CN106478994B - 一种基于海藻多糖的聚电解质高吸水材料的制备方法 - Google Patents
一种基于海藻多糖的聚电解质高吸水材料的制备方法 Download PDFInfo
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Abstract
本发明属于高分子复合材料领域,涉及一种基于海藻多糖的聚电解质高吸水材料的制备方法。首先将适量海藻多糖和羧甲基壳聚糖溶解于去离子水中,通过降低聚电解质混合物水溶液的pH值,使海藻多糖分子和羧甲基壳聚糖分子间通过库仑力相互作用形成复合物并凝胶化,聚电解质复合物凝胶经干燥后得到具有超高吸水能力的海藻多糖聚电解质高吸水材料。本发明利用生物质可再生资源海藻多糖为主要成分获得的高吸水材料可生物降解,生物相容性好,吸水倍率高,制备方法简单,生产过程无污染。
Description
技术领域
本发明属于高分子复合材料领域,涉及一种基于海藻多糖的聚电解质高吸水材料的制备方法。
背景技术
高吸水树脂(Super Absorbent Polymer,SAP)是具有强亲水性和特殊吸水保湿能力的一种功能型高分子材料,结构上由含有大量亲水性基团(如:羧基、羟基、羧酸盐基、酰基等)的低交联度的三维空间网络构成,一方面具有高分子电解质的分子扩张性能,另一方面其微交联三维网络结构阻碍分子的进一步扩张,使得高吸水树脂在水中显著溶胀而不溶解。同海绵、纤维素、硅胶等传统吸水材料相比,高吸水树脂可以吸收和保持自身重量几百甚至千倍的水,同时保水性强,即使在受压下也不容易失水。
20世纪60年代美国的Fanta等人利用淀粉和丙烯晴接技共聚技术首次开发成功高吸水性树脂,引起了各国研究人员的浓厚兴趣。进入80年代,美国、德国、法国等发达国家陆续投入工业生产,使全世界高吸水性树脂工业化发展迅猛,使用量大幅增加。目前高吸水性树脂已被大量应用于农业园林、土木建筑、食品加工、石油化工及医疗卫生等领域。
除了广泛采用的淀粉、纤维素等原料以外,采用海藻多糖、蛋白质、壳聚糖等天然化合物及衍生物为原料制造的高吸水性树脂也得到了重视。海藻多糖以钙、镁、钾和钠盐等形式大量存在于多种藻类的细胞壁和细胞间粘液中,在干燥褐藻中可达40%。从海藻中提取海藻多糖已形成了从海藻养殖、加工到海藻多糖综合利用的产业链,广泛应用于纺织印染、食品、医疗卫生、日用化工、生物技术及水处理等领域中。
海藻多糖是由古洛糖醛酸(记为G段)与其立体异构体甘露糖醛酸(记为M段)两种结构单元构成的一种天然多糖,这两种结构单元以MM段、GG段和MG段等三种方式通过1,4糖苷键链接形成线性的嵌段共聚物。海藻多糖的这种独特的结构使其表现出良好的生物降解性、生物相容性和生物粘附性。海藻多糖是一种高纤维食物,并具有医疗和保健作用,如:减缓脂肪糖和胆盐的吸收,降低血清胆固醇、血中甘油三酯和血糖,预防高血压、糖尿病、肥胖症等。海藻多糖还具有柔韧性好,透气性佳,易加工成型等特点,是一种重要的生物医用材料,可用作药物缓释剂、聚合物薄膜、细胞封装、伤口敷料、手术海绵和栓塞剂等,在生物医用材料学、临床医学、组织工程学和药物学等领域正在受到越来越多的关注,特别是利用海藻多糖充当选择性免疫屏障保护移植细胞免受宿主的免疫系统进攻而进行移植和细胞疗法等研究等正成为当前生物工程领域的热点。
海藻多糖分子链上的羟基和羧基与水分子间以氢键缔合而具有吸水性,但天然海藻多糖树脂的吸水性能和力学性能还达不到实际使用要求。一般采用对海藻多糖与很多种类的单体、交联剂、醚化剂进行接枝、聚合、交联、互穿等合成方法制得吸水剂。
壳聚糖易于溶解在大多数有机酸和无机酸中,但不溶水,从而限制了它的应用范围。羧甲基壳聚糖是壳聚糖羧甲基化后的产物。根据羧甲基取代位置的不同可将羧甲基化产物分为O-羧甲基壳聚糖、N-羧甲基壳聚糖和N,O-羧甲基壳聚糖。羧甲基壳聚糖保持了壳聚糖良好的安全、无毒、无害、生物相容性和生物降解性,同时羧甲基的引入使之成为一种既含有氨基又含有羧基的两性聚电解质,破坏了壳聚糖原有的晶体结构,提高了其溶解适应性。由于羧基及氨基都是亲水基团,羧甲基壳聚糖表现出较强的吸水保湿性和成膜、增稠、保湿、絮凝、螯合、胶化和乳化等多种特性,在农业、环保、医药、化妆品、食品加工等领域都有应用。
羧甲基壳聚糖中氨基的pKa值大约为6.5,当溶液的pH值低于6.0时,羧甲基壳聚糖中氨基将因为被质子化而带正电。海藻酸钠中羧基的pKa值大约为3.5,所以当pH值大于3.5时,海藻酸钠中羧基将会带负电。因此,当pH值在3.5和6之间时,海藻多糖分子能够同羧甲基壳聚糖分子通过库仑相互作用力而瞬时形成一种无规则的复合物。这种复合物为一种非平衡状态,随着时间的推移,通过氢键、范德瓦耳斯力、电荷转移及疏水缔合作用力等其它次级相互作用而逐渐形成更稳定的复合物。利用这种聚电解质复合物形成的三维网络结构,在材料制备过程中可以避免使用(如:戊二醛等)有一定毒性的化学交联剂,并能够较好的保留聚电解质材料本身优异的性能。
发明内容
本发明目的在于提供一种基于海藻多糖的聚电解质高吸水材料的制备方法,获得的海藻多糖聚电解质高吸水材料具有优异的生物相容性、生物可降解性和超高吸水保湿性能。
本发明的技术方案是:
一种基于海藻多糖的聚电解质高吸水材料的制备方法,首先配制含有海藻多糖和羧甲基壳聚糖的聚电解质混合物水溶液,调节该溶液的pH值至3.5~6.0区间,使海藻多糖分子与羧甲基壳聚糖分子间通过库仑力相互作用形成复合物凝胶,复合物凝胶经干燥得到海藻多糖聚电解质高吸水材料。
所述的基于海藻多糖的聚电解质高吸水材料的制备方法,采用的海藻多糖分子量在1.8万至210万之间,海藻多糖在聚电解质混合物水溶液中的浓度为0.2~10wt.%。
所述的基于海藻多糖的聚电解质高吸水材料的制备方法,采用的羧甲基壳聚糖的脱乙酰度在65%~100%间,羧甲基化度在30%~110%间,分子量在0.9万至200万间,羧甲基壳聚糖在聚电解质混合物水溶液中的浓度为0.1~13wt.%。
所述的基于海藻多糖的聚电解质高吸水材料的制备方法,调节聚电解质混合物水溶液pH值在3.5~6.0区间时,采用在聚电解质混合物水溶液中加入质子释放剂、聚电解质混合物水溶液浸入酸性溶剂或聚电解质混合物水溶液在酸性气氛中处理方法中的一种或两种以上。
所述的基于海藻多糖的聚电解质高吸水材料的制备方法,质子释放剂采用葡萄糖酸内酯,加入量为聚电解质混合物水溶液总质量的0.03~5wt.%,处理时间为30分钟至8小时。
所述的基于海藻多糖的聚电解质高吸水材料的制备方法,酸性溶液为酸的水或醇水溶液,采用无机酸或有机酸:盐酸、硫酸、磷酸、硝酸、甲酸、乙酸、丙酸、丁酸、辛酸、己二酸、乙二酸、丙二酸、丁二酸、马来酸、酒石酸、苯甲酸、苯乙酸、邻苯二甲酸、对苯二甲酸、戊酸、己酸、癸酸、硬脂酸、软脂酸、丙烯酸、酒石酸、苹果酸、枸椽酸、抗坏血酸,处理时间为0.5小时至20小时。
所述的基于海藻多糖的聚电解质高吸水材料的制备方法,酸性气氛采用盐酸、硝酸、甲酸、乙酸、丙酸、乙二酸易于挥发的无机酸或有机酸,处理时间为20分钟至18小时。
所述的基于海藻多糖的聚电解质高吸水材料的制备方法,聚电解质复合物经过常压干燥、减压干燥、喷雾干燥、流化干燥、冷冻干燥、红外线干燥、干燥剂干燥或微波干燥,得到具有超高吸水性的海藻多糖聚电解质高吸水材料。
所述的基于海藻多糖的聚电解质高吸水材料的制备方法,干燥后的聚电解质复合物经过粉碎机、球磨机或破碎机使颗粒细化,得到具有超高吸水性的粉末状海藻多糖聚电解质高吸水材料。
本发明的优点及有益效果是:
1、本发明利用羧甲基壳聚糖可以在中性水中溶解的特性,配制含有海藻多糖和羧甲基壳聚糖的聚电解质混合物水溶液。在中性条件下羧甲基壳聚糖分子上的氨基没有被质子化,不会同海藻多糖分子相互作用。通过调节该溶液的pH值使羧甲基壳聚糖分子的氨基质子化并带上正电荷,与溶液中的阴离子聚电解质海藻多糖通过库仑力相互作用形成复合物,复合物经干燥后得到海藻多糖聚电解质高吸水材料。
2、本发明利用这种聚电解质复合物形成的三维网络结构,避免了使用(如:戊二醛等)有一定毒性的化学交联剂,并能够较好的保留了海藻多糖和羧甲基壳聚糖材料本身优异的性能,具有明显的优点:吸水倍率高,可以吸收自身重量40至800倍以上的水;抗拉强度大于70MPa,延伸率大于4.5%;具备良好的生物相容性和生物可降解性;制备工艺简单,易于工业化。
附图说明
图1A-图1B.海藻多糖聚电解质高吸水薄膜材料吸水前后照片。其中,图1A为吸水前;图1B为吸水后。
具体实施方式
在具体实施方式中,本发明基于海藻多糖的聚电解质高吸水材料的制备方法,首先将适量海藻多糖和羧甲基壳聚糖溶解于去离子水中,通过降低聚电解质混合物水溶液的pH值,使海藻多糖分子和羧甲基壳聚糖分子间通过库仑力相互作用形成复合物并凝胶化。聚电解质复合物凝胶经干燥后,得到具有超高吸水能力的海藻多糖聚电解质高吸水材料。所采用的具体步骤为:
1)制备含有海藻多糖和羧甲基壳聚糖的聚电解质混合物水溶液。
2)采用在聚电解质混合物水溶液中加入质子释放剂、聚电解质混合物水溶液浸入酸性溶剂中或聚电解质混合物水溶液在酸性气氛中处理等方法中的一种或两种以上,调节聚电解质混合物水溶液的pH值至3.5~6.0区间,使羧甲基壳聚糖分子的氨基被质子化,同阴离子聚电解质海藻多糖通过库仑力相互作用,形成聚电解质复合物;
3)聚电解质复合物经过常压干燥、减压干燥、喷雾干燥、流化干燥、冷冻干燥、红外线干燥、干燥剂干燥或微波干燥等技术干燥,得到具有超高吸水性的海藻多糖聚电解质高吸水材料。
4)干燥后的聚电解质复合物经过粉碎机、球磨机或破碎机等使颗粒细化,得到具有超高吸水性的粉末状的海藻多糖聚电解质高吸水材料。
为使本发明的技术方案和优点更加清楚,下面将结合具体实施方案进行详细描述。
实施例1
30克海藻多糖、30克羧甲基壳聚糖和3g葡萄糖酸内酯在1升去离子水中溶解,然后注入10cm×100cm×30cm长方形玻璃模具中。50℃下保温10小时后,溶液形成聚电解质复合物凝胶。聚电解质复合物凝胶在60℃下鼓风干燥60小时,得到海藻多糖聚电解质高吸水材料薄膜。该聚电解质高吸水材料薄膜厚86μm,抗拉强度110MPa,延伸率7.1%、吸水率450mL/克。
实施例2
10克海藻多糖、30克羧甲基壳聚糖和3g葡萄糖酸内酯在1升去离子水中溶解,然后注入10cm×100cm×30cm长方形玻璃模具中。50℃下保温10小时后,溶液形成聚电解质复合物凝胶。聚电解质复合物凝胶在60℃下鼓风干燥60小时,得到海藻多糖聚电解质高吸水材料薄膜。该聚电解质高吸水材料薄膜厚58μm,抗拉强度130MPa,延伸率4.7%,吸水率130mL/克。
实施例3
30克海藻多糖、10克羧甲基壳聚糖和3g葡萄糖酸内酯在1升去离子水中溶解,然后注入10cm×100cm×30cm长方形玻璃模具中。50℃下保温10小时后,溶液形成聚电解质复合物凝胶。聚电解质复合物凝胶在60℃下鼓风干燥60小时,得到海藻多糖聚电解质高吸水材料薄膜。该聚电解质高吸水材料薄膜厚66μm,抗拉强度106MPa,延伸率6.3%,吸水率712mL/克。
实施例4
30克海藻多糖、30克羧甲基壳聚糖和3g葡萄糖酸内酯在1升去离子水中溶解,然后在50℃下保温10小时后,溶液形成聚电解质复合物。聚电解质复合物在70℃下鼓风干燥60小时,采用球磨机球磨1小时得到海藻多糖聚电解质高吸水材料粉末。该聚电解质高吸水材料粉末颗粒在12μm,吸水率520mL/克。
实施例5
30克海藻多糖、30克羧甲基壳聚糖在1升去离子水中溶解,然后注入10cm×100cm×30cm长方形玻璃模具中。0.3ml浓盐酸溶解于3升去离子水中,缓慢注入到模具中的聚电解质混合物水溶液表面。在室温下处理4小时后,聚电解质混合物水溶液形成凝胶。取出盐酸溶液,聚电解质复合物凝胶在60℃下鼓风干燥60小时,得到海藻多糖聚电解质高吸水材料薄膜。该聚电解质高吸水材料薄膜厚74μm,抗拉强度113MPa,延伸率4.5%,吸水率620mL/克。
实施例6
30克海藻多糖、30克羧甲基壳聚糖在1升去离子水中溶解,然后注入10cm×100cm×30cm长方形玻璃模具中。装有聚电解质混合物水溶液的模具放入乙酸气氛中。在室温下处理15小时后,聚电解质混合物水溶液形成凝胶。聚电解质复合物凝胶在60℃下鼓风干燥60小时,得到海藻多糖聚电解质高吸水材料薄膜。该聚电解质高吸水材料薄膜厚70μm,抗拉强度120MPa,延伸率5.1%,吸水率580mL/克。
实施例7
30克海藻多糖溶解于0.45升去离子水中,30克羧甲基壳聚糖溶解于0.45升去离子水中,7g葡萄糖酸内酯溶解于0.1升去离子水。合并海藻多糖、羧甲基壳聚糖和葡萄糖酸内酯溶液,然后在50℃下保温10小时后,溶液形成聚电解质复合物。聚电解质复合物在70℃下鼓风干燥60小时,采用球磨机球磨1小时得到海藻多糖聚电解质高吸水材料粉末。该聚电解质高吸水材料粉末颗粒在15μm,吸水率550mL/克。
实施例8
30克海藻多糖、30克羧甲基壳聚糖和3g葡萄糖酸内酯在1升去离子水中溶解,然后注入10cm×100cm×30cm长方形玻璃模具中。30℃下保温20小时后,溶液形成聚电解质复合物凝胶。聚电解质复合物凝胶在真空干燥箱中30℃真空干燥48小时,得到海藻多糖聚电解质高吸水材料。该聚电解质高吸水材料吸水率660mL/克。
如图1A-图1B所示,从海藻多糖聚电解质高吸水薄膜材料吸水前后照片可以看出,本发明利用生物质可再生资源海藻多糖为主要成分获得的高吸水材料可生物降解,生物相容性好,吸水倍率高,制备方法简单,生产过程无污染。
Claims (1)
1.一种基于海藻多糖的聚电解质高吸水材料的制备方法,其特征在于:30克海藻多糖、10克羧甲基壳聚糖和3g葡萄糖酸内酯在1升去离子水中溶解,然后注入10cm×100cm×30cm长方形玻璃模具中;50℃下保温10小时后,溶液形成聚电解质复合物凝胶;聚电解质复合物凝胶在60℃下鼓风干燥60小时,得到海藻多糖聚电解质高吸水材料薄膜;该聚电解质高吸水材料薄膜厚66μm,抗拉强度106MPa,延伸率6.3%,吸水率712mL/克。
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Title |
---|
"Preparation and characterization of O-carboxymethyl chitosan-sodium alginate polyelectrolyte complexes";Guo-Qing Huang et al.;《Colloid Polymer Science》;20141022;第401-407页 * |
"海藻酸钠-高甲氧基果胶复合体系凝胶特性的研究";周爱梅等;《食品科技》;20030830(第8期);第66-68页和第71页 * |
"羧甲基壳聚糖/海藻酸钠水凝胶pH值对溶胀行为的影响";闻燕等;《天津商学院学报》;20071125;第27卷(第6期);第12-16页 * |
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