CN113214504A - 一种基于天然高分子的半互穿网络抑菌凝胶的制备方法 - Google Patents
一种基于天然高分子的半互穿网络抑菌凝胶的制备方法 Download PDFInfo
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Abstract
本发明公开了一种通过水中氨基与酸酐的点击反应制备基于天然高分子的半互穿网络抑菌凝胶的方法,包括如下步骤:首先,用季铵盐对天然产物纤维素、壳聚糖等天然高分子进行修饰,得到具有抑菌性的聚合物;用埃洛石负载金属银,制备出具有抑菌性的纳米粒子,然后将季铵盐化的天然大分子、纳米粒子、含有酸酐与氨基的共聚物溶解于水中形成均匀的溶液,利用水中氨基与酸酐之间的点击反应得到水凝胶,用水浸泡除去未交联的成分,经冷冻干燥后可得到具有抑菌性的气凝胶。本发明凝胶在水中快速生成,制备过程简单、所得凝胶具有pH响应性,可用于药物缓释、组织工程、水处理等诸多领域。
Description
技术领域
本发明属于高分子材料领域,涉及一种利用水中氨基与酸酐的点击反应制备基于天然高分子的半互穿网络抑菌凝胶的方法。
背景技术
由于水凝胶的特殊性能,水凝胶在水处理、药物缓释、农业等领域具有巨大的应用潜力。其中,能够对环境刺激(温度、pH、电场、磁场等)做出响应的智能水凝胶格外引人注目。由于pH是生物体内及自然界中普遍存在的环境变化,研究pH敏感型智能水凝胶具有重要意义。根据水凝胶的结构不同,水凝胶可以分为单网络水凝胶、半互穿网络水凝胶和全互穿网络水凝胶。其中,半互穿网络水凝胶由一种或多种线性大分子和一个交联的聚合网络组成,线性大分子链穿插在交联聚合物的网络之中,而且交联的聚合物与穿插的线性大分子之间不存在共价连接。半互穿网络水凝胶保留了半互穿网络水凝胶中的每种聚合物的特性,同时也增强了水凝胶的整体机械强度及对环境的刺激响应速度。
水凝胶根据其形成原理,可分为物理交联的水凝胶与化学交联的水凝胶。物理交联的水凝胶是通过范德华力、氢键、结晶、离子络合等作用力形成的凝胶,该凝胶一般具有可逆性触变性,然而其机械强度低。而化学交联的水凝胶机械强度较高,制备化学交联的水凝胶常用到的反应是自由基聚合,然而往往需要使用引发剂,这就限制了水凝胶的应用。为此,人们不断开发制备水凝胶的新方法。在这些方法中,基于点击反应的水凝胶的制备方法备受关注。点击反应是一类具有反应模块化、高效、快速、条件温和等特点的反应的统称。目前,点击反应的种类正在不断拓展,如氨基-醛基、氨基-烯基、氨基-环氧基之间的反应也被归类于点击反应。虽说传统的叠氮-炔基Husigen环加成点击反应具有选择性强、条件温和、产率高等优点,但产品中残存的难以除去的铜催化剂会影响水凝胶的生物相容性,虽然使用含有高张力环的炔基化合物可免除铜催化剂的使用,但其制备过程复杂,这就限制了其应用推广。因此,开发无需催化剂、无需有机溶剂、操作简单的点击反应制备水凝胶具有重要意义。
另一方面,如何赋予凝胶抑菌性是凝胶使用过程中需考虑的问题。抑菌材料可分为天然的、无机的、有机的「杨明等,广州化工,2010,38(12):18-20」。天然抑菌材料包括壳聚糖,生物肽等,无机主要有银抗菌材料,锌抗菌材料,铜抗菌材料等,有机类有季铵盐,双胍等。壳聚糖具有广谱抗菌性,对霉菌、细菌都有很好的抗菌性能,在金属离子抗菌剂中,银离子抗菌剂是既对人体无害而抗菌效果最好的抗菌剂。季铵盐类抑菌剂是依靠铵阳离子紧紧附于细菌的细胞壁表面,导致细胞膜和细胞壁的破坏,从而抑制细菌生长。近年来,人们非常注重复合型抑菌材料的研究,以充分提高材料的抑菌性能。
发明内容
本发明目的是通过水中无催化剂的酸酐与氨基之间的点击反应制备基于天然大分子的半互穿网络抑菌凝胶,以克服传统凝胶制备与应用中存在的问题。该方法通过酸酐与氨基之间的点击反应制备了半互穿网络抑菌水凝胶,反应条件温和、反应时间短、简单易行。通过对天然大分子进行季铵盐化,同时在制备凝胶的过程中添加具有抑菌性的无机纳米粒子,采用“一锅法”制备了具有抑菌性的半互穿网络凝胶。
为实现上述目的,本发明采取下述技术方案:
(1)含有酸酐的水溶性聚合物的制备。
(2)用季铵盐化合物对天然产物纤维素、壳聚糖等天然产物进行修饰。
(3)将含有氨基与酸酐的聚合物、季铵盐修饰的天然产物、无机纳米粒子溶解于水中。
(4)加入少量的碱调节溶液的pH>7,加热,通过氨基与酸酐之间的点击反应发生凝胶化,形成水凝胶。
(5)将制备的半互穿网络水凝胶放入蒸馏水中,去除残留在亲水网络水凝胶中的杂质,冷冻干燥可得到气凝胶。
所述步骤(1)中采用设定的方法合成含有氨基与酸酐的水溶性聚合物。含有氨基的聚合物可以是超支化聚合物,也可以是线性聚合物,既可以含有游离的氨基也可以含有氨基的盐酸盐。含有酸酐的聚合物可采用马来酸酐或衣康酸酐与不同的亲水单体聚合制备,可以是二元共聚物,也可以是多元共聚物。采用的亲水性单体可以是丙烯酰胺、N-异丙基丙烯酰胺、(甲基)丙烯酸、2-丙烯酰胺基-2-甲基丙磺酸等单体中的一种或几种。
所述步骤(2)中季铵盐修饰的天然产物,天然产物可以是纤维丝、壳聚糖等,修饰所用的季铵盐可以是3-氯-2-羟丙基三甲基氯化氨或其它可与天然产物反应的季铵盐化合物。
所述步骤(3)中的无机纳米粒子是具有抑菌性的纳米粒子,可以是银纳米粒子或CuO纳米粒子等。
所述步骤(4)溶液的pH的调节可以采用NaOH溶液调节,也可采用弱碱三乙胺、吡啶或碳酸钠来调节。为了提高反应速度,反应时可适当加热,一般不超过50°C。
所述步骤(5)蒸馏水的浸泡时间一般不少于48小时,中间经常换水以除去未交联的成分。
本发明的技术优势主要体现在:
本发明首先合成含有氨基与酸酐的亲水聚合物,然后在水中通过氨基与酸酐之间的反应原位形成水凝胶,该反应符合点击反应的特点,不需要催化剂,在水中可快速进行;氨基与酸酐反应后产生羧基,可赋予凝胶pH敏感性。采用季铵盐修饰的天然大分子,赋予水凝胶抑菌性,在制备半互穿网络水凝胶的过程中,也可以通过原位添加无机纳米增加凝胶的抑菌性。采用“一锅法”制备基于天然大分子的半互穿网络抑菌气凝胶,操作过程简单,反应时间短,具有广泛的应用前景。
以下结合实施例对本发明进行详细说明。但应理解,以下实施例仅是对本发明实施方式的举例说明,而非是对本发明的范围限定。
附图说明
图1改变溶液的总质量浓度时制的半互穿网络凝胶的红外谱图。
图2改变丙烯酰胺/马来酸酐摩尔比时制的凝胶的凝胶质量分数(左)及溶胀度(右)。
图3 改变季铵盐含量时凝胶的凝胶质量分数(左)及溶胀度(右)。
图4 半互穿网络水凝胶的溶胀度随pH的变化曲线(左)及溶胀度的循环曲线(右)。
具体实施方式
实施例1
在单口烧瓶中依次加入适量的马来酸酐、丙烯酰胺、偶氮二异丁腈和60 mL1,4-二氧六环,室温下搅拌溶解后抽真空充氮气,循环3-4次后,加热升温到75℃,搅拌反应8 h后,抽滤,得到白色固体,70℃下真空干燥12 h。单体总浓度控制为1 mol·L-1,AIBN浓度控制为0.005 mol·L-1,通过控制丙烯酰胺与马来酸酐的摩尔比,可以得到不同组成的共聚物。同样地,用衣康酸酐代替马来酸酐,可得到衣康酸酐与丙烯酰胺的共聚物。
实施例2
在单口烧瓶中依次加入适量的马来酸酐、N,N-二甲基丙烯酰胺、偶氮二异丁腈和60 mL1,4-二氧六环,室温下搅拌溶解后抽真空充氮气,循环3-4次后,加热升温到75℃,搅拌反应8 h,降温,用石油醚沉淀,抽滤,得到白色固体,75℃下真空干燥12 h。单体总浓度控制为1 mol·L-1,AIBN浓度控制为0.005 mol·L-1,通过控制N,N-二甲基丙烯酰胺与马来酸酐的摩尔比,可以得到不同组成的共聚物。
实施例3
在三口烧瓶中依次加入6.4809 g N-丙基丙烯酰胺、0.8024 g马来酸酐、1.7446 g丙烯酰胺、0.0738 g偶氮二异丁腈(AIBN),再加入60 mL的1,4-二氧六环,室温条件下搅拌溶解后开始抽真空充氮气,循环3-4次后停止,开始加热升温,升到75℃计时搅拌反应8 h,自然冷却至室温,有白色物质析出,抽滤,得到白色固体,60℃下真空干燥12小时。得到N-异丙基丙烯酰胺:丙烯酰胺:马来酸酐摩尔比为7:3:1的三元共聚物。
实施例4
以无水乙醇作为反应溶剂,先加入正丁胺搅拌再加入埃洛石纳米管0.055 g,最后加入0.0849 g硝酸银(硝酸银与正丁胺按照摩尔比为1: 0.5)快速搅拌10 min,然后放入50℃油浴锅中反应50 min,最后静置分离上清液,得到的样品用无水乙醇洗涤,在60℃下真空干燥24 h,得到灰黑色样品。即为埃洛石负载银离子的纳米粒子。
实施例5
将0.1961g NaOH溶于40 mL蒸馏水,再加入1.0000 g 羧基壳聚糖,溶解之后加入2.23 g 2,3-环氧丙基三甲基氯化铵,溶解后在50℃下搅拌反应6 h, 反应结束后将反应液装入透析袋中,用去离子水透析3天,然后冷冻干燥得到季铵盐化的羧甲基壳聚糖。
实施例 6
准确称取2.00 g纤维素棉短绒木浆,置于250 mL的烧杯中,加入NaOH、CO(NH2)2和H2O(质量比6:15: 79)的混合溶液,机械搅拌5 min后置于-12℃冰箱中冷冻12小时,室温下解冻后机械搅拌至形成均相溶液。然后将5.89 g醚化剂(3-氯-2-羟丙基三甲基氯化氨)加入上述纤维素溶液中,在25℃条件下反应24 h,使纤维素单元在醚化剂作用下发生季铵化反应,生成纤维素季铵盐。
实施例5
首先将0.0333 g纤维素季铵盐溶于2mL水中,再加入丙烯酰胺与马来酸酐摩尔比为6:1的二元共聚物0.1316 g,同时,将0.1179 g聚丙烯胺盐酸盐溶解于1 mL水中,用NaOH水溶液调成中性,将两种溶液混合,在25℃下,发生凝胶化,凝胶质量分数是80.50%,溶胀度是1690.19%。
实施例6
首先将0.0200 g纤维素季铵盐溶于2 mL水中,再加入丙烯酰胺与马来酸酐摩尔比为6:1的二元共聚物0.0790 g,同时,将0.0707 g聚丙烯胺盐酸盐溶解于1 mL水中,用NaOH水溶液调成中性,将两种溶液混合,在25℃下,发生凝胶化,凝胶质量分数是86.91%,溶胀度是1342.73%。
实施例7
首先将0.0166 g壳聚糖季铵盐溶于2mL水中,再加入N-异丙基丙烯酰胺、丙烯酰胺与马来酸酐摩尔比为7:3:1的三元共聚物0.0759 g,同时,将0.0741 g聚丙烯胺盐酸盐溶解于1 mL水中,用NaOH水溶液调成中性,将两种溶液混合,在30℃下,30 min发生凝胶化,凝胶质量分数是69.00%,溶胀度是4564.09%。
实施例8
首先将0.0500壳聚糖季铵盐溶于2 mL水中,再加入N-异丙基丙烯酰胺、丙烯酰胺与马来酸酐摩尔比为7:3:1的三元共聚物0.0759 g,同时,将0.0741 g聚丙烯胺盐酸盐溶解于1 mL水中,用NaOH水溶液调成中性,将两种溶液混合,在30℃下,30 min发生凝胶化,凝胶质量分数是84.60%,溶胀度是1160.41%。
实施例9
首先将0.0333 g纤维素季铵盐溶于2 mL水中,再加入0.05 g埃洛石负载银离子的纳米粒子与丙烯酰胺-马来酸酐共聚物(摩尔比为8:1)0.1488 g,同时,将0.1059 g聚丙烯胺盐酸盐溶解于1 mL水中,用NaOH水溶液调成中性,将两种溶液混合,在25℃下,发生凝胶化。
Claims (6)
1.一种通过水中氨基与酸酐之间的点击反应制备具有抑菌性的半互穿网络气凝胶的制备方法,其特征在于,该方法包括以下步骤:
1)用季铵盐化合物对天然产物纤维素、壳聚糖等天然产物进行修饰;
2)合成含有酸酐与氨基的水溶性聚合物;
3)将含有氨基与酸酐的聚合物、季铵盐修饰的天然产物、具有抑菌性的无机纳米粒子分散于水中;加入少量的碱调节溶液的pH>7,加热,通过氨基与酸酐之间的点击反应发生凝胶化,形成水凝胶;
4)将制备的半互穿网络水凝胶放入蒸馏水中,去除残留在亲水网络水凝胶中的杂质,冷冻干燥可得到气凝胶。
2.根据权利要求1所述的点击反应,其特征在于,含有氨基的聚合物可以是氨基化合物或其盐酸盐,如聚丙烯胺盐酸盐、聚赖氨酸等,含有酸酐的聚合物可以是马来酸酐或衣康酸酐与不同单体(丙烯酰胺、N-异丙基丙烯酰胺、N, N-二甲基丙烯酰胺等)的共聚物,可以是二元共聚物也可是多元共聚物,单体的摩尔比可以根据需要进行调整。
3.根据权利要求1所述的点击反应,其特征在于,氨基与酸酐的反应在水中进行,并且水的pH需用碱调到pH>7;所用的碱可以是强碱氢氧化钠,也可是弱碱碳酸钠、三乙胺、吡啶等。
4.根据权利要求1所述的点击反应,其特征在于,氨基与酸酐的摩尔比可以根据需要进行调节,从而调节水凝胶的性能;反应温度控制在18-50℃,反应时间为0.1-10分钟。
5.根据权利要求1所述的季铵盐修饰的天然产物,天然产物可以是纤维素、壳聚糖等,修饰所用的季铵盐可以是3-氯-2-羟丙基三甲基氯化氨或其它可与天然产物反应的季铵盐化合物。
6.根据权利要求1所述的制备半互穿网络气凝胶的方法,是将得到的水凝胶用水浸泡至溶胀平衡后进行冷冻干燥或超临界干燥得到气凝胶。
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