CN106589410B - 一种光热双重响应高强度水凝胶及其制备方法和应用 - Google Patents
一种光热双重响应高强度水凝胶及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种基于螺吡喃的光热双重响应高强度双网络水凝胶及其制备方法和应用。本发明以聚(γ‑谷氨酸)甲基丙烯酸缩水甘油酯交联形成第一网络,然后将其溶胀在含有2‑[1‑丙烯酯‑3′,3′‑二甲基‑6‑硝基螺[吲哚啉‑2′,2‑[2H‑1]]‑苯并吡喃]甲基丙烯酸乙酯与N‑异丙基丙烯酰胺的预聚体溶液中,直至溶胀完全,取出后交联形成双网络水凝胶。因含有光致变色的螺吡喃单体和温度响应型NIPAAm单体,该双网络水凝胶不仅具有良好的机械性能,还可以对光和温度刺激产生响应,在药物负载、生物传感器和智能窗等方面具有良好的应用前景。
Description
技术领域
本发明涉及一种基于螺吡喃修饰光热双重响应高强度水凝胶及其制备方法和应用,属于光控阀、智能窗和生物医药领域。
背景技术
智能材料是指能够对温度、pH、磁场和光等刺激进行响应进而改变其物理化学性质的一类材料。在这些刺激类型中,光刺激因其来源简单易得,非入侵式等特点而受到日益关注。螺吡喃是一类可以对多种刺激,例如光、pH、机械外力、电场及某些金属离子响应的一类有机物。在紫外光的照射时,螺吡喃可发生开环反应,单体由疏水性的无色闭环体结构转化为亲水性的有色开环体(部花菁),并且上述反应在可见光的照射下可逆进行。通过在水凝胶中引入螺吡喃结构,当紫外光照射时,水凝胶的亲水性增强,颜色变深;当经过可见光的照射后,水凝胶疏水性增加发生体积收缩,颜色变浅。
聚(N-异丙基丙烯酰胺)(简称PNIPAAm)水凝胶是一类对温度刺激产生响应的材料。当温度高于其最低临界温度(LCST)时,聚合物链段疏水作用增加,水凝胶体积收缩;当温度低于LCST时,聚合物链段亲水作用增加,水凝胶体积溶胀。而且由于其响应温度为32-35℃,该温度接近室温和人体温度,因此,基于PNIPAAm的水凝胶在智能窗和生物医用材料等领域有较大的应用前景。然而,传统水凝胶的力学性能较差,限制了其应用。
发明内容
针对现有技术中存在的问题,本发明提供一种高强度的光热双重响应水凝胶,该水凝胶是一种由两种网络组成双网络水凝胶,第一网络为具有优异的生物相容性和亲水性的聚(γ-谷氨酸)(γ-PGA),第二网络由一定比例的对温度响应的N-异丙基丙烯酰胺(NIPAAm)和对光响应的螺吡喃组成,通过两种网络的相互作用,不仅可以大幅度提高水凝胶的力学性能,还提高了水凝胶的生物相容性、亲水性、温敏性和光敏性。
本发明所提供的技术方案具体如下:
一种基于螺吡喃的光热双重响应高强度双网络水凝胶的制备方法,包括以下步骤:
(1)将γ-PGA加入5wt%的碳酸氢钠水溶液中,搅拌至充分溶解,然后缓慢滴加甲基丙烯酸缩水甘油酯,避光室温搅拌反应,将反应后的溶液装入截留分子量为3500的透析袋中透析,最后将透析后的溶液真空冻干,得到白色固体产物γ-PGA-GMA;
(2)配制γ-PGA-GMA水溶液,加入Irgacure 2959作为光引发剂,混匀后于波长为365nm的紫外灯下照射,得到第一网络水凝胶;
(3)将二甲基-6-硝基螺[吲哚啉-2′,2-[2H-1]]-苯并吡喃]甲基丙烯酸乙酯、N-异丙基丙烯酰胺、N,N’-异丙基双丙烯酰胺(Bis)和Irgacure 819溶于水-二恶烷的混合液中,得到预聚体溶液;将第一网络水凝胶浸泡在预聚体溶液中,待第一网络水凝胶充分溶胀后取出,于波长为450nm的蓝光灯下照射,即得到基于螺吡喃的光热双重响应高强度双网络水凝胶;
所述的二甲基-6-硝基螺[吲哚啉-2′,2-[2H-1]]-苯并吡喃]甲基丙烯酸乙酯,其化学结构式为:
所述的γ-PGA的分子量为500000-1000000g/mol。
步骤(1)制得的γ-PGA-GMA中GMA的接枝率为5%-12%。
步骤(2)中,γ-PGA-GMA水溶液的浓度为1-10g/100mL,Irgacure 2959光引发剂用量为0.01-1g/100mL,紫外灯照射时间为5-30分钟。
步骤(3)中二甲基-6-硝基螺[吲哚啉-2′,2-[2H-1]]-苯并吡喃]甲基丙烯酸乙酯的浓度为0.1-2.5g/100mL,N-异丙基丙烯酰胺的浓度为5-20g/100mL,N,N’-异丙基双丙烯酰胺的浓度为0.1-2g/100mL,Irgacure 819的浓度为0.2-1g/100mL,水和二恶烷的体积比为1:3,蓝光灯下照射时间为10-30分钟。
所述的二甲基-6-硝基螺[吲哚啉-2′,2-[2H-1]]-苯并吡喃]甲基丙烯酸乙酯的合成方法包括以下步骤:
(1)避光条件下,将摩尔比为1:1的2,3,3-三甲基-3H-吲哚和3-碘丙酸混合均匀,然后于氮气保护下加热至100℃反应3小时,纯化,得到中间体A,其结构式如下:
(2)避光条件下,将摩尔比为1:1:1的中间体A、5-硝基水杨醛和哌啶一同溶解在甲基乙基酮中,回流反应3小时,纯化得中间体B,其结构式如下:
(3)避光条件下,将摩尔比为5:5:1的中间体B、二环己基碳二亚胺(DCC)和4-二甲氨基吡啶(DMAP)一同加入到装有恒压滴液漏斗的圆底烧瓶中,加入溶剂THF,在氮气保护下磁力搅拌均匀;然后将反应液冷却至0℃,缓慢滴加甲基丙烯酸羟乙酯(HEMA)的THF溶液,滴加完毕,0℃继续搅拌2小时,然后升温至25℃搅拌24小时,纯化,即得到二甲基-6-硝基螺[吲哚啉-2′,2-[2H-1]]-苯并吡喃]甲基丙烯酸乙酯。
一种基于螺吡喃的光热双重响应高强度双网络水凝胶,由上述制备方法制备得到。
上述基于螺吡喃的光热双重响应高强度双网络水凝胶在生物、医药、智能窗、光控微流阀领域的应用。
与现有技术相比,本发明具有以下优点和有益效果:
1.本发明制备的双网络水凝胶不仅具有良好的机械性能,并且可以同时对光和热进行快速的可逆响应,抗疲劳性好且不改变产品的理化性质。
2.本发明制备的双网络水凝胶可以通过控制水凝胶组分和含量可以很方便地调节水凝胶的机械性能和光热响应时间和响应程度,旨在满足不同的需要。
3.本发明制备的双网络水凝胶中光敏感单体含量很少但能显著改变该产品的亲疏水性。
附图说明
图1为实施例6中水凝胶的光致变色性能示意图;其中,图1(A)为UV光照射前的水凝胶,图1(B)为UV光照射30s后的水凝胶,图1(C)为LED灯照射30s的水凝胶。
图2为实施例7中水凝胶的热响应性能示意图;其中,图2(A)为室温的水凝胶,图2(B)为40℃的水凝胶,图2(C)为由40℃恢复到室温的水凝胶。
具体实施方式
以下结合具体实施例对本发明作进一步详细的说明。
实施例1
γ-PGA-GMA(Mn=1000000g/mol)的合成:先准确称取γ-PGA 4.01g溶于100mL的5wt%NaHCO3水溶液中,缓慢搅拌至γ-PGA充分溶解后,静置除气泡;然后加入0.1g 4-二甲氨基吡啶(DMAP),搅拌充分溶解后,继续缓慢滴加4.1mL甲基丙烯酸缩水甘油酯(GMA)。然后将上述溶液避光缓慢搅拌反应60小时,再将反应后的溶液装入截留分子量为3500的透析袋于蒸馏水中透析三天,每天至少换水三次,最后冻干得到目标产物γ-PGA-GMA。采用核磁技术表征其结构,计算得到其接枝率为10%。
实施例2
螺吡喃单体SPMA的合成:所有反应容器均用铝箔纸包住避光处理。
(1)准确量取10.1mL(0.06mol)2,3,3-三甲基-3H-吲哚和12.6g(0.06mol)3-碘丙酸于氮气下加热至100℃反应3小时;反应后剩下的固体在去离子水中溶解并经三氯甲烷洗涤,然后蒸发除水得到碘化中间产物—中间体A,产率为75%;其结构式如下:
(2)取中间体A 14g(0.04mol)、6.5g(0.04mol)5-硝基水杨醛和3.8mL(0.04mol)哌啶一同溶于甲基乙基酮中,得到红色反应液,回流反应3小时;然后静置过夜,沉淀析出黄色粉末状固体。然后过滤并用甲醇反复洗涤得到中间体B,产率为78%。其结构式如下:
(3)准确称取中间体B(3.8,10mmol),DCC(2.06g,10mmol)和DMAP(0.272g,2mmol)加入到装有恒压滴液漏斗的100mL圆底烧瓶中,加入80mL THF,在氮气中磁力搅拌混合均匀,将反应液冷却到0℃(红棕色液体)。
另准备一个小的圆底烧瓶,将HEMA(2.6g,20mmol)溶于20mL THF中配成溶液。HEMA的THF溶液经恒压滴液漏斗逐滴加入到中间体B/DCC混合液中,45分钟内加完。圆底烧瓶在0℃下低温搅拌2小时,后于升温至25℃搅拌24小时。加入0℃50mL THF溶解,过滤,重复三次,收集滤液(红色)。滤液经旋转蒸馏除去溶剂,然后经去离子水反复洗涤除去未反应的HEMA后得到紫红色沉淀物。紫红色沉淀物经柱层析得到目标产物二甲基-6-硝基螺[吲哚啉-2′,2-[2H-1]]-苯并吡喃]甲基丙烯酸乙酯(简称SPMA),淋洗剂为石油醚:二氯甲烷=4:1。
实施例3
分别配制质量浓度为0.02g/mL和0.03g/mL的γ-PGA-GMA(Mn=1000000g/mol,接枝率为10%)水溶液,并加入光引发剂Irgacure 2959,使其浓度为0.0005g/mL,离心除气泡。移取上述溶液置于模具中,于波长为365nm的紫外光下照射10分钟,得到第一网络水凝胶γ-PGA水凝胶,分别命名为PGA2和PGA3,并于万能试验机上测试其力学性能。
实施例4
准确称取SPMA 0.0080g、NIPAAm 0.20g和Bis 0.008g,加入到去离子水:二恶烷=1:3(v/v)的混合液中,配制成NIPAAm单体浓度为0.08g/mL、质量比为SPMA:NIPAAm=1.06:100的单体混合液;然后向上述单体混合液中加入Irgacure 819,使其质量浓度为0.01g/mL,得到预聚体溶液;将实施例3制备的第一网络水凝胶PGA2和PGA3浸没在预聚体溶液中,溶胀5天直至溶胀平衡后取出,用蒸馏水清洗表面,并于波长为450nm的蓝光下照射15分钟,分别得到双网络水凝胶DN2-8和DN3-8,命名中的2和3分别表示γ-PGA的浓度值,8表示NIPAAm的浓度值。并于万能试验机上测试水凝胶的力学性能。
实施例5
准确称取SPMA 0.0080g、NIPAAm 0.40g和Bis 0.008g,加入到去离子水:二恶烷=1:3(v/v)的混合液中,配制成NIPAAm单体浓度为0.16g/mL、质量比为SPMA:NIPAAm=1.06:200的单体混合液;然后向单体混合液中加入Irgacure 819,使其浓度为0.01g/mL,得到预聚体溶液;将上述制备的第一网络水凝胶PGA2和PGA3浸没于上述预聚体溶液中,溶胀5天直至溶胀平衡后取出,用蒸馏水清洗表面,并于波长为450nm的蓝光下照射15min,分别得到双网络水凝胶DN2-16和DN3-16,命名中的2和3分别表示γ-PGA的浓度值,16表示NIPAAm的浓度值。于万能试验机上测试水凝胶的力学性能。
实施例6
准确称取SPMA 0.0008g、NIPAAm 0.2g、Bis 0.00924g,加入到去离子水:二恶烷=1:3(v/v)的混合液中,配成NIPAAm单体浓度为0.08g/mL、质量比为SPMA:NIPAAm=1.06:1000的单体混合液;接着向单体混合液中加入0.004g Irgacure 819,得到预聚体溶液;然后将上述制备的第一网络水凝胶PGA2浸没于预聚体溶液中,溶胀5天直至溶胀平衡后取出,用蒸馏水清洗表面,并于波长为450nm的蓝光下照射15分钟,得到双网络水凝胶,并经波长为365nm的UV光照射30秒后拍照,再用LED光源下照射30秒拍照记录,详见图1。
实施例7
准确称取SPMA 0.0008g、NIPAAm 0.2g、Bis 0.00924g、0.004g Irgacure 819配成NIPAAm单体浓度为0.08g/mL、SPMA:NIPAAm=1.06:1000的预聚体溶液,溶剂为去离子水:二恶烷=1:3(v/v)的混合液。然后将实施例3制备的第一网络水凝胶PGA2浸没于预聚体溶液中,溶胀5天直至溶胀平衡后取出,用蒸馏水清洗表面,并于波长为450nm的蓝光下照射15分钟。将所制备的水凝胶置于40℃热水中升温30秒拍照,待温度降至室温后拍照记录,详见图2。
实施例3、4、5单网络水凝胶和双网络水凝胶的机械性能如表1所示。
表1.水凝胶的机械性能
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (8)
1.一种基于螺吡喃的光热双重响应高强度双网络水凝胶的制备方法,其特征在于,包括以下步骤:
(1)将γ-PGA加入5wt%的碳酸氢钠水溶液中,搅拌至充分溶解,然后缓慢滴加甲基丙烯酸缩水甘油酯,避光室温搅拌反应,将反应后的溶液装入截留分子量为3500的透析袋中透析,最后将透析后的溶液真空冻干,得到白色固体产物γ-PGA-GMA;
(2)配制γ-PGA-GMA水溶液,加入Irgacure 2959作为光引发剂,混匀后于波长为365nm的紫外灯下照射,得到第一网络水凝胶;
(3)将二甲基-6-硝基螺[吲哚啉-2′,2-[2H-1]]-苯并吡喃]甲基丙烯酸乙酯、N-异丙基丙烯酰胺、N,N’-异丙基双丙烯酰胺和Irgacure 819溶于水-二恶烷的混合液中,得到预聚体溶液;将第一网络水凝胶浸泡在预聚体溶液中,待第一网络水凝胶充分溶胀后取出,于波长为450nm的蓝光灯下照射,即得到基于螺吡喃的光热双重响应高强度双网络水凝胶;
所述的二甲基-6-硝基螺[吲哚啉-2′,2-[2H-1]]-苯并吡喃]甲基丙烯酸乙酯,其化学结构式为:
2.根据权利要求1所述的制备方法,其特征在于:所述的γ-PGA的分子量为500000-1000000g/mol。
3.根据权利要求1所述的制备方法,其特征在于:步骤(1)制得的γ-PGA-GMA中GMA的接枝率为5%-12%。
4.根据权利要求1所述的制备方法,其特征在于:步骤(2)中,γ-PGA-GMA水溶液的浓度为1-10g/100mL,Irgacure 2959光引发剂用量为0.01-1g/100mL,紫外灯照射时间为5-30分钟。
5.根据权利要求1所述的制备方法,其特征在于:步骤(3)中二甲基-6-硝基螺[吲哚啉-2′,2-[2H-1]]-苯并吡喃]甲基丙烯酸乙酯的浓度为0.1-2.5g/100mL,N-异丙基丙烯酰胺的浓度为5-20g/100mL,N,N’-异丙基双丙烯酰胺的浓度为0.1-2g/100mL,Irgacure 819的浓度为0.2-1g/100mL,水和二恶烷的体积比为1:3,蓝光灯下照射时间为10-30分钟。
6.根据权利要求1所述的制备方法,其特征在于:所述的二甲基-6-硝基螺[吲哚啉-2′,2-[2H-1]]-苯并吡喃]甲基丙烯酸乙酯的合成方法包括以下步骤:
(1)避光条件下,将摩尔比为1:1的2,3,3-三甲基-3H-吲哚和3-碘丙酸混合均匀,然后于氮气保护下加热至100℃反应3小时,纯化,得到中间体A,其结构式如下:
(2)避光条件下,将摩尔比为1:1:1的中间体A、5-硝基水杨醛和哌啶一同溶解在甲基乙基酮中,回流反应3小时,纯化得中间体B,其结构式如下:
(3)避光条件下,将摩尔比为5:5:1的中间体B、二环己基碳二亚胺和4-二甲氨基吡啶一同加入到装有恒压滴液漏斗的圆底烧瓶中,加入溶剂THF,在氮气保护下磁力搅拌均匀;然后将反应液冷却至0℃,缓慢滴加甲基丙烯酸羟乙酯的THF溶液,滴加完毕,0℃继续搅拌2小时,然后升温至25℃搅拌24小时,纯化,即得到二甲基-6-硝基螺[吲哚啉-2′,2-[2H-1]]-苯并吡喃]甲基丙烯酸乙酯。
7.一种基于螺吡喃的光热双重响应高强度双网络水凝胶,其特征在于,由权利要求1-6任一项所述的制备方法制备得到。
8.权利要求7所述的基于螺吡喃的光热双重响应高强度双网络水凝胶在智能窗、光控微流阀领域的应用。
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CN105646905A (zh) * | 2016-01-19 | 2016-06-08 | 湖南工业大学 | 一种光、热双敏感快速响应复合凝胶的制备方法 |
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CN101891954A (zh) * | 2010-06-23 | 2010-11-24 | 南开大学 | 一种聚谷氨酸水凝胶的制备方法 |
CN103408683A (zh) * | 2013-07-15 | 2013-11-27 | 东华大学 | 一种物理/化学交联的光热响应水凝胶的制备方法 |
CN104987473A (zh) * | 2013-10-11 | 2015-10-21 | 天津大学 | 高强度光敏感水凝胶在调节细胞贴附行为中的应用 |
CN104829779A (zh) * | 2015-05-07 | 2015-08-12 | 宁波大学 | 一种光响应的聚合物微凝胶粒子及其制备方法 |
CN105646905A (zh) * | 2016-01-19 | 2016-06-08 | 湖南工业大学 | 一种光、热双敏感快速响应复合凝胶的制备方法 |
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