CN110079042A - 一种双网络自主变形凝胶及其制备方法 - Google Patents
一种双网络自主变形凝胶及其制备方法 Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F265/10—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of amides or imides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
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- Materials For Medical Uses (AREA)
Abstract
本发明公开了一种双网络自主变形凝胶及其制备方法,其制备方法包括以下步骤,丙烯酰胺类单体、丙烯酸单体、交联剂和水溶性引发剂在乳液中发生自由基共聚合反应,再与甲基丙烯酸缩水甘油酯混合,得到表面含有乙烯基的微凝胶;将丙烯酰胺类单体、表面含有乙烯基的微凝胶和水溶性引发剂混合,注入模具,自由基共聚合反应结束后,冷冻干燥,得到聚合物网络凝胶制品;将表面含有乙烯基的微凝胶与丙烯酰胺类单体、乙烯基金属配合物单体、光引发剂的甲醇溶液混合,将聚合物网络凝胶制品的一端浸入到混合溶液中,静置,再在紫外光下聚合反应,交换溶剂,制得自主变形凝胶。通过调节单体种类等,改变动态变形模式,满足不同使用场景的需求。
Description
技术领域
本发明属于刺激响应变形材料技术领域,具体涉及一种动态模式可控的双网络自主变形凝胶及其制备方法。
背景技术
作为一种新型智能高分子材料,刺激响应变形材料能够响应外界刺激(如温度、pH值、光等),改变自身的几何形状。近年来,刺激响应变形材料(SRPs)因其拥有刺激响应种类多样、可实现远程控制、易加工成型和质地柔软等特性,成为高分子材料领域研究、开发及应用的一个新热点,尤其在制动器、传感器和微型机器人等领域具有广泛的潜在应用价值。
随着对刺激响应变形材料研究的深入,如何通过分子设计、结构设计及合成方法精确控制刺激响应变形材料的动态变形模式,已经成为刺激响应变形材料领域急需解决的问题。对于刺激响应变形材料来说,其动态变形模式决定于两个方面:其一,刺激源的本征属性;其二,材料的响应变形能力(如响应速度、变形幅度等)。目前已有的刺激响应变形材料,一般基于“开-关”刺激,材料的响应变形行为不可持续;刺激源与响应材料分立,不存在相互影响的关系,导致材料的动态变形模式不可控。
发明内容
本发明的目的之一在于:解决上述现有技术中的不足,提供一种变形动态模式可控的自主变形凝胶,基于化学振荡反应的自主、循环、可逆特征,实现凝胶的自主变形;依靠梯度结构双网络实现非对称弯曲-伸展变形;通过调节凝胶网络的密度,实现对于凝胶自主变形动态模式的精准控制。
本发明的目的之二在于,提供一种制备自主变形凝胶的制备方法,采用乳液自由基聚合构筑网络凝胶,再以网络凝胶作为基体,通过溶液自由基共聚合,在网络凝胶上构筑刺激响应网络,实现双网络结构。并且在构筑刺激响应网络结构的过程中,通过紫外光聚合反应快速固定自然渗透过程中形成的浓度梯度,得到具有浓度梯度的网络结构。通过调节单体种类、含量、交联剂含量等,改变网络凝胶制备的网络结构、自主变形动态模式等。
为了实现上述目的,本发明采用的技术方案为:一种双网络自主变形凝胶的制备方法,包括以下步骤,
(a)丙烯酰胺类单体、丙烯酸单体、交联剂和水溶性引发剂在乳液中发生自由基共聚合反应,得到表面含有羧基的微凝胶,将所述表面含有羧基的微凝胶与甲基丙烯酸缩水甘油酯混合,发生开环反应,得到表面含有乙烯基的微凝胶;
(b)将丙烯酰胺类单体、表面含有乙烯基的微凝胶和水溶性引发剂混合,注入模具,自由基共聚合反应结束后,冷冻干燥,得到聚合物网络凝胶制品;
(c)将所述步骤(a)制得的表面含有乙烯基的微凝胶与丙烯酰胺类单体、乙烯基金属配合物单体、光引发剂的甲醇溶液混合,得到混合溶液,将所述步骤(b)制备的聚合物网络凝胶制品的一端浸入到所述混合溶液中,静置,使所述混合溶液向所述聚合物网络凝胶制品的另一端扩散,再将浸润后的聚合物网络凝胶制品置于紫外光下,待光引发聚合反应结束后,采用浸润法交换所述聚合物网络凝胶制品的溶剂,制得自主变形凝胶。
在本申请中,步骤(a)和步骤(b)中,通过自由基共聚合反应,制备得到呈网络结构的聚合物,该聚合物作为构建凝胶的主体结构,通过改变该聚合物的网络结构(如密度、交联程度等),实现对凝胶自主变形的调节。在步骤(b)中,将步骤于(b)制备的凝胶制品浸入到含反应物的混合溶液,使得混合液呈梯度变化扩散到凝胶制品中,混合液在凝胶制品中呈梯度分布,在紫外光的作用下,迅速光固化,在凝胶制品中形成具有浓度梯度的刺激响应网络结构。由于在刺激响应网络结构中含有金属钌配合物,在化学振荡反应中,金属钌配合物处于还原态或氧化态,以使刺激响应网络倾向亲水状态或疏水状态,当为亲水状态时,凝胶处于溶胀状态,相反的凝胶处于消溶胀状态,通过化学振荡反应的周期变化,使得凝胶出现周期性的溶胀和消溶胀状态,实现凝胶的周期变形。在本申请制备的自主变形凝胶中,刺激源为凝胶结构的一部分,刺激源与响应结构为一个整体,相互影响,使凝胶的变形动态模式可控。
在本申请的步骤(c)中,通过扩散和紫外光固化相结合,使得刺激响应网络的浓度在凝胶制品中形成梯度变化,以实现凝胶制品的非对称弯曲变形。
进一步的,所述丙烯酰胺类单体为N-异丙基丙烯酰胺、丙烯酰胺、N-叔丁基丙烯酰胺中的一种。
进一步的,所述交联剂为N,N’-亚甲基双丙烯酰胺。
进一步的,在所述步骤(a)中,所述水溶性引发剂为过硫酸钾、过氧化二苯甲酰中的一种。
进一步的,在所述步骤(c)中,所述乙烯基金属配合物单体为二六氟磷酸(2,2’-联吡啶)-4-乙烯基-4’-甲基-2,2’-联吡啶、
二六氟磷酸4′-(4-丙烯氧基苯基)-2,2′:6′,2″-三联吡啶-4′-(4-甲基苯基)-2,2′:6′,2″-三联吡啶钌、
二六氟磷酸乙烯基二茂铁中的一种。
进一步的,在所述步骤(c)中,所述光引发剂为2-羟基-2-甲基-1-苯基丙酮、安息香双甲醚、
2-甲基-2-(4-吗啉基)-1-[4-(甲硫基)苯基]-1-丙酮、
2,4-二羟基二苯甲酮、硫代丙氧基硫杂蒽酮、
2-羟基-2-甲基-1-[4-(2-羟基乙氧基)苯基]-1-丙酮中的一种。
进一步的,在所述步骤(c)中,所述混合溶液中还包括二甲亚砜。
进一步的,在所述步骤(a)中,所述丙烯酰胺类单体、所述丙烯酸单体、所述交联剂和所述水溶性引发剂摩尔比为55:45:1:0.1;
在所述步骤(a)中,所述表面含有羧基的微凝胶和所述甲基丙烯酸缩水甘油酯的摩尔比为1:3;
在所述步骤(b)中,所述丙烯酰胺类单体、所述表面含有乙烯基的微凝胶和所述水溶性引发剂的摩尔比为90:10:0.1;
在所述步骤(c)中,所述表面含有乙烯基的微凝胶、所述丙烯酰胺类单体、所述乙烯基金属配合物单体、所述光引发剂的摩尔比为5:50:50:0.2。
进一步的,在所述步骤(c)中,所述浸润法为,将所述聚合物网络凝胶制品依次浸润在呈不同梯度浓度的甲醇水溶液中,直至所述聚合物网络凝胶制品中的甲醇全部浸出。
一种双网络自主变形凝胶,由上述双网络自主变形凝胶的制备方法制得。
由于采用了上述技术方案,本发明的有益效果是:
本发明的自主变形凝胶在化学振荡反应条件下自主变形动态模式可精准控制,可以通过改变基体网络凝胶的结构,以对凝胶的变形周期、变形幅度、变形延迟等进行调控,赋予了凝胶更加优异的自主变形性能,使其在制动器、传感器和微型机器人等领域具有更加广泛的潜在应用价值。
本发明采用乳液自由基聚合构筑网络凝胶,再以网络凝胶作为基体,通过溶液自由基共聚合,在网络凝胶上构筑刺激响应网络,实现双网络结构。并且在构筑刺激响应网络结构的过程中,通过紫外光聚合反应快速固定自然渗透过程中形成的浓度梯度,得到具有浓度梯度的网络结构,在化学振荡反应液中实现非对称弯曲变形。在实际的应用过程中,可通过调节单体种类、含量,交联剂含量等,改变聚合物网络凝胶制品的网络结构,进而改变凝胶的自主变形动态模式,以满足不同使用场景的需求。
附图说明
图1为本发明的实施例1中步骤(c)中浸润状态示意图;
图2为本发明的实施例1中凝胶变形状态示意图;
附图标记:1-式样,2-混合溶液,3-化学振荡溶液。
具体实施方式
实施例1:
在500mL圆底烧瓶中分别加入7.8g(29.8mmol)RuCl3·3H2O,9.36g(60.0mmol)2,2’-联吡啶,8.4g(2mmol)LiCl和50mL二甲基甲酰胺,加热回流9小时,冷却后加入250mL丙酮,保持0℃过夜,过滤得到紫红色滤液和暗绿色固体,去离子水冲洗固体三次,直到滤液呈淡绿色,随后用10mL乙醚冲洗三次,真空干燥,得到固体产物二氯二联吡啶钌;
将24.0mL的2.35mol/L正丁基锂(LDA)、8.0mL二异丙胺和30mL四氢呋喃混合于500mL三口烧瓶,搅拌15min后,将溶有10g 4,4’-二甲基-2,2’-联吡啶的250mL四氢呋喃经分液漏斗缓慢加入溶液中,溶液变为橘黄色。反应2小时后,向溶液中加入1.7g多聚甲醛,反应直到溶液颜色变为绿色,继续搅拌1小时后,停止反应,将烧瓶放入冷水中冷却,用乙醚萃取溶液。回收乙醚层,蒸发全部乙醚,得到产物4-羟乙基-4’-甲基-2,2’-联吡啶;
将溶有8.7g 4-羟乙基-4’-甲基-2,2’-联吡啶和30g五氧化二磷的二甲苯回流2小时后停止反应,将反应液静置冷却。当反应物冷却到5℃,向反应液中加入碎冰,去除过量的五氧化二磷,溶液开始分层,并且pH上升至5.0。用二氯甲烷萃取产物,然后蒸发溶剂即得到产物4-乙烯基-4’-甲基-2,2’-联吡啶;
将1.315g二氯二联吡啶钌,0.5009g 4-乙烯基-4’-甲基-2,2’-联吡啶,0.76g碳酸氢钠加入60mL甲醇/水(2:3w/w)混合液中,回流直到二氯二联吡啶钌反应完全为止。向溶液中加入3mol/L六氟磷酸铵溶液4mL,溶液产生红色沉淀,用丙酮/二氯甲烷重结晶得到产物二六氟磷酸(2,2’-联吡啶)-4-乙烯基-4’-甲基-2,2’-联吡啶;
自主变形凝胶的制备:
(a)将0.99g的N-异丙基丙烯酰胺、0.495g丙烯酸、0.015g的N,N’-亚甲基双丙烯酰胺、0.034g的过硫酸钾、50mL去离子水加入烧瓶中,机械搅拌5分钟,加入0.338g十二烷基硫酸钠,加热至60℃,反应5小时,机械搅拌300转/分钟。得到的表面含有羧基的微凝胶颗粒,再用水透析1周;
将0.8g甲基丙烯酸缩水甘油酯加入50mL的微凝胶悬浮液,加热到50℃,机械搅拌350转/分钟,反应8小时。得到的表面含有乙烯基的微凝胶颗粒悬浮液,再用乙醇透析一周;
(b)将0.56g的N-异丙基丙烯酰胺、22.6mg过硫酸钾加入到10mL的表面含有乙烯基的微凝胶颗粒悬浮液中,机械搅拌5分钟,加入20μL四甲基乙二胺,将混合液注入模具中,在0℃下反应6小时,脱模,将凝胶制成1mm*1mm*3mm的式样条,冷冻干燥备用;在本实施例中,选择在0℃下反应,低于异丙基丙烯酰胺的相转变温度,使得异丙基丙烯酰胺在水溶液中聚合,在聚合的过程中,异丙基丙烯酰胺分子链均匀的分布在溶液中。并且在实际的操作过程中发现,当温度在20℃下时,聚合反应较为迅速,导致在注模的过程中,还未将混合液全部注入到模具时,其余的混合液已交联,注模失败,而在0℃下,通过在混合液中加入四甲基乙二胺,适当的提高反应速率,方便注模。
(c)将0.4g的N-异丙基丙烯酰胺、0.2g的二六氟磷酸(2,2’-联吡啶)-4-乙烯基-4’-甲基-2,2’-联吡啶、30mg安息香双甲醚、1.5mL二甲亚砜加入至10mL表面含有乙烯基的微凝胶颗粒悬浮液,机械搅拌5分钟,制得混合容液;
将冷冻干燥的式样1的下部分浸入上述混合液2,如附图1所示,静置15分钟后,将式样1转移至365nm紫外灯下,光引发聚合30分钟,在光引发聚合后,将式样1依次浸入体积分数为25%、50%、75%、100%水-甲醇溶液(需说明的是,该体积分数指的是水的体积分数)中各2天,得到目标梯度结构双网络凝胶。
凝胶式样的变形动态模式测试:
将式样1放置在纯水中浸润,再将该试样1浸泡在含有0.89mol/L硝酸、84mmol/L溴酸钠、62.5mmol/L丙二酸的水溶液(化学振荡溶液3)中,在显微镜下观察式样的变形,凝胶式样1在溶液经过一定的诱导期后,式样1进行往复的弯曲-伸展运动,并记录相应的时间节点,得到本实施例的凝胶的自主变形延迟时间为:127秒,变形周期:103秒,弯曲变形幅度:18%。
实施例2:
本实施例与实施例1的不同之处在于,本实施例中,使用的乙烯基金属配合物为二六氟磷酸乙烯基二茂铁,使用的丙烯酰胺类单体为N-叔丁基丙烯酰胺,使用的光引发剂为2-羟基-2-甲基-1-苯基丙酮,使用的水溶性引发剂为过氧化二苯甲酰,在制备聚合物网络凝胶制品时N-叔丁基丙烯酰胺的用量为1.17g,其余的反应条件以及各反应物的用量均与实施例1的相同。
本实施例的式样的自主变形延迟时间为:250秒,变形周期:543秒,弯曲变形幅度:65%。
实施例3:
本实施例与实施例1的不同之处在于,本实施例中,使用的乙烯基金属配合物为二六氟磷酸4′-(4-丙烯氧基苯基)-2,2′:6′,2″-三联吡啶-4′-(4-甲基苯基)-2,2′:6′,2″-三联吡啶钌,使用的光引发剂为2-羟基-2-甲基-1-[4-(2-羟基乙氧基)苯基]-1-丙酮,在聚合物网络凝胶制品时N-异丙基丙烯酰胺的用量为2.3g,其余的反应条件以及各反应物的用量均与实施例1的相同。
本实施例的式样的自主变形延迟时间为:447秒,变形周期:1130秒,弯曲变形幅度92%。
实施例4:
本实施例与实施例1的不同之处在于,在本实施例中,用丙烯酰胺代替N-异丙基丙烯酰胺,其余的反应条件和用量与实施例的相同。
本实施例制备的凝胶式样的自主变形延迟时间为:218秒,变形周期:230秒,弯曲变形幅度34%。
需说明的是,在实施例1-4中,自主变形延迟时间指的是从凝胶式样放置在化学振荡反应溶液中开始至第一次变形的时间间隔,变形周期为从最伸展-弯曲-最伸展状态的时间间隔,弯曲变形幅度计算公式为:F=(Rs-Rb)/Rb*100%,其中Rs为式样完全伸展时的曲率半径,Rb为式样完全弯曲时的曲率半径。
从上述实施例1-4中可以得出,通过调节聚合物网络凝胶的单体种类、单体的浓度等,改变聚合物网络凝胶的密度,从而改变凝胶的动态变形模式,调控凝胶的动态变形模式,根据不同的需求设计不同的变形模式的凝胶。当聚合物网络凝胶的密度越低,变形的周期越短,变形幅度越小;当聚合物网络凝胶的密度越大,变形的周期越长,变形幅度越大。
Claims (9)
1.一种双网络自主变形凝胶的制备方法,其特征在于:包括以下步骤,
(a)丙烯酰胺类单体、丙烯酸单体、交联剂和水溶性引发剂在乳液中发生自由基共聚合反应,得到表面含有羧基的微凝胶,将所述表面含有羧基的微凝胶与甲基丙烯酸缩水甘油酯混合,发生开环反应,得到表面含有乙烯基的微凝胶;
(b)将丙烯酰胺类单体、所述步骤(a)制得的表面含有乙烯基的微凝胶和水溶性引发剂混合,注入模具,自由基共聚合反应结束后,冷冻干燥,得到聚合物网络凝胶制品;
(c)将所述步骤(a)制得的表面含有乙烯基的微凝胶与丙烯酰胺类单体、乙烯基金属配合物单体、光引发剂的甲醇溶液混合,得到混合溶液,将所述步骤(b)制备的聚合物网络凝胶制品的一端浸入到所述混合溶液中,静置,使所述混合溶液向所述聚合物网络凝胶制品的另一端扩散,再将浸润后的聚合物网络凝胶制品置于紫外光下,待光引发聚合反应结束后,采用浸润法交换所述聚合物网络凝胶制品的溶剂,制得自主变形凝胶。
2.根据权利要求1所述的双网络自主变形凝胶的制备方法,其特征在于:所述丙烯酰胺类单体为N-异丙基丙烯酰胺、丙烯酰胺、N-叔丁基丙烯酰胺中的一种。
3.根据权利要求1所述的双网络自主变形凝胶的制备方法,其特征在于:所述交联剂为N,N’-亚甲基双丙烯酰胺。
4.根据权利要求1所述的双网络自主变形凝胶的制备方法,其特征在于:在所述步骤(a)中,所述水溶性引发剂为过硫酸钾、过氧化二苯甲酰中的一种。
5.根据权利要求1所述的双网络自主变形凝胶的制备方法,其特征在于:在所述步骤(c)中,所述乙烯基金属配合物单体为二六氟磷酸(2,2’-联吡啶)-4-乙烯基-4’-甲基-2,2’-联吡啶、
二六氟磷酸4′-(4-丙烯氧基苯基)-2,2′:6′,2″-三联吡啶-4′-(4-甲基苯基)-2,2′:6′,2″-三联吡啶钌、
二六氟磷酸乙烯基二茂铁中的一种。
6.根据权利要求1所述的双网络自主变形凝胶的制备方法,其特征在于:在所述步骤(c)中,所述光引发剂为2-羟基-2-甲基-1-苯基丙酮、
安息香双甲醚、
2-甲基-2-(4-吗啉基)-1-[4-(甲硫基)苯基]-1-丙酮、
2,4-二羟基二苯甲酮、硫代丙氧基硫杂蒽酮、
2-羟基-2-甲基-1-[4-(2-羟基乙氧基)苯基]-1-丙酮中的一种。
7.根据权利要求1所述的双网络自主变形凝胶的制备方法,其特征在于:在所述步骤(a)中,所述丙烯酰胺类单体、所述丙烯酸单体、所述交联剂和所述水溶性引发剂摩尔比为55:45:1:0.1;
在所述步骤步骤(a)中,所述表面含有羧基的微凝胶和所述甲基丙烯酸缩水甘油酯的摩尔比为1:3;
在所述步骤(b)中,所述丙烯酰胺类单体、所述表面含有乙烯基的微凝胶和所述水溶性引发剂的摩尔比为90:10:0.1;
在所述步骤(c)中,所述表面含有乙烯基的微凝胶、所述丙烯酰胺类单体、所述乙烯基金属配合物单体、所述光引发剂的摩尔比为5:50:50:0.2。
8.根据权利要求1所述的双网络自主变形凝胶的制备方法,其特征在于:在所述步骤(c)中,所述浸润法为,将所述聚合物网络凝胶制品依次浸润在浓度呈梯度变化的甲醇水溶液中,至所述聚合物网络凝胶制品中的甲醇全部浸出。
9.一种双网络自主变形凝胶,其特征在于,由权利要求1-8任一所述的双网络自主变形凝胶的制备方法制得。
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CN113087849A (zh) * | 2021-05-06 | 2021-07-09 | 长春工业大学 | 一种高强韧导电水凝胶的制备方法 |
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CN112812328A (zh) * | 2021-02-09 | 2021-05-18 | 安徽美科迪智能微胶囊科技有限公司 | 一种可热致原位凝胶化共聚纳米水凝胶及其制备方法 |
CN112812328B (zh) * | 2021-02-09 | 2023-06-06 | 安徽美科迪智能微胶囊科技有限公司 | 一种可热致原位凝胶化共聚纳米水凝胶及其制备方法 |
CN113087849A (zh) * | 2021-05-06 | 2021-07-09 | 长春工业大学 | 一种高强韧导电水凝胶的制备方法 |
CN113087849B (zh) * | 2021-05-06 | 2022-05-10 | 长春工业大学 | 一种高强韧导电水凝胶的制备方法 |
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