CN112961325B - 基于嵌段共聚物的一维光子晶体及其制备方法和在力学响应领域的应用 - Google Patents
基于嵌段共聚物的一维光子晶体及其制备方法和在力学响应领域的应用 Download PDFInfo
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- CN112961325B CN112961325B CN201911275668.6A CN201911275668A CN112961325B CN 112961325 B CN112961325 B CN 112961325B CN 201911275668 A CN201911275668 A CN 201911275668A CN 112961325 B CN112961325 B CN 112961325B
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Abstract
基于嵌段共聚物的一维光子晶体及其制备方法和在力学响应领域的应用。本发明公开了一种基于嵌段共聚物的一维光子晶体,采用带有端基溴降冰片烯结构的引发剂R1,利用ATRP方法分别合成基于PS和PHEA单体的两种大分子单体R1‑PS和R1‑PEHA;然后通过ROMP进行R1‑PS大分子单体的活性聚合,待R1‑PS大分子单体转化率达到100%后,再将R1‑PHEA大分子单体进行投料,最终形成嵌段共聚物刷,该嵌段共聚物刷即为一维光子晶体材料。本发明的一维光子晶体可作为视觉检测的力传感器使用,提供了一种新型、高效的无损可视化压力检测方法,具有简单、快速和实时性无损检测力学状态变化的潜在应用。
Description
技术领域
本发明涉及一种基于嵌段共聚物的一维光子晶体及其制备方法和在力学响应领域的应用,具体涉及采用原子转移自由基聚合(ATRP)得到两种大分子单体降冰片烯苯乙烯(R1-PS)、降冰片烯丙烯酸-2-乙基己酯(R1-PEHA),再利用开环易位聚合(ROMP)连续投料的方法合成聚降冰片烯苯乙烯-b-聚降冰片烯丙烯酸-2-乙基己酯(P[R1-PS]-b-P[R1-PHEA])的嵌段共聚物刷,该嵌段共聚物即为一维光子晶体,通过原位受压力自组装可形成具有良好层状结构的一维光子晶体薄膜从而结构显色,可用作力传感器,具有简单、快速和实时性无损检测力学状态变化的潜在应用。
背景技术
对于工程材料的应用环境,实时监控工程塑料和橡胶等材料受力状态对安全性评估来说尤为重要。无损检测是工业发展必不可少的有效工具,一定程度上其反映了一个国家的工业发展水平。目视检测在国内实施的比较少,但在国际上,无损检测是作为检测第一阶段的首要方法,如目视检测钢材结构焊缝及外观缺陷。但对大型塑料制品受力状态,老化变形等目视检测较为少见。近几年,文献报道了将含有力化学的基团引入聚合物中,在拉力或者超声的作用下实现化学键的断裂,从而导致聚合物颜色的变化,可用于聚合物材料受应力的裸眼检测(nature,2009,459,68-72;ACS Macro Lett.2018,7,556-560等)。然而,对于聚合物材料受到压力应力变化的检测比较少。如果能将具有力学响应性的聚合物基光子晶体涂层赋予材料表面或内层,能够通过薄膜颜色改变来长期实时监控材料局部关键部位受压力变化,在工程安全实时检测上具有重要的意义。
光子晶体是指由两种及以上具有不同折光指数的材料,在空间按照一定的周期顺序排列而成的有序结构材料,光子晶体具有类似于半导体的能带结构,因此电磁波在光子晶体中传播会产生光子禁带,不同光子禁带的光子晶体会呈现不同的结构色。目前大部分光子晶体的制备主要是基于平板印刷法、胶体自组装、蛋白石和反蛋白石结构模板法等,这些制备方法多为二维或三维光子晶体,合成较为复杂,而且易在任意位点产生晶格缺陷,改变光的传播方向,而具有周期性层状结构的一维光子晶体具有结构简单的优点。近年来,利用开环易位聚合得到的嵌段共聚物刷,将其自组装构成的一维光子晶体,由于其特有的光子禁带可调节性而被广泛的应用于光学领域。而刷形嵌段聚合物的种类及聚合度的差异导致其力学、热学及光学性质发生变化,使其具有了广泛的应用前景。
近年来,结构色光子晶体作为检测器已经引起了越来越多科研工作者的兴趣,在检测器方面相比于其他方法,光子晶体具有简单、快速和裸眼检测的巨大优势。目前许多文献中都报道了以光子晶体作为视觉检测的传感器使用。如利用甲基丙烯酸甲酯与丙烯酸乙酯共聚物嵌入聚(丙烯酸乙酯)弹性体基质得到三维光子晶体弹性体,能够在拉伸状态下发生颜色的转变(T.Ito,C.Katsura,H.Sugimoto,E.Nakanishi,and K.Inomata,Langmuir,2013,29,13951-13957)和利用有机/无机杂化的一维光子晶体在不同有机溶剂中基于颜色变化的裸眼检测(Z.Wang,J.Zhang,Z.Tian,Z.Wang,Y.Li,S.Liang,L.Cui,L.Zhang andB.Yang,Chemical communications,2010,46,8636-8638.)。但是,直到目前为止,很少有涉及到利用一维光子晶体的可视变化来进行关于压力的检测。
发明内容
本发明的目的在于克服现有技术的不足,提供了一种基于嵌段共聚物的一维光子晶体及其制备方法和在力学响应领域的应用。
本发明的技术目的通过下述技术方案予以实现。
一种嵌段共聚物刷,具有如下化学结构通式:
其中,m、n和I为聚合度,m为20-60,n为10-40,I为100-600;所述嵌段共聚物刷的数均分子量为50-1200k,分散性小于2.0。
所述嵌段共聚物刷通过下述步骤制备得到:
步骤1:将90-100mg的降冰片烯苯乙烯(R1-PS)大分子单体充分溶解于1mL的无水无氧的二氯甲烷(DCM)中,然后加入110-320μL的浓度为1mg/mL的Grubbs 3催化剂的DCM溶液,在20-30℃室温下搅拌反应5-30min,得到聚降冰片烯苯乙烯(P[R1-PS]);
在步骤1中,利用Grubbs 3催化剂进行活性开环易位聚合,在整个活性聚合过程中,可实现聚合物的分子结构、分子量以及分子量分布的可控;
在步骤1中,为提高R1-PS的转化率,可适当延长聚合反应时间。
步骤2:将降冰片烯丙烯酸-2-乙基己酯(R1-PHEA)大分子单体溶解于1.2mL无水无氧的DCM中,然后将所述溶液加入到步骤1的反应体系中,继续在20-30℃室温下搅拌反应20-60min,最后加入乙烯基乙醚终止剂使反应终止,得到聚降冰片烯苯乙烯-b-聚降冰片烯丙烯酸-2-乙基己酯嵌段共聚物刷(P[R1-PS]-b-P[R1-PHEA]);其中,R1-PHEA大分子单体与步骤1中的R1-PS大分子单体的摩尔比为1:1,Grubbs 3催化剂的用量与R1-PS和R1-PHEA两种大分子单体总量的摩尔比为1:(100-600),优选1:(120-300);
在步骤2中,为提高R1-PHEA的转化率,可适当延长聚合反应时间;
在步骤2中,加入乙烯基乙醚终止剂后,继续搅拌10-30min以使体系均匀停止反应,反应结束后使用甲醇/二氯甲烷混合溶剂沉淀提纯三次,然后将固体产物在30-40℃下真空干燥,得到P[R1-PS]-b-P[R1-PHEA]嵌段共聚物刷。
在本发明的聚合物制备过程中,使用的催化剂为Grubbs三代试剂,由它催化的聚合是活性的聚合,其具有反应条件温和、反应高效快速等优点。该聚合得到的聚合物具有分子量可控,分散性窄(一般分散系数小于1.3)的特性。因此采取Grubbs三代试剂催化的开环易位聚合的方法,可实现对磁性聚合物的分子量和分子量分布的控制和调节。其中聚合物端基的苯环Ph来自于Grubbs三代试剂中的苯环Ph,而聚合物另一端基的基团则来源于聚合反应结束时所添加的终止剂,所用的终止剂是乙烯基乙醚,所以聚合物另一端基是乙醚的结构(参考文献Y.Qiao,Y.Zhao,X.Yuan,Y.Zhao,L.Ren,Journal of Materials Science,2018,53:16160-16168.)。
在本发明的P[R1-PS]-b-P[R1-PHEA]嵌段共聚物刷的制备方法中,采用带有端基溴降冰片烯结构的引发剂R1,利用原子转移自由基聚合(ATRP)方法分别合成基于苯乙烯(PS)单体和丙烯酸-2-乙基己酯(PHEA)单体的两种大分子单体R1-PS和R1-PEHA;然后通过开环易位聚合(ROMP)进行R1-PS大分子单体的活性聚合,待R1-PS大分子单体转化率达到100%后,再将R1-PHEA大分子单体进行投料,最终形成嵌段共聚物刷,其化学反应方程式大致如下:
其中,m、n和I为聚合度,m为20-60,n为10-40,I为100-600;通过改变不同的投料比,可以制备不同数均分子量和不同嵌段比例的的刷形嵌段共聚物,其数均分子量在50-1200k范围之内,分散性小于2.0。
带有降冰片烯结构的引发剂R1,其化学式如下:
两种带有降冰片烯结构大分子单体R1-PS和R1-PEHA,其化学式如下:
其中,m和n为聚合度,m为20-60,n为10-40,两大分子单体R1-PS和R1-PEHA的数均分子量都为1000-5000,分散性都小于1.2;
两种均聚物刷P[R1-PS]、P[R1-PHEA],其化学式如下:
其中,I为主链聚合度,I为100-600,两种均聚物刷P[R1-PS]和P[R1-PHEA]的数均分子量都为150-500k,P[R1-PS]分散性小于1.3,P[R1-PHEA]分散性小于1.2。
P[R1-PS]-b-P[R1-PHEA]嵌段共聚物刷的制备过程中,首先进行R1-PS大分子单体的活性聚合,待R1-PS大分子单体转化率达到100%后,再将R1-PHEA大分子单体进行投料,最终形成嵌段共聚物刷,其反应方程式如下:
其中,m、n和I为聚合度,m为20-60,n为10-40,I为100-600;通过改变不同的投料比,可以制备不同数均分子量和不同嵌段比例的的刷形嵌段共聚物,其数均分子量在50-1200k范围之内,分散性小于2.0。
本发明制备得到的P[R1-PS]-b-P[R1-PHEA]嵌段共聚物刷就是一种一维光子晶体材料。
本发明还公开了嵌段共聚物刷作为一维光子晶体在力学响应领域的应用。
当向基于所述嵌段共聚物刷的一维光子晶体施加一定压力时,受压力的区域颜色发生变化,而未受压力的区域颜色不发生变化。
基于所述嵌段共聚物刷的一维光子晶体初始状态为白色,当向其施加一定压力时,受压力的区域变成蓝色,而未受压力的区域仍为白色。
本发明的有益效果在于:本发明利用Grubbs三代试剂作为催化剂进行开环易位聚合来保证制备得到较窄分子量分布和较高分子量的P[R1-PS]-b-P[R1-PHEA]嵌段共聚物刷,基于本发明的嵌段共聚物的一维光子晶体受压力后进行自组装形成良好的层状结构,从而表现出良好的光学性能,即结构显色,因此本发明的一维光子晶体可作为视觉检测的力传感器使用,提供了一种新型、高效的无损可视化压力检测方法,具有简单、快速和实时性无损检测力学状态变化的潜在应用;并且得到一维光子晶体的嵌段聚合物的主链和侧链最优化设计的结构,为后期优化力学响应性能提供了理论支持。
附图说明
图1为本发明的P[R1-PS]-b-P[R1-PHEA]嵌段共聚物刷的核磁氢谱图。
图2为本发明的单体、大分子单体和嵌段共聚物刷的DSC图。
图3为本发明的PR1、R1-PS、P[R1-PS]的TG图。
图4为本发明的R1-PHEA和P[R1-PHEA]的TG图。
图5为本发明的P[R1-PS]-b-P[R1-PHEA]嵌段共聚物刷的TG图。
图6为本发明的P[R1-PS]-b-P[R1-PHEA]嵌段共聚物刷压力自组装后薄膜的照片。
图7为本发明的内嵌P[R1-PS]-b-P[R1-PHEA]嵌段共聚物刷的PDMS材料局部受压变色的照片。
图8为本发明的P[R1-PS]-b-P[R1-PHEA]嵌段共聚物刷按压自组装后薄膜的反射光谱图。
图9为本发明的P[R1-PS]-b-P[R1-PHEA]嵌段共聚物刷按压自组装后薄膜的SAXS的图。
具体实施方式
下面通过具体实施例和附图对本发明做进一步说明,但并不限制本发明的权利范围。
本发明实施例所使用的试剂来源如下:
名称 | 来源 | 纯度 |
顺-5-降冰片烯-外-2,3-二羧酸酐 | 萨恩化学技术(上海)有限公司 | 99% |
5-降冰片烯-2-甲醇 | 萨恩化学技术(上海)有限公司 | 99% |
苯乙烯 | 天津江天化工有限公司 | 99% |
丙烯酸-2-乙基己酯 | 天津希恩思普德科技有限公司 | 99% |
溴化亚铜 | 上海阿拉丁生化科技股份有限公司 | 98% |
N,N,N’,N”,N”-五甲基二乙烯三胺 | 上海阿拉丁生化科技股份有限公司 | 95% |
三乙胺 | 天津元立化工有限公司 | 97% |
聚二甲基硅氧烷 | 美国道康宁股份有限公司 |
带有溴端基的降冰片烯引发剂R1的合成:
步骤1:将2.00g(12.18mmol)顺-5-降冰片烯-外-2,3-二酸酐和0.71mL(12.18mmol)2-氨基乙醇置于100mL的圆底烧瓶中,加入30mL DCM溶解后搅拌10h,旋干溶剂后,将整个反应体系置于100℃油浴中加热5h,将得到的粗产物用DCM溶解后过中性氧化铝柱除去杂质,再次旋干后将产物置于50℃真空烘箱中干燥5h,得到白色固体粉末;
步骤2:取2.00g(9.65mmol)步骤1制得的白色固体粉末溶于30mL的DCM中,加入2摩尔当量的三乙胺,溶解后在冰水浴中搅拌10min;将3mL 2-溴-2-甲基丙酰溴溶于10mL的DCM中,然后将其滴加入反应体系中,室温搅拌5h;先后用饱和碳酸氢钠水溶液(20mL×3),去离子水(40mL×3))分别萃取三次,收集有机相并用无水硫酸钠干燥;以体积比为4:1的石油醚/乙酸乙酯为淋洗剂过硅胶柱提纯,旋干得到的产物在二氯甲烷/石油醚体系中再重结晶3次,最终得到白色柱状晶体,即引发剂R1。
大分子单体R1-PS的合成:
将0.22g(0.63mmol)上述合成的R1引发剂和8.0mL(69mmol)除阻聚剂的苯乙烯加入到50mL的施兰克瓶中,冻融三次除氧;然后在液氮冷却状态下迅速加入25.70mg(0.46mmol)CuBr和36μL PMDETA,抽放气三次除氧;氮气氛围下,反应体系解冻后室温下搅拌5min,然后置于温度恒定的80℃油浴中反应1.5h;反应结束后迅速用液氮骤冷,加入几滴四氢呋喃(THF)淬灭;最后以THF为淋洗液过中性氧化铝柱子,浓缩后用甲醇沉淀三次提纯,将产物置于50℃真空烘箱干燥5h得到白色粉末产物,即R1-PS。
大分子单体R1-PEHA的合成:
将0.20g(0.56mmol)上述合成的R1引发剂、10mL除阻聚剂的丙烯酸-2-乙基己酯和5.8mL丙酮加入到25mL的施兰克瓶中,冻融三次除氧;然后在液氮冷却状态下迅速加入84mg(0.60mmol)CuBr和116μL(0.56mmol)PMDETA,抽放气三次除氧;氮气氛围下,反应体系解冻后室温下搅拌5min,然后置于温度恒定的80℃油浴中反应3h;反应结束后迅速用液氮骤冷,加入几滴四氢呋喃(THF)淬灭;最后以THF为淋洗液过中性氧化铝柱子,旋干后用体积比为9:1的甲醇/水沉淀一次,浓缩后用甲醇沉淀三次提纯,将产物置于50℃真空烘箱干燥5h得到无色粘稠产物,即R1-PEHA。
涉及到的化学反应式如下:
实施例1
步骤1:称取93.00mg的R1-PS,在手套箱中将其放入10mL小瓶中,再加入1mL无水无氧的DCM,搅拌使R1-PS充分溶解于DCM,然后现配质量分数为1mg/mL的Grubbs3催化剂DCM溶液,用移液枪取165μL并快速加入到上述反应体系中,在25℃室温下搅拌反应10min,得到P[R1-PS];
步骤2:称取96.00mg的R1-PEHA溶于1.2mL无水无氧的DCM中,然后将该混合溶液快速加入到步骤1的反应体系中,继续在25℃室温下搅拌反应30min;快速将反应体系从手套箱中取出,在搅拌条件下加入乙烯基乙醚淬灭,继续搅拌20min以使体系均匀停止反应,反应结束后用甲醇/DCM混合溶剂沉淀提纯三次,然后将固体产物在35℃下真空干燥,得到P[R1-PS]-b-P[R1-PHEA]嵌段共聚物刷(BCP-1)。
实施例2
步骤1:称取100.00mg的R1-PS,在手套箱中将其放入10mL小瓶中,再加入1mL无水无氧的DCM,搅拌使R1-PS充分溶解于DCM,然后现配质量分数为1mg/mL的Grubbs3催化剂DCM溶液,用移液枪取320μL并快速加入到上述反应体系中,在25℃室温下搅拌反应30min,得到P[R1-PS];
步骤2:称取103.00mg的R1-PEHA溶于1.2mL无水无氧的DCM中,然后将该混合溶液快速加入到步骤1的反应体系中,继续在25℃室温下搅拌反应60min;快速将反应体系从手套箱中取出,在搅拌条件下加入乙烯基乙醚淬灭,继续搅拌30min以使体系均匀停止反应,反应结束后用甲醇/DCM混合溶剂沉淀提纯三次,然后将固体产物在35℃下真空干燥,得到P[R1-PS]-b-P[R1-PHEA]嵌段共聚物刷(BCP-1)。
实施例3
步骤1:称取90.00mg的R1-PS,在手套箱中将其放入10mL小瓶中,再加入1mL无水无氧的DCM,搅拌使R1-PS充分溶解于DCM,然后现配质量分数为1mg/mL的Grubbs3催化剂DCM溶液,用移液枪取110μL并快速加入到上述反应体系中,在25℃室温下搅拌反应5min,得到P[R1-PS];
步骤2:称取93.00mg的R1-PEHA溶于1.2mL无水无氧的DCM中,然后将该混合溶液快速加入到步骤1的反应体系中,继续在25℃室温下搅拌反应2min;快速将反应体系从手套箱中取出,在搅拌条件下加入乙烯基乙醚淬灭,继续搅拌10min以使体系均匀停止反应,反应结束后用甲醇/DCM混合溶剂沉淀提纯三次,然后将固体产物在35℃下真空干燥,得到P[R1-PS]-b-P[R1-PHEA]嵌段共聚物刷(BCP-1)。
实施例1至3的反应过程如下:
对实施例1制得的嵌段共聚物刷进行1H NMR-表征,如图1所示,在δ=6.28ppm处降冰片烯的双键上的氢原子共振峰完全消失,并在δ=5.53ppm处附近出现了ROMP反应后生成的双键上氢原子的吸收峰,证明两种大分子单体R1-PS和R1-PHEA已经完全转化,成功制得了P[R1-PS]-b-P[R1-PHEA]嵌段共聚物刷。
分别对R1-PS和R1-PHEA大分子单体、P[R1-PS]和P[R1-PHEA]均聚物及所制备的P[R1-PS]-b-P[R1-PHEA]嵌段共聚物刷进行了热失重表征。在氮气氛围下,控制样品的升温速度为10℃/min,测试温度为35-800℃。如图2所示,R1-PS和R1-PHEA大分子单体、P[R1-PS]和P[R1-PHEA]均聚物及所制备的P[R1-PS]-b-P[R1-PHEA]嵌段共聚物刷在240℃以下均无分解,大分子单体R1-PS和均聚物P[R1-PS]在失重10%的热分解温度分别为357℃和369℃,大分子单体R1-PEHA和均聚物P[R1-PEHA]在失重10%的热分解温度分别为321℃和285℃,P[R1-PS]-b-P[R1-PHEA]嵌段共聚物刷在失重10%的热分解温度为350℃,这一结果表明R1-PS和R1-PHEA大分子单体及其均聚物和P[R1-PS]-b-P[R1-PHEA]嵌段共聚物刷在较高温度下的热稳定性优良,为P[R1-PS]-b-P[R1-PHEA]嵌段共聚物刷的组装产物在较高温度条件下的应用提供了保障。
随后又分别对PR1、R1-PS、P[R1-PS]、R1-PHEA 、P[R1-PHEA]和P[R1-PS]-b-P[R1-PHEA]的玻璃化转变温度(Tg)进行了表征。如图3至5所示,两种大分子单体R1-PS和R1-PHEA的Tg分别为88℃和-70℃,表明PEHA体系大分子单体常温下呈黏流态,相比于PS体系在室温下具有更好的粘弹性,从而达到软硬相结合的目的;引发剂R1经ROMP形成的主链均聚物PR1的Tg为107℃,表明PR1主链较为刚硬,进而能更好地去设计主链结构来研究BCP力学性质;两种均聚物P[R1-PS]和P[R1-PHEA]的Tg分别为95℃和-62℃,相比于其对应的大分子单体R1-PS和R1-PEHA,Tg略微增高,这是由于PR1主链玻璃化温度较高,导致形成均聚物刷之后,虽然使无序度减少,但是链缠结现象严重,导致链段运动所需克服的能垒增加所致;P[R1-PS]-b-P[R1-PHEA]嵌段共聚物的Tg有2个,分别为-62℃和101℃,这个结果与上述均聚物刷的趋势相同,充分证明了该体系嵌段共聚物的可设计性,为之后类似体系的设计与研究提供了实验依据。
将本发明实施例制得的P[R1-PS]-b-P[R1-PHEA]嵌段共聚物刷通过压力自组装法制备成一维光子晶体薄膜,具体步骤如下:将10mg实施例1制得的P[R1-PS]-b-P[R1-PHEA]嵌段共聚物刷置于玻璃片上,然后用另一片玻璃片在25℃室温下按压进行自组装,得到一维光子晶体薄膜。如图6所示,在25℃室温下按压自组装后,由于P[R1-PS]-b-P[R1-PHEA]嵌段共聚物刷的粘弹性优异,在压力或剪切力下嵌段之间的排列更为规整,自组装得到的一维光子晶体薄膜呈明显的蓝色,这个现象的出现是因为嵌段共聚物体系在受力时两嵌段相分离而使得自组装程度不同,以及聚合物存在多分散性。
如图7所示,将本发明制得的P[R1-PS]-b-P[R1-PHEA]嵌段共聚物镶嵌在高弹性的透明聚二甲基硅氧烷(PDMS)硅胶片中,嵌段共聚物在初始状态下是白色的,当对PDMS硅胶片局部施加一定的压力时,压力也会间接作用到内部的嵌段共聚物上而呈现蓝色。所以在基质材料局部受到压力时,镶嵌或复合在基质材料中的P[R1-PS]-b-P[R1-PHEA]嵌段共聚物会产生一定的颜色响应,受到压力的部位变为蓝色,没有受到压力的部位仍为白色,因此本发明的P[R1-PS]-b-P[R1-PHEA]嵌段共聚物为局部力直观裸眼监测提供了可能。
为了进一步研究本发明的一维光子晶体的光学性质,采用配备积分球的紫外/可见/近红外分光光度计针对受压力自组装后的一维光子晶体薄膜进行了反射光谱测试。如图8所示,P[R1-PS]-b-P[R1-PHEA]嵌段共聚物刷在25℃室温下按压自组装形成一维光子晶体薄膜后,其最大反射波长在366nm处,反射率在37%左右。P[R1-PS]-b-P[R1-PHEA]嵌段共聚物刷的主链全部由刚性R1构成,使得体系刚性较大,体系局部规整性较好,一定程度上出现了相分离,从而不利于自组装为长程有序的周期性结构,但是由于PEHA软段的引入赋予了P[R1-PS]-b-P[R1-PHEA]嵌段共聚物刷一定的粘弹性,使得其在受压力是显示出一定的自组装效果,片层结构的形成使得薄膜的最大反射波长在366nm处,从而使薄膜在宏观上显示出蓝色,即本发明的一维光子晶体薄膜的显色为结构显色,由此证明本发明的P[R1-PS]-b-P[R1-PHEA]嵌段共聚物刷可作为力学响应性一维光子晶体材料。
还对本发明的一维光子晶体薄膜进行了小角X射线散射表征,如图9所示,本发明的一维光子晶体薄膜具有非常明显的1q、2q衍射峰,且1q、2q、3q呈倍数变化,由此证明本发明的P[R1-PS]-b-P[R1-PHEA]嵌段共聚物刷在25℃室温下按压自组装后具有最好的层状相自组装形貌;其中,一级衍射峰均为q=0.040左右,根据布拉格反射方程(d=2π/q),可以计算出层间距为157nm左右。
本发明的P[R1-PS]-b-P[R1-PHEA]嵌段共聚物刷,其结构为主链与侧链玻璃化转变温度均较低的软段区域和主链与侧链玻璃化转变温度均较高的硬段区域的交替组合,使其在室温下受力时能自组装呈良好的层状结构,从而将力学状态信号出色地转变为光学信号,从而为可视化力传感器提供了可能,同时也为力学响应材料的设计提供了优化设计思路。
根据本发明内容进行工艺参数的调整,均可实现嵌段聚合物和光子晶体的制备,经测试表现出与实施例基本一致的性能,即本发明的嵌段共聚物及其光子晶体薄膜在机械响应方面的应用,根据受力的颜色变化进行定性检测,为力学状态检测提供了一种新型、可行、高效的可视化检测方法。以上对本发明做了示例性的描述,应该说明的是,在不脱离本发明的核心的情况下,任何简单的变形、修改或者其他本领域技术人员能够不花费创造性劳动的等同替换均落入本发明的保护范围。
Claims (10)
2.根据权利要求1所述的嵌段共聚物刷,其特征在于:通过下述步骤制备得到:
步骤1:将90-100mg的降冰片烯苯乙烯大分子单体充分溶解于无水无氧的二氯甲烷中,然后加入110-320μL的浓度为1mg/mL的Grubbs 3催化剂的二氯甲烷溶液,在20-30℃室温下搅拌反应5-30min,得到聚降冰片烯苯乙烯;
步骤2:将降冰片烯丙烯酸-2-乙基己酯大分子单体溶解于无水无氧的二氯甲烷中,然后将所述溶液加入到步骤1的反应体系中,继续在20-30℃室温下搅拌反应20-60min,最后加入乙烯基乙醚终止剂使反应终止,得到聚降冰片烯苯乙烯-b-聚降冰片烯丙烯酸-2-乙基己酯嵌段共聚物刷;其中,降冰片烯丙烯酸-2-乙基己酯大分子单体与步骤1中的降冰片烯苯乙烯大分子单体的摩尔比为1:1,Grubbs 3催化剂的用量与降冰片烯苯乙烯和降冰片烯丙烯酸-2-乙基己酯两种大分子单体总量的摩尔比为1:(100-600)。
3.根据权利要求2所述的嵌段共聚物刷,其特征在于:在步骤2中,Grubbs 3催化剂的用量与降冰片烯苯乙烯和降冰片烯丙烯酸-2-乙基己酯两种大分子单体总量的摩尔比为1:(120-300)。
4.根据权利要求2所述的嵌段共聚物刷,其特征在于:在步骤2中,加入乙烯基乙醚终止剂后,继续搅拌10-30min以使体系均匀停止反应,反应结束后使用甲醇/二氯甲烷混合溶剂沉淀提纯三次,然后将固体产物在30-40℃下真空干燥,得到聚降冰片烯苯乙烯-b-聚降冰片烯丙烯酸-2-乙基己酯嵌段共聚物刷。
5.一种嵌段共聚物刷的制备方法,其特征在于:包括以下步骤:
步骤1:将90-100mg的降冰片烯苯乙烯大分子单体充分溶解于1mL的无水无氧的二氯甲烷中,然后加入110-320μL的浓度为1mg/mL的Grubbs 3催化剂的二氯甲烷溶液,在20-30℃室温下搅拌反应5-30min,得到聚降冰片烯苯乙烯;
步骤2:将降冰片烯丙烯酸-2-乙基己酯大分子单体溶解于1.2mL无水无氧的二氯甲烷中,然后将所述溶液加入到步骤1的反应体系中,继续在20-30℃室温下搅拌反应20-60min,最后加入乙烯基乙醚终止剂使反应终止,得到聚降冰片烯苯乙烯-b-聚降冰片烯丙烯酸-2-乙基己酯嵌段共聚物刷;其中,降冰片烯丙烯酸-2-乙基己酯大分子单体与步骤1中的降冰片烯苯乙烯大分子单体的摩尔比为1:1,Grubbs 3催化剂的用量与降冰片烯苯乙烯和降冰片烯丙烯酸-2-乙基己酯两种大分子单体总量的摩尔比为1:(100-600)。
6.根据权利要求5所述的嵌段共聚物刷的制备方法,其特征在于:在步骤2中,Grubbs 3催化剂的用量与降冰片烯苯乙烯和降冰片烯丙烯酸-2-乙基己酯两种大分子单体总量的摩尔比为1:(120-300).
7.根据权利要求5所述的嵌段共聚物刷的制备方法,其特征在于:在步骤2中,加入乙烯基乙醚终止剂后,继续搅拌10-30min以使体系均匀停止反应,反应结束后使用甲醇/二氯甲烷混合溶剂沉淀提纯三次,然后将固体产物在30-40℃下真空干燥,得到聚降冰片烯苯乙烯-b-聚降冰片烯丙烯酸-2-乙基己酯嵌段共聚物刷。
8.权利要求1至4任一项所述的嵌段共聚物刷作为一维光子晶体在力学检测中的应用。
9.根据权利要求8所述的嵌段共聚物刷作为一维光子晶体在力学检测中的应用,其特征在于:当向所述嵌段共聚物施加一定压力时,所述嵌段共聚物受压力的区域颜色发生变化,而未受压力的区域颜色不发生变化。
10.根据权利要求9所述的嵌段共聚物刷作为一维光子晶体在力学检测中的应用,其特征在于:所述嵌段共聚物初始状态为白色,当向所述嵌段共聚物施加一定压力时,受压力的区域变成蓝色,而未受压力的区域仍为白色。
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