CN108467449B - 一种聚二乙炔基热致可逆变色复合材料及其制备方法 - Google Patents
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Abstract
本发明公开了一种聚二乙炔基热致可逆变色复合材料,是将10,12‑二十五碳二炔酸单体充分溶解于二甲亚砜‑水混合溶液中,再加入表面羟基化无机氧化物,然后将混合溶液于70~80℃下超声处理50~60 min,冷却至0~5℃,静置使其自组装孵育得到无色超分子溶液;然后将无色超分子溶液在紫外光照射下聚合,即得聚二乙炔/羟基化氧化物蓝色溶液。本发明通过制备表面多羟基的无机粒子与二乙炔酸分子端基的‑COOH之间的氢键作用,自组装后通过紫外光照聚合,得到普适性的聚二乙炔/羟基化无机物体系的热致可逆变色材料。由于不同的聚二乙炔/羟基化无机物复合材料具有不同的热致变色温度,因此可实现逆变色传感器的温度可控。
Description
技术领域
本发明涉及一种热致变色智能材料,尤其涉及一种聚二乙炔基热致可逆变色复合材料的制备方法,属于复合材料领域和智能材料领域。
背景技术
材料是人类生活和生产的支柱,主要将其分为功能材料和结构材料。功能材料注重的是其特殊的功能,结构材料注重其机械强度。智能材料是将功能材料和结构材料相结合,最终实现功能智能化和结构智能化。它能够通过自身的感知而获得外界环境变化,根据变化适时做出判断和处理,且发出指令、调节自身状态行为从而适应外界环境的变化,继而实现自检测、自诊断与校正、自修复等各种特殊功能。感应、反馈和响应是智能材料的三大基本要素。
聚二乙炔对外界环境刺激有灵敏的响应性,即在外界刺激下能发生蓝色到红色的转变,基于这种特殊的光学性质,人们将聚二乙炔制备成不同的形态作为传感器使用。但是,聚二乙炔在环境改变时只呈现不可逆的颜色变化,即当移出外界刺激时,其颜色不能从红色恢复至蓝色状态。这种不可逆的变色行为影响了聚二乙炔传感器的可重复使用性。
发明内容
本发明的目的是提供一种聚二乙炔基热致可逆变色复合材料的制备方法。
一、聚二乙炔基热致可逆变色复合材料的制备
本发明聚二乙炔基热致可逆变色复合材料的制备,是将10,12-二十五碳二炔酸单体充分溶解于二甲亚砜-水混合溶液中,再加入表面羟基化无机氧化物的水溶液,然后将混合溶液于70~80℃下超声50~60 min,冷却至0~5℃, 静置使其自组装孵育10~12 h,得到无色超分子溶液;然后将无色超分子溶液在紫外光照射下聚合,即得聚二乙炔/羟基化氧化物蓝色溶液。
所述10,12-二十五碳二炔酸单体的结构式为CH3-(CH2)11-C≡C-C≡C-(CH2)8-COOH。
所述二甲亚砜-水混合溶液中,二甲亚砜与水的体积比为1:9~1:8;10,12-二十五碳二炔酸单体与羟基化无机氧化物的质量比为4: 1~3: 1;混合溶液中,10,12-二十五碳二炔酸单体的浓度为0.5~0.6 mg/mL。
所述紫外光照射下聚合是在波长254 nm的紫外光下照射10~12 min。
所述表面羟基化无机氧化物的制备方法为:将无机氧化物粒子加入到H2O2/H2O混合溶液中,用硅酸钠调节溶液pH至9~11,于45~50℃反应5~7 h,过滤,固体用去离子水洗涤直洗出液为中性,真空干燥,即得表面羟基化无机氧化物。H2O2/H2O混合溶液中,H2O2与H2O的体积为1:2~1:3;所述无机氧化物为三氧化二铝、二氧化钛、二氧化硅。
二、热致变色性能测试
将复合材料在水浴25℃~80℃条件下进行10℃间隔的升温变化,检测聚二乙炔/羟基化无机氧化物复合材料水溶液颜色随温度的变化,并且测得在不同温度下三种复合材料的紫外-可见吸收光谱。
结果发现,聚二乙炔/羟基化无机氧化物复合材料在升温过程中,颜色均逐渐变浅,当温度达到热转变温度时,聚二乙炔/羟基化无机氧化物复合材料颜色完全变为红色,当降低温度至25℃后,颜色由红色恢复至初始的蓝色状态,因此,该聚二乙炔/羟基化无机氧化物复合材料具有由“蓝-红-蓝”的可逆变色性能,作为液态传感材料,能够进行明显的裸眼观察。而且不同的聚二乙炔/羟基化无机物复合材料具有不同的热致变色温度,有助于新型智能界面开关材料可控性的开发。
聚二乙炔/羟基化无及氧化物复合材料的紫外-可见吸收光谱中(图2、3、4),蓝色相的复合材料在650 nm处有明显的吸收峰;随着温度升高至热转变温度时,对应的紫外-可见吸收光谱中650 nm处吸收峰逐渐降低而543 nm处的吸收峰升高,并且伴有498 nm处肩峰的出现,对应聚二乙炔/羟基化无机氧化物复合材料的红色相。因此,本发明制备的聚二乙炔/羟基化无机氧化物复合材料为热致可逆变色智能材料,以此来实现热致可逆变色的传感器的应用。
本发明通过制备表面多羟基的无机粒子与二乙炔酸分子端基的-COOH之间的氢键作用,自组装后通过紫外光照聚合,得到普适性的聚二乙炔/羟基化无机物体系的热致可逆变色材料。由于不同的聚二乙炔/羟基化无机物复合材料具有不同的热致变色温度,因此可实现逆变色传感器的温度可控。
附图说明
图1为本发明实施的羟基化无机氧化物与未羟基化无机氧化物红外谱图;
图2为本发明实施例1制备的聚二乙炔/羟基化三氧化二铝复合材料在不同温度下的紫外-可见吸收光谱。
图3为本发明实施例2制备的聚二乙炔/羟基化二氧化钛复合材料在不同温度下的紫外-可见吸收光谱。
图4为本发明实施例3制备的聚二乙炔/羟基化二氧化硅复合材料在不同温度下的紫外-可见吸收光谱。
具体实施方式
下面通过具体实施例对本发明聚二乙炔基热致可逆变色复合材料的制备和性能做进一步说明。
实施例1、聚二乙炔/羟基三氧化二铝复合材料的制备
(1)羟基化三氧化二铝的制备:称取3 g三氧化二铝,加入到30 ml H2O2/H2O混合溶液中(H2O2:H2O=1:2~1:3v/v),加入硅酸钠调节溶液的pH至10,于50℃反应5~7 h,过滤,固体用去离子水洗涤数次,直至洗出液为中性,真空干燥,即得羟基化三氧化二铝;羟基化三氧化二铝和未羟基化三氧化二铝的红外图谱见图1。
(2)聚二乙炔/羟基化三氧化二铝复合材料的制备:称取12 g 10,12-二十五碳二炔酸单体,加入1 mL的二甲亚砜中搅拌使其充分溶解后加入9 mL去离子水中,超声分散10min后,加入上述3 mg羟基化三氧化二铝的去离子水溶液中,混合后于75~80℃下超声震荡50 min(二炔酸单体的浓度保持在0.5~0.6 mg/mL),冷却至室温,然后置于4℃下自组装孵育12 h,得到无色超分子溶液;将无色超分子溶液在254 nm的紫外灯下照射10 min使其聚合,得到蓝色溶液,即为聚二乙炔/羟基化三氧化二铝体系复合材料。
(3)复合材料的热致变色性能测试:将聚二乙炔/羟基化三氧化二铝体系复合材料在水浴25℃~80℃条件下进行10℃间隔的升温变化,检测复合材料水溶液颜色随温度变化,并且测得在不同温度下三种复合材料的紫外-可见吸收光谱。结果发现,聚二乙炔/羟基化三氧化二铝复合材料升温过程中,温度在50℃时颜色完全变为红色(热转变温度为50℃);当降低温度至25℃后,颜色由红色恢复至初始的蓝色状态。聚二乙炔/羟基化三氧化二铝复合材料的紫外-可见吸收光谱中(图2),蓝色相的复合材料在650 nm处有明显的吸收峰;随着温度的升高,50℃时对应的紫外-可见吸收光谱中650 nm处吸收峰逐渐降低而543 nm处的吸收峰升高,并且伴有498 nm处肩峰的出现,对应聚二乙炔/羟基化三氧化二铝复合材料红色相。
实施例2、聚二乙炔/羟基化二氧化钛复合材料的制备
(1)羟基化三氧化二铝的制备:称取3 g二氧化钛粒子,加入到30 ml H2O2/H2O混合溶液中(H2O2:H2O=1:2~1:3v/v),加入硅酸钠调节溶液的pH至10,于50℃反应5~7 h,过滤,固体用去离子水洗涤数次,直至洗出液为中性,真空干燥,即得羟基化二氧化钛;羟基化二氧化钛和未羟基化二氧化钛的红外图谱见图1。
(2)聚二乙炔/羟基化二氧化钛复合材料的制备:称取12 g 10,12-二十五碳二炔酸单体,加入1 mL的二甲亚砜中搅拌使其充分溶解后加入9 mL去离子水中,超声分散10min后,加入上述3 mg羟基化二氧化钛的去离子水溶液中,混合后于75~80℃下超声震荡50min(二炔酸单体的浓度保持在0.5~0.6 mg/mL),冷却至室温,然后置于4℃下自组装孵育12h,得到无色超分子溶液;将无色超分子溶液在254 nm的紫外灯下照射10 min使其聚合,得到蓝色溶液,即为聚二乙炔/羟基化二氧化钛体系复合材料。
(3)复合材料的热致变色性能测试:将聚二乙炔/羟基化二氧化钛系复合材料在水浴25℃~80℃条件下进行10℃间隔的升温变化,检测复合材料水溶液颜色随温度变化,并且测得在不同温度下三种复合材料的紫外-可见吸收光谱。结果发现,聚二乙炔/羟基化二氧化钛复合材料升温过程中,温度在60℃时颜色完全变为红色(热转变温度为60℃);当降低温度至25℃后,颜色由红色恢复至初始的蓝色状态。聚二乙炔/羟基化二氧化钛复合材料的紫外-可见吸收光谱中(图3),蓝色相的复合材料在650 nm处有明显的吸收峰;随着温度的升高,60℃时对应的紫外-可见吸收光谱中650 nm处吸收峰逐渐降低而543 nm处的吸收峰升高,并且伴有498 nm处肩峰的出现(相对聚二乙炔/羟基化三氧化二铝复合材料,其498nm处肩峰增长明显),对应聚二乙炔/羟基化二氧化钛复合材料的红色相。
实施例3、聚二乙炔/羟基化二氧化硅复合材料的制备
(1)羟基化二氧化硅的制备:称取3 g二氧化硅粒子,加入到30 ml H2O2/H2O混合溶液中(H2O2:H2O=1:2~1:3v/v),加入硅酸钠调节溶液的pH至10,于50℃反应5~7 h,过滤,固体用去离子水洗涤数次,直至洗出液为中性,真空干燥,即得羟基化二氧化硅;羟基化二氧化硅和未羟基化二氧化硅的红外图谱见图1。
(2)聚二乙炔/羟基化二氧化硅复合材料的制备:称取12g10,12-二十五碳二炔酸单体,加入1 mL的二甲亚砜中搅拌使其充分溶解后加入9 mL去离子水中,超声分散10 min后,加入上述3 mg羟基化二氧化硅的去离子水溶液中,混合后于75~80℃下超声震荡50min,(二炔酸单体的浓度保持在0.5~0.6 mg/mL)。冷却至室温,然后置于4℃下自组装孵育12 h,得到无色超分子溶液;将无色超分子溶液在254 nm的紫外灯下照射10 min使其聚合,得到蓝色溶液,即为聚二乙炔/羟基化二氧化硅体系复合材料。
(3)复合材料的热致变色性能测试:将聚二乙炔/羟基化二氧化硅系复合材料在水浴25℃~80℃条件下进行10℃间隔的升温变化,检测复合材料水溶液颜色随温度变化,并且测得在不同温度下复合材料的紫外-可见吸收光谱。结果发现,聚二乙炔/羟基化二氧化硅复合材料升温过程中,温度在70℃时颜色完全变为红色(热转变温度为70℃);当降低温度至25℃后,颜色由红色恢复至初始的蓝色状态。聚二乙炔/羟基化二氧化钛复合材料的紫外-可见吸收光谱中(图4),蓝色相的复合材料在650 nm处有明显的吸收峰;随着温度的升高,60℃时对应的紫外-可见吸收光谱中650 nm处吸收峰逐渐降低而543 nm处的吸收峰升高,并且伴有498 nm处肩峰的出现,对应聚二乙炔/羟基化二氧化硅复合材料的红色相。
Claims (9)
1.一种聚二乙炔基热致可逆变色复合材料的制备方法,是将10,12-二十五碳二炔酸单体充分溶解于二甲亚砜-水混合溶液中,再加入表面羟基化无机氧化物,然后将混合溶液于70~80℃下超声处理50~60 min,冷却至0~5℃,静置使其自组装孵育得到无色超分子溶液;然后将无色超分子溶液在紫外光照射下聚合,即得聚二乙炔/羟基化氧化物蓝色溶液;
所述表面羟基化无机氧化物的制备为:将无机氧化物粒子加入到H2O2/H2O混合溶液中,用硅酸钠调节溶液pH至9~11,于45~50℃反应5~7 h,过滤,固体用去离子水洗涤至 洗出液为中性,真空干燥,即得表面羟基化无机氧化物。
2.如权利要求1所述聚二乙炔基热致可逆变色复合材料的制备方法,其特征在于:10,12-二十五碳二炔酸单体的结构式为CH3-(CH2)11-C≡C-C≡C-(CH2)8-COOH。
3.如权利要求1所述聚二乙炔基热致可逆变色复合材料的制备方法,其特征在于:H2O2/H2O混合溶液中,H2O2与H2O的体积为1:2~1:3。
4.如权利要求1所述聚二乙炔基热致可逆变色复合材料的制备方法,其特征在于:所述无机氧化物为三氧化二铝、二氧化钛、二氧化硅。
5.如权利要求1所述聚二乙炔基热致可逆变色复合材料的制备方法,其特征在于:10,12-二十五碳二炔酸单体与羟基化无机氧化物的质量比为4:1~3:1。
6.如权利要求1所述聚二乙炔基热致可逆变色复合材料的制备方法,其特征在于:二甲亚砜-水混合溶液中,二甲亚砜与水的体积比为1:9~1:8。
7.如权利要求1所述聚二乙炔基热致可逆变色复合材料的制备方法,其特征在于:所述二甲亚砜-水混合溶液中,10,12-二十五碳二炔酸单体的浓度为0.5~0.6 mg/mL。
8.如权利要求1所述聚二乙炔基热致可逆变色复合材料的制备方法,其特征在于:所述静置自组装孵育时间为10~12 h。
9.如权利要求1所述聚二乙炔基热致可逆变色复合材料的制备方法,其特征在于:所述紫外光照射下聚合是在波长254 nm的紫外光下照射10~12 min。
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