CN107057089B - 一种光-温度双重响应的高分子凝胶及其制备方法 - Google Patents
一种光-温度双重响应的高分子凝胶及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种光‑温度双重响应的高分子凝胶。所述高分子凝胶由两组分组成,组分一为侧链型偶氮苯聚合物,组分二为有机溶剂;两组分通过加热法制备成高分子凝胶,此凝胶除了有温敏性之外,由于合成的聚合物含有偶氮苯基团,所以具有良好的光响应,在紫外光下发生凝胶解缔,在可见光的照射下可以迅速恢复凝胶结构。本发明制备过程简单,成本低廉,不需要特殊设备,能制备多种有机溶剂凝胶和多种混合的有机溶剂凝胶,适用于工业化生产。制备出的有机凝胶有着优良的热稳定以及光响应性能,在一些光敏光控开关领域有着可观的前景。
Description
技术领域
本发明涉及超分子技术领域,具体涉及一种侧链型偶氮苯聚合物与有机溶剂形成的光-温度双重响应的高分子凝胶材料及其制备方法。
背景技术
凝胶因子在有机溶剂中通过非共价键自组装形成一种三维网络空间结构,在网络结构中分散着有机溶剂的液体,这种特殊的分散体系称为有机凝胶。近些年来,对于智能响应凝胶材料的研究越发热门,这类凝胶材料对于外界的刺激(例如温度,PH值,光,电,磁等)能够做出迅速的响应,在其中光响应有着准确,响应快的特点,备受科研工作者的青睐。而在光响应凝胶的研究过程中,科研工作者发现其中的偶氮苯类凝胶因子对于光的响应十分优越且迅速。偶氮苯类化合物对于光的响应主要是由于在不同光波长下其分子内的-N=N-基团会发生由trans→cis或cis→trans的构型转变。故将偶氮苯基团引入高分子凝胶体系中制备出具有光响应和温度响应的凝胶。
复旦大学的中国专利(CN101870675A)将凝胶化合物与二胺或多胺分别按所含羧酸基团和伯胺基团以1:1当量进行混合,在有机溶剂中加热至溶解状态,冷却至室温后形成凝胶,该凝胶化合物是以萘酐为发色团的烷链羧酸。这种凝胶化合物虽然合成简单,但是化合物不具有凝胶的特性,不能单独在有机溶剂里凝胶,只能与二胺或多胺混合之后的混合物才具有凝胶性质,应用非常局限,不能满足工业化生产的需求。
吉利大学的中国专利(CN102702020A)公开了两种偶氮基团取代的Na-(4-氧代-4-氨基)丁酰基-N-十二烷氧基-L-缬氨酰胺小分子凝胶因子,其制备方法为将小分子化合物与有机溶剂共混之后加热完全溶解,冷却至室温得凝胶。此类凝胶因子可以使多种有机溶剂凝胶,但是,小分子化合物的制备过程长且繁琐,在实际操作的过程中困难大,成本高,难以实现大规模的工业化生产。
Liu等(Liu Z X,Feng Y,Yan Z C,et al.Multistimuli responsive dendriticorganogels based on azobenzene-containing poly(aryl ether)dendron[J].Chem.Mater.,2012,24(19):3751-3757.)合成了一种超支化的凝胶因子,该凝胶因子巧妙地将偶氮苯基团引入到超支化分子的支化链上,因此在紫外或可见光的作用下,整个树枝状分子实现了异构化,从而实现凝胶-溶胶的转换,从其紫外可见吸收光谱可以看出,在浓度为2.86×10-6mol/L的甲苯溶液中反式结构转变为顺式结构的UV响应的时间为35s,从顺式结构转变为反式结构的可见光的响应时间为8min(1mm光程);Kato等(Moriyama,M.;Mizoshiita,N.;Yokota,T.;Kishimoto,K.;Kato,T.Adv.Mater.2003,15,1335.)设计合成了含有偶氮苯的手性凝胶因子,研究发现在环己烷中形成橙色透明凝胶,在紫外光照射下凝胶转变成橙红色溶液,此溶液再用可见光照射重新形成凝胶,这种相转变可以重复的进行;等(S.;Frkanec,L.;M.Eur.J.Org.Chem.2006,1323.)合成了一系列的4位或者4,4'位上连有一个或者两个草酰胺的顺式或者反式的二苯基乙烯衍生物,研究发现,在室温下此化合物的顺式异构体的乙醇溶液用高压汞灯(250nm<λ<520nm)照射,会转变成不透明的凝胶,其光照形成凝胶需要60min左右,且随着时间的推移,凝胶因子会从体系中结晶出来,加热凝胶或者晶体沉淀又得到溶液,冷却后重新形成凝胶;贾欣茹等(Ji,Y.;Kuang,G.C.;Jia,X.R.;Chen,E.Q.;Wang,B.B.;Li,W.S.;Wei,Y.;Lei,J.Chem.Commun.2007,4233.)将偶氮苯连接到树枝状分子上形成凝胶因子,发现该化合物形成的凝胶是光致可逆的有机凝胶。用λ=365nm的光照射,室温下凝胶逐渐的转变成清澈的溶液,自然光照射此溶液又转变成凝胶;黄春辉(Zhou,Y.F.;Xu,M.;Yi,T.;Xiao,S.Z.;Zhou,Z.G.;Li,F.Y.;Huang,C.H.Langmuir 2007,23,202.)研究组设计合成了光响应的边缘带有三个偶氮苯基团的化合物,研究发现,此类化合物是很好的凝胶因子,能使很多有机溶剂凝胶化,所形成的凝胶具有光响应。此化合物在三氯甲烷中形成的凝胶相转化温度为58℃,紫外光照射,凝胶变成溶液,在室温下可见光照射,溶液又可直接转变成凝胶,从其紫外可见吸收光谱可以看出,在浓度为1×10-5mol/L的二氧六环溶液中反式结构转变为顺式结构的UV响应的时间为8min,从顺式结构转变为反式结构的可见光的响应时间为30min(1mm光程);以上几种报道的小分子凝胶因子都有光响应,但是,小分子凝胶因子都有着凝胶解缔温度不高,热稳定性能不好的缺陷,会束缚其在生产生活中的应用,小分子凝胶因子由于其本身分子间作用力的原因,其光响应的速度会变得迟缓,而本发明制备的凝胶在光照下可以拥有迅速的光响应,同时又能在较高的温度下保持稳定的凝胶结构。
发明内容
针对现有凝胶的光响应时间容易受分子间作用力干扰、热稳定性能差等问题,本发明提供一种侧链型偶氮苯类的光-温度双重响应的高分子凝胶及其制备方法,具有制备成本低,工艺流程简单,热稳定性能优异,光响应迅速等诸多优点。
为实现本发明的目的,总体发明构思为:通过自由基聚合合成出一定分子量的侧链型偶氮苯聚合物,再将此聚合物按照一定的质量比加入到有机溶剂或混合有机溶剂中,加热搅拌至聚合物完全溶解至透明,放入冰箱或室温冷却形成凝胶。通过紫外光的照射会使凝胶发生光致变色且发生凝胶-溶胶的转变,在可见光的照射下又能使凝胶结构恢复。
本发明是通过如下方式实现的:
一种光-温度双重响应的高分子凝胶,包含按质量百分比计的如下组分:有机溶剂或混合溶剂80~99.5%,侧链型偶氮苯聚合物0.5~20%。
进一步地,所述的有机溶剂为烷烃、胺或酯中的一种或两种以上。
进一步地,所述的烷烃优选正庚烷或环己烷;所述的胺优选三乙胺或正丁胺;所述的酯优选乙酸丁酯。
进一步地,所述的混合溶剂优选丙酮和石油醚,石油醚和二氯甲烷,乙酸丁酯和石油醚,乙酸丁酯和二氯甲烷,环己烷和丙酮中的一种。
进一步地,所述的侧链型偶氮苯聚合物,其化学结构式如I所示:
式I中,R1为氢和甲基的一种;M为或无取代基(即不存在M而直接相连),其中m为1~18之间的整数;R2为烷氧基。
上述的光-温度双重响应型高分子凝胶的制备方法,包括如下步骤:
(1)按质量百分比称取有机溶剂或混合溶剂80~99.5%、侧链型偶氮苯聚合物0.5~20%;
(2)将步骤(1)得到的侧链型偶氮苯聚合物加入到有机溶剂或混合溶剂中,加热搅拌至完全溶解成透明溶液;
(3)将步骤(2)得到的溶液静置自然冷却,得到高分子凝胶。
以响应性能和恢复性能考察上述高分子凝胶的性能,用于上述高分子凝胶响应的紫外光的波长为365nm,光强为30mW/cm2,用于恢复的为可见光,光强为30mW/cm2。
与现有技术相比,本发明的有益效果在于:
(1)本发明是由聚合物的凝胶因子制备的凝胶,制备的凝胶热稳定性能优越,光响应的性能非常灵敏。
(2)光响应的基团为偶氮苯基团,对于紫外光的响应十分迅速,在室温下转变为透明的溶液之后在可见光的照射下又可以恢复凝胶结构。
(3)在聚合物的质量分数为0.5%左右即可凝胶,制备成本低廉且聚合物可回收。
(4)本发明的制备工艺简单,制备条件易于控制,所需的试剂皆为常用试剂,制备成本较低,具有良好的应用性能和广阔的应用前景。
(5)本发明的溶剂适用范围很广,可以使用混合溶剂如丙酮和石油醚,石油醚和二氯甲烷,乙酸丁酯和石油醚,乙酸丁酯和二氯甲烷,环己烷和丙酮等。
附图说明
图1为紫外光-温度双重响应凝胶转变示意图。
图2为PMAzo-18C在环己烷里UV响应时间(1.5×10-5M 1mm光程)。
图3为PMAzo-18C在环己烷里VIS响应时间(1.5×10-5M 1mm光程)。
图4为PMAzo-14C在环己烷里UV响应时间(1.5×10-5M 1mm光程)。
图5为PMAzo-14C在环己烷里VIS响应时间(1.5×10-5M 1mm光程)。
具体实施方式
下面结合实施例对本发明做进一步详细说明,但本发明并不限于此。
凝胶解缔温度(TD)和凝胶-溶胶温度(TGS)测试采用试管倾斜法:将装有凝胶材料的试管底部朝下插入透明油浴中,再将油浴以2℃/min的速度升温。当升温到一定温度时,将试管倾斜,若凝胶恰好可以流动,则确定该温度为凝胶聚集体结构解缔温度(TD)。当出现TD后继续升温,并将凝胶全部溶解为液体时的温度确定为凝胶—溶胶相转变温度(TGS)。
实施例1
将1g单体4’4-十八烷氧偶氮苯基甲基丙烯酸甲酯(MAzo-18),0.314mg引发剂偶氮二异丁腈和3.4g氯苯溶液一起加入到干净的玻璃试管中,经过冷冻-抽真空-通氮气循环三次以后封管。真空封管后,将聚合试管放入70℃得恒温油浴锅中,一段时间后,体系粘度增加。取出玻璃管,放入冰水浴冷却,使聚合停止。打开玻璃管,用12ml四氢呋喃(THF)稀释其聚合物粘度,然后在500ml丙酮中沉淀,加热至微沸之后,趁热抽滤,收集聚合物,干燥即得所需侧链型偶氮苯聚合物PMAzo-18,结构式如下:
称取正庚烷0.95g与25mm×40mm样品瓶中,然后向其加入0.05gPMAzo-18,使PMAzo-18的质量分数为5%,两者共混加热至聚合物完全溶解,体系呈现透明,自然冷却至室温即得光-温度双重响应型高分子凝胶,凝胶解缔温度(TD)为76℃,凝胶—溶胶相转变温度(TGS)为80℃。
实施例2
侧链型偶氮苯聚合物同实施例1
称取乙酸丁酯0.95g与25mm×40mm样品瓶中,然后向其加入0.05g PMAzo-18,使PMAzo-18的质量分数为5%,两者共混加热至聚合物完全溶解,体系呈现透明,自然冷却至室温即得光-温度双重响应型高分子凝胶,凝胶解缔温度(TD)为50℃,凝胶—溶胶相转变温度(TGS)为54℃。
实施例3
侧链型偶氮苯聚合物同实施例1
称取三乙胺0.95g与25mm×40mm样品瓶中,然后向其加入0.05g PMAzo-18,使PMAzo-18质量分数为5%,两者共混加热至聚合物完全溶解,体系呈现透明,自然冷却至室温即得光-温度双重响应型高分子凝胶,凝胶解缔温度(TD)为37℃,凝胶—溶胶相转变温度(TGS)为40℃。
实施例4
将1g单体4’4-十四烷氧偶氮苯基甲基丙烯酸甲酯(MAzo-14),0.314mg引发剂偶氮二异丁腈和3.4g氯苯溶液一起加入到干净的玻璃试管中,经过冷冻-抽真空-通氮气循环三次以后封管。真空封管后,将聚合试管放入70℃得恒温油浴锅中,一段时间后,体系粘度增加。取出玻璃管,放入冰水浴冷却,使聚合停止。打开玻璃管,用12mlTHF稀释其聚合物粘度,然后在500ml丙酮中沉淀,加热至微沸之后,趁热抽滤,收集聚合物,干燥即得所需聚合物PMAzo-14,结构式如下:
称取正庚烷0.95g与25mm×40mm样品瓶中,然后向其加入0.05g PMAzo-14,使PMAzo-14的质量分数为5%,两者共混加热至聚合物完全溶解,体系呈现透明,自然冷却至室温即得光-温度双重响应型高分子凝胶,凝胶解缔温度(TD)为100℃,凝胶—溶胶相转变温度(TGS)为102℃。
实施例5
侧链型偶氮苯聚合物同实施例4
称取乙酸丁酯0.95g与25mm×40mm样品瓶中,然后向其加入0.05g PMAzo-14,使PMAzo-14的质量分数为5%,两者共混加热至聚合物完全溶解,体系呈现透明,自然冷却至室温即得光-温度双重响应型高分子凝胶,凝胶解缔温度(TD)为38℃,凝胶—溶胶相转变温度(TGS)为38℃。
实施例6
侧链型偶氮苯聚合物同实施例4
称取三乙胺0.95g与25mm×40mm样品瓶中,然后向其加入0.05g PMAzo-14,使PMAzo-14的质量分数为5%,两者共混加热至聚合物完全溶解,体系呈现透明,自然冷却至室温即得光-温度双重响应型高分子凝胶凝胶解缔温度(TD)为36℃,凝胶—溶胶相转变温度(TGS)为40℃。
实施例7
将1g单体4’4-十八烷氧偶氮苯基甲基丙烯酸己酯(M6Azo-18),0.314mg引发剂偶氮二异丁腈和3.4g氯苯溶液一起加入到干净的玻璃试管中,经过冷冻-抽真空-通氮气循环三次以后封管。真空封管后,将聚合试管放入70℃得恒温油浴锅中,一段时间后,体系粘度增加。取出玻璃管,放入冰水浴冷却,使聚合停止。打开玻璃管,用12mlTHF稀释其聚合物粘度,然后在500ml丙酮中沉淀,加热至微沸之后,趁热抽滤,收集聚合物,干燥即得所需聚合物PM6Azo-18,结构式如下:
称取正庚烷0.95g与25mm×40mm样品瓶中,然后向其加入0.05g PM6Azo-18,使PM6Azo-18的质量分数为5%,两者共混加热至聚合物完全溶解,体系呈现透明,自然冷却至室温即得光-温度双重响应型高分子凝胶,凝胶解缔温度(TD)为70℃,凝胶—溶胶相转变温度(TGS)为75℃。
实施例8
侧链型偶氮苯聚合物同实施例8
称取乙酸丁酯0.95g与25mm×40mm样品瓶中,然后向其加入0.05g PM6Azo-18,使PM6Azo-18的质量分数为5%,两者共混加热至聚合物完全溶解,体系呈现透明,自然冷却至室温即得光-温度双重响应型高分子凝胶,凝胶解缔温度(TD)为84℃,凝胶—溶胶相转变温度(TGS)为85℃。
实施例9
侧链型偶氮苯聚合物同实施例8
称取三乙胺0.95g与25mm×40mm样品瓶中,然后向其加入0.05g PMAzo-18,使PMAzo-18的质量分数为5%,两者共混加热至聚合物完全溶解,体系呈现透明,自然冷却至室温即得光-温度双重响应型高分子凝胶,凝胶解缔温度(TD)为60℃,凝胶—溶胶相转变温度(TGS)为65℃。
实施例10
将1g单体4’4-癸烷氧偶氮苯基甲基丙烯酸己酯(M6Azo-10),0.314mg引发剂偶氮二异丁腈和3.4g氯苯溶液一起加入到干净得玻璃试管中,经过冷冻-抽真空-通氮气循环三次以后封管。真空封管后,将聚合试管放入70℃得恒温油浴锅中,一段时间后,体系粘度增加。取出玻璃管,放入冰水浴冷却,使聚合停止。打开玻璃管,用12mlTHF稀释其聚合物粘度,然后在500ml丙酮中沉淀,加热至微沸之后,趁热抽滤,收集聚合物,干燥即得所需聚合物PM6Azo-10,结构式如下:
称取正庚烷0.95g与25mm×40mm样品瓶中,然后向其加入0.05g PM6Azo-10,使PM6Azo-10的质量分数为5%,两者共混加热至聚合物完全溶解,体系呈现透明,自然冷却至室温即得光-温度双重响应型高分子凝胶,凝胶解缔温度(TD)为90℃,凝胶—溶胶相转变温度(TGS)为92℃。
实施例11
侧链型偶氮苯聚合物同实施例11
称取乙酸丁酯0.95g与25mm×40mm样品瓶中,然后向其加入0.05g PM6Azo-10,使PM6Azo-10的质量分数为5%,两者共混加热至聚合物完全溶解,体系呈现透明,自然冷却至室温即得光-温度双重响应型高分子凝胶,凝胶解缔温度(TD)为73℃,凝胶—溶胶相转变温度(TGS)为75℃。
实施例12
侧链型偶氮苯聚合物同实施例11
称取三乙胺0.95g与25mm×40mm样品瓶中,然后向其加入0.05g PM6Azo-10,使PM6Azo-10的质量分数为5%,两者共混加热至聚合物完全溶解,体系呈现透明,自然冷却至室温即得光-温度双重响应型高分子凝胶。凝胶解缔温度(TD)为40℃,凝胶—溶胶相转变温度(TGS)为43℃。
实施例13
侧链型偶氮苯聚合物同实施例1
称取石油醚0.885g和二氯甲烷0.095g(9:1)与25mm×40mm样品瓶中,然后向其加入0.05g PMAzo-18,使PMAzo-18的质量分数为5%,两者共混加热至聚合物完全溶解,体系呈现透明,自然冷却至室温即得光-温度双重响应型高分子凝胶。凝胶解缔温度(TD)为44℃,凝胶—溶胶相转变温度(TGS)为45℃。
实施例14
侧链型偶氮苯聚合物同实施例1
称取乙酸丁酯0.665g和二氯甲烷0.285g(7:3)与25mm×40mm样品瓶中,然后向其加入0.05g PMAzo-18,使PMAzo-18的质量分数为5%,两者共混加热至聚合物完全溶解,体系呈现透明,自然冷却至室温即得光-温度双重响应型高分子凝胶。凝胶解缔温度(TD)为57℃,凝胶—溶胶相转变温度(TGS)为60℃。
实施例15
侧链型偶氮苯聚合物同实施例1
制备浓度为1.5×10-5M的PMAzo-18聚合物溶液,加入至光程为1mm的比色皿中,通过UV照射不同时间之后,分别放入紫外可见光谱仪中进行检测,待其曲线不再变化后,确定其响应时间为2s(见图2);将之前的溶液通过可见光照射不同时间,检测其曲线,待其曲线不再变化后确定其可见光的恢复时间为50s(见图3)。
实施例16
侧链型偶氮苯聚合物同实施例4
制备浓度为1.5×10-5M的PMAzo-10聚合物溶液,加入至光程为1mm的比色皿中,通过UV照射不同时间之后,分别放入紫外可见光谱仪中进行检测,待其曲线不再变化后,确定其响应时间为2s(见图4);将之前的溶液通过可见光照射不同时间,检测其曲线,待其曲线不再变化后确定其可见光的恢复时间为40s(见图5)。
Claims (2)
1.一种光-温度双重响应的高分子凝胶,其特征在于,包含按质量百分比计的如下组分:单一溶剂或混合溶剂80~95%,侧链型偶氮苯聚合物5~20%;
所述的侧链型偶氮苯聚合物,其化学结构式如式(I)所示:
(I)
式(I)中,R1为氢和甲基的一种;R2为烷氧基;
所述的单一溶剂为烷烃、胺或酯中的一种;
所述的烷烃为正庚烷或环己烷;所述的胺为三乙胺或正丁胺;所述的酯为乙酸丁酯;
所述的混合溶剂为丙酮和石油醚,石油醚和二氯甲烷,乙酸丁酯和石油醚,乙酸丁酯和二氯甲烷,环己烷和丙酮中的一种。
2.权利要求1所述的光-温度双重响应的高分子凝胶的制备方法,其特征在于,包括如下步骤:
(1)按质量百分比称取单一溶剂或混合溶剂80~95%、侧链型偶氮苯聚合物5~20%;
(2)将步骤(1)得到的侧链型偶氮苯聚合物加入到单一溶剂或混合溶剂中,加热搅拌至完全溶解成透明溶液;
(3)将步骤(2)得到的溶液静置自然冷却,得到高分子凝胶。
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CN1958626A (zh) * | 2006-11-01 | 2007-05-09 | 天津工业大学 | 一种紫外光响应型高分子水凝胶及其制备方法和用途 |
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