CN109400851B - 一种树枝状嵌段共聚物、合成方法及其自组装物、自组装方法 - Google Patents
一种树枝状嵌段共聚物、合成方法及其自组装物、自组装方法 Download PDFInfo
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Abstract
本发明公开了一种树枝状嵌段共聚物、合成方法及其自组装物、自组装方法,本发明的树枝形嵌段共聚物的合成是通过一些列活性可控的开环易位聚合(ROMP)方法得到的,通过简单的溶剂挥发自组装,得到了一系列具有长程有序的大尺寸层状结构的光子晶体材料。通过反射光谱测试我们得到了高反射率且带宽较窄的反射图谱,这使得发明的光子晶体材料可以应用于更加精密的光学器件方面。
Description
技术领域
本发明涉及树枝状嵌段共聚物的制备技术及其自组装技术,具体涉及通过一系列有机合成精确得到树枝状嵌段共聚物,并通过自组装制备一维光子晶体材料。
背景技术
光子晶体是一类由不同介电常数材料组成的周期性有序纳米结构材料。因为内部存在的光子禁带结构可以调控光的传播,使得光子晶体制成的器件具有很广泛的应用范围,如硅光子集成电路,光子晶体纤维,癌症治疗,发光二极管的增强发射等。根据内部周期性结构在不同维度的排列,可以分为一维,二维和三维光子晶体。其中一维光子晶体是最简单的一种,在一维方向有序,又被称为布拉格反射镜,内部表现为周期性纳米层状结构。常见的一维光子晶体的制作方法是自上而下的方法,如光刻法,共挤出和层积法等,尽管通过这些方法可以得到周期性层状结构,但是往往需要特殊的装置,过程复杂,成本较高。因此发明一种简单可行,低成本的技术来制备一维光子晶体材料尤为重要。
近年来,利用嵌段聚合物自组装制备光子晶体成为研究的热点之一,嵌段共聚物中不同的组份在自组装过程中可以产生明显的微相分离,从而得到有序的纳米结构,例如囊泡,胶束,管,球形,圆柱形,层状,六方晶形等结构。相比于传统一维光子晶体的制造方法,该技术具有制备简单,成本较低的优势。但是自组装过程也存在着一些挑战,如分子链的链缠结行为,这种聚合物固有的性质可以大大地影响自组装过程和效果,尤其是在高分子量条件下,较难自组装成长程有序的纳米结构。树枝形嵌段共聚物因其单分散刚性侧链结构的存在,可以极大的降低分子链的链缠结行为。
发明内容
本发明的目的是针对现有技术中存在的技术缺陷,而提供一种新型的树枝状嵌段共聚物(PNAM-b-PNBzM)及其制备方法,并且所述树枝状嵌段共聚物通过简单自组装得到了长程有序的大尺寸层状纳米结构,有望在光学涂料等方面得到实际应用。
为实现本发明的目的所采用的技术方案是:
一种树枝状嵌段共聚物,其结构式为:
其中:A为正癸烷基,Bz为苄基,m为NAM的聚合度,m=100-1000,n为NBzM的聚合度,n=100-1000,主链聚合度为200-2000。
优选的,m=n。
本发明的另一方面,还包括所述树枝状嵌段共聚物的合成方法,包括以下步骤:
取带有烷基链的降冰片烯单体NAM溶解到有机溶剂中,加入G-3催化剂,在20-40℃下搅拌反应,以使单体NAM均聚,然后将溶解好的带有苄苯结构的降冰片烯单体NBzM的加入到上述反应液中继续反应,以实现NAM、NBzM的共聚,反应完成后加入终止剂淬灭反应,最终得到目标树枝形嵌段共聚物(PNAM-b-PNBzM)。
优选的,所述G-3、NAM和NBzM的摩尔比为:1:(100-1000):(100-1000)。
其中:NAM的结构式为:
NBzM的结构式为:
(PNAM-b-PNBzM)的结构式为:
本发明的另一方面,还包括所述树枝状嵌段共聚物的自组装物。
优选的,所述NAM的聚合度m为280-320、NBzM的聚合度n为280-320时,所述自组装物呈蓝色,优选m=300,n=300。
优选的,所述NAM的聚合度m为380-420、NBzM的聚合度n为380-420时,所述自组装物呈黄绿色,优选m=400,n=400。
优选的,所述NAM的聚合度m为480-520、NBzM的聚合度n为480-520时,所述自组装物呈橙色,优选m=500,n=500。
本发明的另一方面,还包括所述树枝状嵌段共聚物的自组装方法,包括以下步骤:将合成的树枝形嵌段共聚物(PNAM-b-PNBzM)均匀分散在四氢呋喃(THF)中,将混合液涂布在玻璃片上,室温下溶剂挥发以后得到聚合物薄膜。
优选的,所述涂布方式包括滴凃、利用毛笔蘸取书写或利用喷枪喷涂。
优选的,所述自组装方法还包括淬火步骤,具体为取所述的聚合物薄膜置于DCM或THF氛围中,在20-40℃条件下保持24-36h。
本发明的另一方面,还包括所述树枝状嵌段共聚物的自组装方法在调控聚合产物颜色上的应用。
优选的,所述NAM的聚合度m为280-320、NBzM的聚合度n为280-320时,所述自组装物呈蓝色,优选m=300,n=300;所述NAM的聚合度m为380-420、NBzM的聚合度n为380-420时,所述自组装物呈黄绿色,优选m=400,n=400;所述NAM的聚合度m为480-520、NBzM的聚合度n为480-520时,所述自组装物呈橙色,优选m=500,n=500。
本发明的另一方面,还包括所述自组装物在制备一维光子晶体材料、颜料和染料上的应用。
与现有技术相比,本发明的有益效果是:
本发明的树枝形嵌段共聚物的合成是通过一些列活性可控的开环易位聚合(ROMP)方法得到的,通过简单的溶剂挥发自组装,得到了一系列具有长程有序的大尺寸层状结构的光子晶体材料。通过反射光谱测试我们得到了高反射率且带宽较窄的反射图谱,这使得发明的光子晶体材料可以应用于更加精密的光学器件方面。更重要的是我们首次得到了主反射波长在1250nm的光子晶体材料,这已经达到了通讯波段,大大地提高了光子晶体的应用前景。此外通过简单溶剂挥发自组装得到的反射不同颜色的光子晶体材料,有望代替传统的颜料和染料,具有极大的实用价值。
附图说明
图1是树枝状嵌段共聚物(PNAM-b-PNBzM)的合成线路。
图2是实施例1树枝状嵌段共聚物(PNAM-b-PNBzM)的核磁图谱。
图3是实施例2所合成的BCP1-BCP6的溶剂挥发自组装图片。
图4是实施例2BCP1-BCP6溶剂挥发自组装后的反射光谱图。
图5是实施例3毛笔书写自组装后图片。
具体实施方式
以下结合附图和具体实施例对本发明作进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
实施例1
树枝形嵌段共聚物BCP1-6的制备方法:其制备路线如图1所示,
BCP1-6的结构通式为:
在10mL聚合瓶中加入NAM(160mg,0.11mmol),1mL干燥二氯甲烷,加入G-3(0.48mg,5.5×10-3mmol)的二氯甲烷溶液0.1mL,在常温下搅拌反应30分钟,然后将1.1mL含有NBzM(120mg,0.11mmol)的二氯甲烷的溶液加入到上述反应液中继续反应1小时,整个加料和反应过程均在手套箱中进行。反应完成后加入1mL乙烯基乙醚淬灭反应。移出手套箱,在无水甲醇中沉淀,离心,真空干燥得到主链聚合度为400的树枝形嵌段共聚物BCP1,其中NAM的聚合度为200,NBzM的聚合度为200。
在10mL聚合瓶中加入NAM(160mg,0.11mmol),1mL干燥二氯甲烷,加入G-3(0.32mg,3.7×10-3mmol)的二氯甲烷溶液0.1mL,在常温下搅拌反应30分钟,然后将1.1mL含有NBzM(120mg,0.11mmol)的二氯甲烷的溶液加入到上述反应液中继续反应1小时,整个加料和反应过程均在手套箱中进行。反应完成后加入1mL乙烯基乙醚淬灭反应。移出手套箱,在无水甲醇中沉淀,离心,真空干燥得到主链聚合度为600的树枝形嵌段共聚物BCP2,其中NAM的聚合度为300,NBzM的聚合度为300。
在10mL聚合瓶中加入NAM(160mg,0.11mmol),1mL干燥二氯甲烷,加入G-3(0.24mg,2.7×10-3mmol)的二氯甲烷溶液0.1mL,在常温下搅拌反应30分钟,然后将1.1mL含有NBzM(120mg,0.11mmol)的二氯甲烷的溶液加入到上述反应液中继续反应1小时,整个加料和反应过程均在手套箱中进行。反应完成后加入1mL乙烯基乙醚淬灭反应。移出手套箱,在无水甲醇中沉淀,离心,真空干燥得到主链聚合度为800的树枝形嵌段共聚物BCP3,其中NAM的聚合度为400,NBzM的聚合度为400。
在10mL聚合瓶中加入NAM(160mg,0.11mmol),1mL干燥二氯甲烷,加入G-3(0.19mg,2.2×10-3mmol)的二氯甲烷溶液0.1mL,在常温下搅拌反应30分钟,然后将1.1mL含有NBzM(120mg,0.11mmol)的二氯甲烷的溶液加入到上述反应液中继续反应1小时,整个加料和反应过程均在手套箱中进行。反应完成后加入1mL乙烯基乙醚淬灭反应。移出手套箱,在无水甲醇中沉淀,离心,真空干燥得到主链聚合度为1000的树枝形嵌段共聚物BCP4,其中NAM的聚合度为500,NBzM的聚合度为500。
在10mL聚合瓶中加入NAM(160mg,0.11mmol),1mL干燥二氯甲烷,加入G-3(0.17mg,2.0×10-3mmol)的二氯甲烷溶液0.1mL,在常温下搅拌反应30分钟,然后将1.1mL含有NBzM(120mg,0.11mmol)的二氯甲烷的溶液加入到上述反应液中继续反应1小时,整个加料和反应过程均在手套箱中进行。反应完成后加入1mL乙烯基乙醚淬灭反应。移出手套箱,在无水甲醇中沉淀,离心,真空干燥得到主链聚合度为1100的树枝形嵌段共聚物BCP5,其中NAM的聚合度为550,NBzM的聚合度为550。
在10mL聚合瓶中加入NAM(160mg,0.11mmol),1mL干燥二氯甲烷,加入G-3(0.15mg,1.7×10-3mmol)的二氯甲烷溶液0.1mL,在常温下搅拌反应30分钟,然后将1.1mL含有NBzM(120mg,0.11mmol)的二氯甲烷的溶液加入到上述反应液中继续反应1小时,整个加料和反应过程均在手套箱中进行。反应完成后加入1mL乙烯基乙醚淬灭反应。移出手套箱,在无水甲醇中沉淀,离心,真空干燥得到主链聚合度为1300的树枝形嵌段共聚物BCP6,,其中NAM的聚合度为650,NBzM的聚合度为650。
如图2所示为嵌段聚合物BCP1聚合度为400的核磁氢谱图,可知所有单体已经完全转化,且各个峰都可以很好的得到归属。
实施例2
所合成的系列树枝形嵌段共聚物(BCP1-BCP6)溶剂挥发自组装:
将合成的树枝形嵌段共聚物(BCP1-BCP6)分别配制10mg/mL的四氢呋喃溶液,将混合液逐滴滴涂在洁净的水平玻璃片上,待溶剂挥发完全后得到6种不同的聚合物薄膜,即为制成的一维光子晶体材料。如图3所示为BCP1-BCP6自组装完成后的图片,表现出了明显的光反射现象。图4为BCP1-BCP6自组装完成后的反射光谱图,表明发明的树枝状嵌段共聚物发生了较为理想的自组装,得到了高反射率且带宽分布较窄的反射光谱。
实施例3
所合成的系列树枝形嵌段共聚物(BCP1-BCP6)毛笔书写自组装:
将合成的树枝形嵌段共聚物(BCP1-BCP6)分别配制15mg/mL的四氢呋喃溶液,用洁净的毛笔蘸取聚合物溶液,在洁净的水平玻璃基质上书写,随着书写得进行,溶剂逐渐挥发完全,最终得到有望代替染料的一维光子晶体材料。如图4所示为BCP2-BCP4毛笔书写自组装完成后的图片,表现出了明显的光反射现象。
实施例4
所合成的系列树枝形嵌段共聚物(BCP1-BCP6)喷枪喷涂自组装:
将合成的树枝形嵌段共聚物(BCP1-BCP6)分别配制15mg/mL的四氢呋喃溶液,利用洁净的气泵喷枪(口径0.3-0.5mm)将聚合物溶液均匀的喷涂在玻璃基质表面,随着喷涂的进行,溶剂迅速挥发,自组装成一维光子晶体材料。
实施例5
所合成的系列树枝形嵌段共聚物(BCP1-BCP6)溶剂淬火自组装:
将自组装得到的薄膜放置于盛放有THF溶液的玻璃腔内,保持腔内THF氛围饱和状态,在室温条件下保持24h,使得链段得到充分运动。
以上所述仅是本发明的优选实施方式,应当指出的是,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (17)
2.如权利要求1所述的树枝状嵌段共聚物,其特征在于,m=n。
4.如权利要求3所述的树枝状嵌段共聚物的合成方法,其特征在于,所述G-3、NAM和NBzM的摩尔比为:1:(100-1000):(100-1000)。
5.如权利要求1所述的树枝状嵌段共聚物的自组装方法,其特征在于,包括以下步骤:
将合成的树枝形嵌段共聚物(PNAM-b-PNBzM)均匀分散在四氢呋喃中,将混合液涂布在玻璃片上,室温下溶剂挥发以后得到聚合物薄膜。
6.如权利要求5所述的自组装方法,其特征在于,所述涂布方式包括滴凃、利用毛笔蘸取书写或利用喷枪喷涂。
7.如权利要求5所述的自组装方法,其特征在于,所述自组装方法还包括淬火步骤,具体为取所述的聚合物薄膜置于DCM或四氢呋喃氛围中,在20-40℃条件下保持24-36h。
8.如权利要求5所述的树枝状嵌段共聚物的自组装方法在调控聚合产物颜色上的应用,其特征在于,所述NAM的聚合度m为280-320、NBzM的聚合度n为280-320时,自组装物呈蓝色;所述NAM的聚合度m为380-420、NBzM的聚合度n为380-420时,自组装物呈黄绿色;所述NAM的聚合度m为480-520、NBzM的聚合度n为480-520时,自组装物呈橙色。
9.如权利要求8所述的树枝状嵌段共聚物的自组装方法在调控聚合产物颜色上的应用,其特征在于,所述NAM的聚合度m=300、NBzM的聚合度n=300时,所述自组装物呈蓝色;所述NAM的聚合度m=400、NBzM的聚合度n=400时,所述自组装物呈黄绿色;所述NAM的聚合度m=500、NBzM的聚合度n=500时,所述自组装物呈橙色。
10.如权利要求6所述的树枝状嵌段共聚物的自组装方法制备得到的自组装物。
11.如权利要求10所述的自组装物,其特征在于:所述NAM的聚合度m为280-320、NBzM的聚合度n为280-320时,所述自组装物呈蓝色。
12.如权利要求11所述的自组装物,其特征在于:所述NAM的聚合度m=300、NBzM的聚合度n=300时,所述自组装物呈蓝色。
13.如权利要求10所述的自组装物,其特征在于:所述NAM的聚合度m为380-420、NBzM的聚合度n为380-420时,所述自组装物呈黄绿色。
14.如权利要求13所述的自组装物,其特征在于:所述NAM的聚合度m=400、NBzM的聚合度n=400时,所述自组装物呈黄绿色。
15.如权利要求10所述的自组装物,其特征在于:所述NAM的聚合度m为480-520、NBzM的聚合度n为480-520时,所述自组装物呈橙色。
16.如权利要求15所述的自组装物,其特征在于:所述NAM的聚合度m=500、NBzM的聚合度n=500时,所述自组装物呈橙色。
17.如权利要求10所述的自组装物在制备一维光子晶体材料、颜料和染料上的应用。
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