的具有高力致变色灵敏性的纳米填料的制备方法,包括以下步骤:
在20g纯水中,溶解150mg表面活性剂lutensol AT50,50mg N-(3-氨基丙基)甲基丙烯盐酸盐得到水相。在1g丙烯酸异丁酯中,溶解60mg光敏引发剂2,2'-双(2-氯苯基)-4,4',5,5'-四苯基-1,2'-联咪唑,50mg螺吡喃衍生物(1',3',3'-三甲基-6-硝基螺[色烯-2,2'-二氢吲哚]-5',8-二基双(2-甲基丙烯酸酯)),得到油相。将水相与油相混合后,使用超声破碎仪对混合体系进行高剪切处理,获得水包油纳米乳液。使用紫外光照射引发聚合,经过72h聚合反应,过滤并烘干,最终得到内部加载了罗丹明力致变色分子的纳米填料。
实施例三
一种所述的具有高力致变色灵敏性的纳米填料的制备方法,包括以下步骤:
在20g纯水中,溶解150mg表面活性剂lutensol AT50,50mg N-(3-氨基丙基)甲基丙烯盐酸盐得到水相。在1g丙烯酸丁酯中,溶解60mg光敏引发剂2,2'-双(2-氯苯基)-4,4',5,5'-四苯基-1,2'-联咪唑,并分散50mg荧光粉ZnS:M 2+(Mn/Cu)@Al 2O 3材料,得到油相。将水相与油相混合后,使用超声破碎仪对混合体系进行高剪切处理,获得水包油纳米乳液。升温至70℃,经过72h聚合反应,过滤并烘干,最终得到内部加载了罗丹明力致变色分子的纳米填料。
实施例四
一种包含高力致变色灵敏性的纳米填料的的聚脲涂层的制备方法,包括以下步骤:
将实施例一反应得到的力致变色纳米填料离心,重新分散于四氢呋喃中,同时将聚四亚甲基醚二醇双对氨基苯甲酸酯溶解于四氢呋喃中,与纳米填料的分散液混合,并旋蒸去除四氢呋喃,得到含有力致变色纳米粒子的P1000树脂;将该树脂与MDI-50交联剂按照质量比4:1溶解于无水二氯甲烷中,得到涂料;最后将该涂料刮涂于玻璃板上,室温固化24h,获得加载了力致变色纳米填料的聚脲涂层。所获得的具有力致变色功能的聚脲涂层的荧光强度随应变的增加变化明显,如附图3,并且555nm波长处的荧光强度与应力随应变变化规律的曲线表明,该涂层的力致变色效果无临界激活应变,如附图4,这与目前现存技术中,力致变色材料普遍需要大于50%应变才表现出荧光强度增加的效果不同,具有明显的先进性。
以上所述,仅为本发明的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,可轻易想到变化或替换,都应涵盖在本发明的保护范围之内。因此,本发明的保护范围应以所述权利要求的保护范围为准。另外需要说明的是,在上述具体实施方式中所描述的各个具体技术特征,在不矛盾的情况下,可以通过任何合适的方式进行组合,为了避免不必要的重复,本发明对各种可能的组合方式不再另行说明。此外,本发明的各种不同的实施方式之间也可以进行任意组合,只要其不违背本发明的思想,其同样应当视为本发明所公开的内容。
Claims (10)
1.一种具有高力致变色灵敏性的纳米填料,其特征在于,包括力致变色基团、聚合物单体、表面活性剂、引发剂,表面修饰剂,各组分的质量百分比如下:
力致变色基团:0.01~90%;
聚合物单体:10~99.98%;
表面活性剂:0.01~50%;
引发剂:0.01~10%;
表面修饰剂:0.1~80%。
2.如权利要求1所述的一种具有高力致变色灵敏性的纳米填料,其特征在于,所述力致变色基团包括罗丹明或其衍生物、螺吡喃或其衍生物、聚集诱导发光分子、稀土掺杂荧光材料中的一种或多种。
3.如权利要求1所述的一种具有高力致变色灵敏性的纳米填料,其特征在于,所述聚合物单体为含有一个或多个双键的聚合物单体,包括丙烯酸酯类、苯乙烯类中的一种或多种。
4.如权利要求1所述的一种具有高力致变色灵敏性的纳米填料,其特征在于,所述表面活性剂包括阴离子表面活性剂、阳离子表面活性剂、非离子型表面活性剂等水包油表面活性剂中的一种或多种。
5.如权利要求1所述的一种具有高力致变色灵敏性的纳米填料,其特征在于,所述引发剂包括光激活或热激活的自由基引发剂中的一种或多种。
6.如权利要求1所述的一种具有高力致变色灵敏性的纳米填料,其特征在于,所述表面修饰剂包括丙烯酸、甲基丙烯酸2-氨基乙基酯盐酸盐、N-(3-氨基丙基)甲基丙烯盐酸盐、烯丙基胺盐酸盐中的一种或多种。
7.一种具有高力致变色灵敏性的纳米填料的制备方法,包括以下步骤:
步骤1,将力致变色基团、引发剂溶解于聚合物单体中,得到油相;
步骤2,将表面活性剂、表面修饰剂溶解于水中,得到水相;
步骤3,将水相与油相混合后,对混合体系进行高剪切处理,得到水包油纳米乳液;
步骤4,通过升温或紫外光照射的方式,激活引发剂,经过聚合反应,得到内部加载力致变色基团的纳米填料分散液;
步骤5,通过离心或过滤的方式去除水分,并烘干,得到内部加载力致变色基团的纳米填料粉末。
8.如权利要求7所述的一种具有高力致变色灵敏性的纳米填料的制备方法,其特征在于,高剪切处理通过超声破碎仪、高速搅拌或微射流高压均质机获得。
9.如权利要求1-6任一项所述的纳米填料或如权利要求7-8任一项所述的制备方法得到的纳米填料在高分子材料内部应力感知领域的用途。
10.一种力致变色树脂,为膜状或纤维状,其含有权利要求1-6中任一项所述的纳米填料或权利要求7-8任一项所述的制备方法得到的纳米填料。
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