CN106543360B - 一种具有紫外屏蔽和常温自修复性能复合水凝胶及其合成和应用 - Google Patents
一种具有紫外屏蔽和常温自修复性能复合水凝胶及其合成和应用 Download PDFInfo
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Abstract
本发明提供了一种二氧化钛掺杂的具有紫外屏蔽和自修复性能的复合水凝胶P(NaSS‑MPTC)/TiO2，是以二氧化钛纳米溶胶作为紫外屏蔽剂、光引发剂和交联剂，阳离子液体和阴离子液体为共聚单体，在NaCl溶液中，通过光引发自由基聚合法聚合而得。通过紫外‑可见光谱检测其透光率，进一步探究了复合水凝胶的紫外防护性能。该复合水凝胶不仅具有优异的常温自修复性能，而且具有很好的紫外保护性能，因此可作为紫外线屏蔽剂应用于紫外屏蔽领域。
Description
技术领域
本发明涉及一种基于二氧化钛纳米粒子的复合水凝胶，尤其涉及一种二氧化钛掺杂的具有紫外屏蔽和常温自修复性能复合水凝胶P(NaSS-MPTC)/TiO2的合成方法，属于复合材料技术领域及紫外屏蔽领域。
背景技术
众所周知，紫外线辐射问题已严重的威胁着人类皮肤、涂料、塑料等有机制品，从而给人的正常生活带来了很大的危害。自从1995年3月在伦敦召开了紫外线防护国际研讨会表明，在世界范围内紫外线的防护已经引起各国的广泛重视。因此紫外屏蔽剂的研究已受到科研工作者广泛且持久的关注。
二氧化钛纳米粒子因具有粒径小、比表面积大、高的热力学和化学稳定性、低毒性，不仅能吸收紫外光透过可见光，同时还可以很大程度的反射和折射紫外光，因而被广泛的应用于紫外屏蔽领域的研究。其中，将二氧化钛掺杂到水凝胶体系中得到的纳米复合水凝胶不仅具有很好的紫外防护性能，同时还具有水凝胶体系所具有的超吸水性、生物相容性、环境响应性、自修复性、黏弹性等特性，具有更大的实际应用价值，因而成为近几年紫外防护领域研究的热点。
二氧化钛纳米粒子不仅因其特殊的结构和可吸收紫外光而作为紫外屏蔽剂和光引发剂，而且由于其表面含有大量的羟基具有亲水性可以均匀的分散到含有亲水性聚合物的矩阵中，同时还因可以与带有羟基、胺基、磺酸根等官能团的亲水性聚合物之间形成氢键作用而交联形成具有优异机械性能的物理水凝胶。已有大量文献报道，以二氧化钛作为交联剂制备的物理水凝胶应用于具有优异机械性能的紫外屏蔽材料中。然而由于其通过一种非共价键很难达到常温自修复而无法重复使用，从而很大程度上限制了它的实际使用范围。
发明内容
本发明的目的是提供一种基于二氧化钛纳米粒子的具有紫外屏蔽和常温自修复性能的复合水凝胶——P(NaSS-MPTC)/TiO2的合成方法。
一、水凝胶P(NaSS-MPTC)/TiO2的合成
以二氧化钛纳米溶胶作为紫外屏蔽剂、光引发剂和交联剂，阳离子液体（MPTC）和阴离子液体(NaSS)为共聚单体，在NaCl溶液中，通过光引发自由基聚合法，合成了复合水凝胶P(NaSS-MPTC)/TiO2——常温自修复的凝胶基紫外线屏蔽剂材料。
其具体合成工艺为：将阳离子液单体和阴离子液单体溶解到超纯水中，充分搅拌后加入氯化钠，超声3~5min使其充分分散后，在氮气气氛下搅拌12~15min；迅速加入二氧化钛溶液，再继续用高纯氮气除去O2，然后置于紫外灯下光照30~36h，得到复合水凝胶P(NaSS-MPTC)/TiO2。
所述阳离子液单体为3-(异丁烯酰胺)丙基三甲基氯化铵(MPTC)，阴离子液单体为对苯乙烯磺酸钠(NaSS)；阳离子液单体与阴离子液单体的质量比为1:1~1:1.1。
二氧化钛纳米粒子的加入量为阳离子液单体与阴离子液单体总质量的0.4~2.4%，得到的复合水凝胶P(NaSS-MPTC)/TiO2中二氧化钛纳米粒子的掺杂量为0.16~0.96%。
氯化钠的添加有助于进一步提高该凝胶的黏弹性，其加入量为阳离子液单体与阴离子液单体的总质量的6.5~6.6%。
二、复合水凝胶P(NaSS-MPTC)/TiO2的紫外屏蔽性能和常温自修复性能
1、紫外屏蔽性能
用于紫外屏蔽性能的水凝胶薄膜，是将上述配置好的含有阳离子液单体3-(异丁烯酰胺)丙基三甲基氯化铵(MPTC)、阴离子液单体对苯乙烯磺酸钠(NaSS)、超纯水、氯化钠以及二氧化钛纳米粒子含量分别为0.16%、0.32%、0.48%和0.96%的四种混合液体分别注入由两片石英玻璃和厚度为0.5mm的硅胶垫所组成的反应池中，然后将此反应装置密封后放到365nm的紫外灯下光照6~10h。通过紫外-可见光谱检测其透光率，进一步探究了该复合水凝胶的紫外防护性能。
图1显示的是厚度均为0.5mm，二氧化钛含量分别为0.16%、0.32%、0.48%、0.96%的复合水凝胶(NaSS-MPTC)/TiO2的紫外透射光谱。由图1可以看出，在可见区（400-900nm）范围内，虽然该凝胶薄膜的透光率随着波长的降低而不断减小，但减小的很慢而且均大于零；然而当波长降低到紫外区（200-400nm），该凝胶薄膜的透光率将迅速下降，直到降低到零，而且二氧化钛含量越大其越先在波长较大处到零，从而表现出更为优异的紫外屏蔽性能。仔细对比二氧化钛含量不同的该凝胶薄膜，虽然随着二氧化钛含量增大而具有更优异的紫外屏蔽性能，但在可见区随着二氧化钛含量的不断增加其透光率也不断降低。
2、自修复性能
图2所示为紫外屏蔽剂P (NaSS-MPTC)/TiO2在室温下的自修复光学照片图，其中（a）为上述制备的直径约为2cm的P (NaSS-MPTC)/TiO2。将其用刀片切开（b）后，在4~6s内切开的新鲜断面合在了一起，用力挤压，然后封装放置2~3h，发现刚切开的切痕基本消失。
为了定性探究其自修复效果，用两个小夹子沿着切面两端拉至原紫外屏蔽剂长度的2倍，自修复好的紫外屏蔽剂仍保持完整，并未从切痕处裂开，由此充分显示，水凝胶P(NaSS-MPTC)/TiO2具有良好的常温自修复性能。
综上所述，以二氧化钛纳米粒子与阴阳离子液单体为基础，“一锅法”成功合成了复合水凝胶P (NaSS-MPTC)/TiO2，不仅具有优异的常温自修复性能，而且具有很好的紫外保护性能，因此可作为紫外线屏蔽剂应用于紫外屏蔽领域。
附图说明
图1为相同厚度不同二氧化钛含量的复合水凝胶P (NaSS-MPTC)/TiO2薄膜的紫外-可见透射光谱；
图2为水凝胶 P(NaSS-MPTC)/TiO2的常温自修复光学照片图。
具体实施方式
下面通过具体实施例对本发明具有紫外屏蔽和自修复性能的复合水凝胶——P(NaSS-MPTC)/TiO2的合成及性能作进一步说明。
实施例1
取3-(异丁烯酰胺)丙基三甲基氯化铵0.9006g，对苯乙烯磺酸钠0.4503g，溶解到盛有0.855g超纯水的反应瓶中充分搅拌；再取氯化钠 0.0585g加入到上述溶液中，超声3~5min，氮气气氛下充分搅拌12~15min，随后迅速将0.045g的二氧化钛溶液注入其中，再继续用高纯氮气鼓泡12~15min除去氧气，最后将反应瓶密封置于365nm紫外灯下光照36h，得到二氧化钛纳米粒子掺杂量为0.16%的复合水凝胶P(NaSS-MPTC)/TiO2。
上述制备的复合水凝胶P(NaSS-MPTC)/TiO2的紫外屏蔽性能；在可见区(400-900nm)范围内，虽然该凝胶薄膜的透光率随着波长的降低而不断减小，但减小的很慢而且均大于零，然而当波长降低到紫外区(200−400 nm)，该凝胶薄膜的透光率将迅速下降，直到当波长为278nm时透光率降低到零，说明波长小于278nm的紫外光可以被厚度为0.5mm的水凝胶(NaSS-MPTC)/TiO2薄膜完全阻挡住，显示出优异的紫外屏蔽效应。
自修复性能：在常温下切开的新鲜断面可在4~6s内合在了一起，用力挤压，然后封装放置2~3h，发现刚切开的切痕基本消失。
实施例 2
取3-(异丁烯酰胺)丙基三甲基氯化铵0.8957g，对苯乙烯磺酸钠0.4505g，溶解到盛有0.81g超纯水的反应瓶中充分搅拌；再取氯化钠 0.0585g加入到上述溶液中，超声3~5min，氮气气氛下充分搅拌12~15min，随后迅速将0.09g的二氧化钛溶液注入其中，再继续用高纯氮气鼓泡12~15min除去氧气，最后将反应瓶密封置于365nm紫外灯下光照34h，得到二氧化钛纳米粒子掺杂量为0.32%的复合水凝胶P(NaSS-MPTC)/TiO2。
上述制备的复合水凝胶P(NaSS-MPTC)/TiO2的紫外屏蔽性能；在可见区(400-900nm)范围内，虽然该凝胶薄膜的透光率随着波长的降低而不断减小，但减小的很慢而且均大于零，然而当波长降低到紫外区(200−400 nm)，该凝胶薄膜的透光率将迅速下降，直到当波长为287nm时透光率降低到零，说明波长小于287nm的紫外光可以被厚度为0.5mm的水凝胶(NaSS-MPTC)/TiO2薄膜完全阻挡住，显示出优异的紫外屏蔽效应。
自修复性能：在常温下切开的新鲜断面可在4~6s内合在了一起，用力挤压，然后封装放置2~3h，发现刚切开的切痕基本消失。
实施例 3
取3-(异丁烯酰胺)丙基三甲基氯化铵0.8914g，对苯乙烯磺酸钠0.4507g，溶解到盛有0.765g超纯水的反应瓶中充分搅拌；再取氯化钠 0.0585g加入到上述溶液中，超声3~5min，氮气气氛下充分搅拌12~15min，随后迅速将0.135g的二氧化钛溶液注入其中，再继续用高纯氮气鼓泡12~15min除去氧气，最后将反应瓶密封置于365nm紫外灯下光照32h，得到二氧化钛纳米粒子掺杂量为0.48%的复合水凝胶P(NaSS-MPTC)/TiO2。
上述制备的复合水凝胶P(NaSS-MPTC)/TiO2的紫外屏蔽性能；在可见区(400-900nm)范围内，虽然该凝胶薄膜的透光率随着波长的降低而不断减小，但减小的很慢而且均大于零，然而当波长降低到紫外区(200−400 nm)，该凝胶薄膜的透光率将迅速下降，直到当波长为335nm时透光率降低到零，说明波长小于335nm的紫外光可以被厚度为0.5mm的水凝胶(NaSS-MPTC)/TiO2薄膜完全阻挡住，显示出优异的紫外屏蔽效应。
自修复性能：在常温下切开的新鲜断面可在4~6s内合在了一起，用力挤压，然后封装放置2~3h，发现刚切开的切痕基本消失。
实施例 4
取3-(异丁烯酰胺)丙基三甲基氯化铵水溶液0.8902g，对苯乙烯磺酸钠0.4509g，溶解到盛有0.63g超纯水的反应瓶中充分搅拌；再取氯化钠0.0585g 加入到上述溶液中，超声3~5min，氮气气氛下充分搅拌12~15min，随后迅速将0.27g的二氧化钛溶液注入其中，再继续用高纯氮气鼓泡12~15min除去氧气，最后将反应瓶密封置于365nm紫外灯下光照30h，得到二氧化钛纳米粒子掺杂量为0.96%的复合水凝胶P(NaSS-MPTC)/TiO2。
上述制备的复合水凝胶P(NaSS-MPTC)/TiO2的紫外屏蔽性能；在可见区(400-900nm)范围内，虽然该凝胶薄膜的透光率随着波长的降低而不断减小，但减小的很慢而且均大于零，然而当波长降低到紫外区(200−400 nm)，该凝胶薄膜的透光率将迅速下降，直到当波长为355nm时透光率降低到零，说明波长小于355nm的紫外光可以被厚度为0.5mm的水凝胶(NaSS-MPTC)/TiO2薄膜完全阻挡住，显示出优异的紫外屏蔽效应。
自修复性能：在常温下切开的新鲜断面可在4~6s内合在了一起，用力挤压，然后封装放置2~3h，发现刚切开的切痕基本消失。
Claims (5)
1.一种具有紫外屏蔽和常温自修复性能复合水凝胶的合成方法，是以二氧化钛纳米溶胶作为紫外屏蔽剂、光引发剂和交联剂，阳离子液体和阴离子液体为共聚单体，在NaCl溶液中，通过光引发自由基聚合法聚合，得到复合水凝胶，即为目标产物；
所述阳离子液单体为3-(异丁烯酰胺)丙基三甲基氯化铵，阴离子液单体为对苯乙烯磺酸钠，阳离子液单体与阴离子液单体的质量比为1:1~1:1.1。
2.如权利要求1所述具有紫外屏蔽和常温自修复性能复合水凝胶的合成方法，其特征在于：将阳离子液单体和阴离子液单体溶解到超纯水中，充分搅拌后加入氯化钠，超声3~5min使其充分分散后，在氮气气氛下搅拌12~15min；迅速加入二氧化钛溶液，再继续用高纯氮气鼓泡以除去O2，然后置于紫外灯下光照30~36h即得产物。
3.如权利要求1或2所述具有紫外屏蔽和常温自修复性能复合水凝胶的合成方法，其特征在于：二氧化钛纳米粒子的加入量为阳离子液单体与阴离子液单体总质量的0.4~2.4%。
4.如权利要求1或2所述具有紫外屏蔽和常温自修复性能复合水凝胶的合成方法，其特征在于：氯化钠的加入量为阳离子液单体与阴离子液单体的总质量的6.5~6.6%。
5.如权利要求1所述方法制备的具有紫外屏蔽和常温自修复性能复合水凝胶作为紫外线屏蔽剂的应用。
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