CN108530652B - 一种变性淀粉复合凝胶及其制备方法和应用 - Google Patents
一种变性淀粉复合凝胶及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种变性淀粉复合凝胶及其制备方法和应用。该变性淀粉复合凝胶的制备方法,主要包括以下步骤:1)将淀粉置于水中糊化,向所得混合物中加入两性离子单体和引发剂,搅拌反应0.5~2h,得到两性离子变性淀粉水溶液;所述的两性离子单体为一种化合物,其同一结构单元中同时含有阳离子基团和阴离子基团,两种基团的摩尔比为1:1,两种基团由亚甲基相连,亚甲基个数在0~3之间;2)向所得水溶液中加入聚乙烯醇,回流反应2h~4h,反应物趁热倒入模具中,冷冻成型,即得;所述淀粉、两性离子单体、引发剂和聚乙烯醇的质量比为1:0.1~1:0.001~0.01:2~10。本发明所述的变性淀粉复合凝胶在盐水中具有良好的吸水溶胀性和吸收重金属离子的能力。
Description
技术领域
本发明涉及一种淀粉基水凝胶,具体涉及一种变性淀粉复合凝胶及其制备方法和应用。
背景技术
淀粉基水凝胶属于高分子树脂范畴,淀粉糊化后大多能形成具有一定弹性和强度的半透明凝胶,胶体质点相互交联形成多维网状结构,具有一定的吸水和保水性能,被广泛应用于医疗卫生、农林绿化、日用化工、食品、建筑等领域。同时,淀粉基水凝胶能够自然降解,是一类值得推广的环保型材料。然而,淀粉分子之间的交联较弱,难以满足吸水材料对于力学强度和加工性能的要求,因此通常需要对淀粉进行化学交联或物理交联来增加其强度。
聚乙烯醇具有良好的力学性能和生物相容性,是常用于医药及生物领域的人工合成高分子。聚乙烯醇经过冷冻-解冻的循环过程可以形成物理交联水凝胶。淀粉的羟基与聚乙烯醇的羟基之间能形成氢键,从而使制备的淀粉基聚乙烯醇复合凝胶具备一定的力学强度,同时克服聚乙烯醇降解性较差的缺点,如《PVA/淀粉接枝P(AA-AM)互穿网络水凝胶的合成与性能研究》(祝宝东、孟静、王鉴等,科学技术与工程,2011,11(10):2234-2238)。
复合凝胶吸水材料相关产品普遍存在吸淡水性能好但吸盐水性能差的问题,如《有机/无机复合高吸水树脂的制备及性能》(韩月云、曹奇领、化全县等,化工学报,2015,66(9):3795-3800)。通常情况下,吸收盐水的能力仅为吸收淡水能力的十分之一至几十分之一,因此,如何兼顾吸水性、耐盐性和力学强度,成为高分子吸水树脂的主要研究方向之一。
发明内容
本发明要解决的技术问题是提供一种在盐水中具有良好的吸水溶胀性和吸收重金属离子的能力的变性淀粉复合凝胶及其制备方法和应用。
本发明所述的变性淀粉复合凝胶,其结构如下式(I)所示:
其中,x=0.1~0.3,y=0.03~0.1,n=0~3。
上述变性淀粉复合凝胶的制备方法,主要包括以下步骤:
1)将淀粉置于水中糊化,向所得混合物中加入两性离子单体和引发剂,搅拌反应0.5~2h,得到两性离子变性淀粉水溶液;其中,所述的两性离子单体为一种化合物,其同一结构单元中同时含有阳离子基团和阴离子基团,两种基团的摩尔比为1:1,两种基团由亚甲基相连,亚甲基个数在0~3之间;
2)向两性离子变性淀粉水溶液中加入聚乙烯醇,回流反应2h~4h,反应物趁热倒入模具中,冷冻成型,得到变性淀粉复合凝胶的水合物;其中,
所述淀粉、两性离子单体、引发剂和聚乙烯醇的质量比为1:0.1~1:0.001~0.01:2~10。
按本发明所述方法制备得到的变性淀粉复合凝胶,其分子中同时具有阳离子基团和阴离子基团,当两种离子比例相等时分子整体呈电中性,存在着电荷近程吸引与远程排斥作用,能形成交联的网络结构,水溶液粘度可以随外加低分子量电解质(如NaCl、CaCl2等)浓度的增加而提高,表现出明显的反聚电解质行为,使聚合物具有良好的抗盐性能。盐的存在屏蔽了阳离子和阴离子间的近程电荷吸引作用,聚合物分子链在盐水中从卷曲变为伸展,流体力学尺寸增大,在宏观上表现为溶胀性和吸水性增强。
本发明所述制备方法中,所述的淀粉和引发剂均为现有技术中的常规选择,具体的,淀粉可以是选自薯类淀粉、谷物淀粉、玉米淀粉和豆类淀粉等中的一种或两种以上的组合。引发剂可以是选自过硫酸铵、过硫酸钾、硝酸铈铵和硫酸高铈等中的一种或两种以上的组合。
上述制备方法的步骤1)中,将淀粉置于水中糊化的操作与现有技术相同,通常是将淀粉置于水中升温至80~90℃糊化1~2h,其中淀粉和水的质量比优选为1:10~100。
上述制备方法的步骤1)中,两性离子单体中的阳离子基团可以是选自铵基和铵基衍生物(具体如可接受质子的叔胺、季铵盐或烷基季铵盐等)中的一种,阴离子基团可以是选自羧基、磺酸基和磷酸基中的一种。
上述制备方法的步骤2)中,聚乙烯醇的醇解度为80~99%,优选为85~89%;所述冷冻的温度具体可以是-20~-15℃,在上述冷冻温度下,冷冻至成型的时间通常为10~12h,用于盛装反应物的模具可根据需要进行选择。
由上述方法制备得到的是变性淀粉复合凝胶的水合物,还可将所得水合物解冻后进一步进行干燥以得到变性淀粉复合凝胶粉末状产品。所述的解冻通常在常温条件下进行,所述的干燥通常在较低的温度下进行,优选是在30~50℃条件下进行。
本发明还包括上述变性淀粉复合凝胶作为重金属吸附剂中的应用,特别是在盐水环境中作为重金属吸附剂中的应用。
与现有技术相比,本发明的特点在于:
本发明通过将两性离子单体引入淀粉分子中,使所得变性淀粉复合凝胶在盐水中具有良好的吸水溶胀性和吸收重金属离子的能力,同时因为聚乙烯醇的加入使所得变性淀粉复合凝胶也具备较好的力学强度。该方法反应条件温和、操作方法简便且无需分离提纯,产率可达到90%以上,所得物质可以自然降解。该物质有望应用于盐碱荒漠治理、医疗卫生、环境保护等方面。
附图说明
图1为本发明实施例1制得的变性淀粉复合凝胶粉末在盐水中的溶胀性能曲线;
图2为本发明实施例1制得的变性淀粉复合凝胶粉末吸收铜离子的性能曲线;
图3为本发明实施例1制得的变性淀粉复合凝胶的水合物自然降解七天后的照片。
具体实施方式
下面结合具体实施例对本发明作进一步的详述,以更好地理解本发明的内容,但本发明并不限于以下实施例。
实施例1
1)将250ml三口烧瓶放入油浴锅中,加入2g淀粉(薯类淀粉)和90ml纯水,升温至85℃,磁力搅拌冷凝回流1h后,加入0.5g两性离子单体(阳离子基团为二甲基乙基胺,阴离子基团为羧基,两种基团的摩尔比为1:1,两种基团由亚甲基相连,亚甲基的个数为0)和0.01g引发剂(过硫酸钾,先用少量水溶解),保温搅拌2h,得两性离子变性淀粉的水溶液;
2)向到步骤1)所得的水溶液中加入8g聚乙烯醇,在90℃下冷凝回流4h,所得反应物趁热倒入模具中,立即放入-18℃条件下冷冻12h,得白色或浅褐色坚硬固体物,即为变性淀粉复合凝胶的水合物;
3)将步骤2)所得水合物置于常温放置解冻(解冻后变为柔软弹性物),之后置于烘箱中于40℃条件下烘干,取出,粉碎,得到变性淀粉复合凝胶粉末状产品,称重为9.6g;其中,所述淀粉、纯水、两性离子单体、引发剂和聚乙烯醇的质量比为1:45:0.25:0.005:4。
实施例2
1)将250ml三口烧瓶放入油浴锅中,加入淀粉(豆类淀粉)和纯水,升温至80℃,磁力搅拌冷凝回流2h后,加入两性离子单体(阳离子基团为三甲基胺,阴离子基团为磺酸基,两种基团的摩尔比为1:1,两种基团由亚甲基相连,亚甲基的个数为1)和引发剂(硝酸铈铵,先用少量水溶解),保温搅拌2h,得两性离子变性淀粉的水溶液;
2)向步骤1)所得的水溶液中加入聚乙烯醇,在80℃下冷凝回流4h,所得反应物趁热倒入模具中,立即放入-20℃条件下冷冻10h,得白色或浅褐色坚硬固体物,即为变性淀粉复合凝胶的水合物;
3)将步骤2)所得水合物置于常温放置解冻(解冻后变为柔软弹性物),之后置于烘箱中于50℃条件下烘干,取出,粉碎,得到变性淀粉复合凝胶粉末状产品,称重为16.4g;其中
所述淀粉的质量为2g,所述淀粉、纯水、两性离子单体、引发剂和聚乙烯醇的质量比为1:100:0.5:0.01:8。
实施例3
1)将250ml三口烧瓶放入油浴锅中,加入淀粉(由谷物淀粉和玉米淀粉按1:1的质量比组成)和纯水,升温至90℃,磁力搅拌冷凝回流1h后,加入两性离子单体(阳离子基团为四甲基氯化铵,阴离子基团为磷酸基,两种基团的摩尔比为1:1,两种基团由亚甲基相连,亚甲基的个数为2)和引发剂(由过硫酸铵和硫酸高铈按2:1的质量比组成),保温搅拌2h,得两性离子变性淀粉的水溶液;
2)向步骤1)所得的水溶液中加入聚乙烯醇,在90℃下冷凝回流2h,所得反应物趁热倒入模具中,立即放入-15℃条件下冷冻10h,得白色或浅褐色坚硬固体物,即为变性淀粉复合凝胶的水合物;
3)将步骤2)所得水合物置于常温放置解冻(解冻后变为柔软弹性物),之后置于烘箱中于50℃条件下烘干,取出,粉碎,得到变性淀粉复合凝胶粉末状产品,称重为20.7g;其中
所述淀粉的质量为2g,所述淀粉、纯水、两性离子单体、引发剂和聚乙烯醇的质量比为1:80:1:0.001:10。
实施例4
1)将250ml三口烧瓶放入油浴锅中,加入淀粉(玉米淀粉)和纯水,升温至90℃,磁力搅拌冷凝回流2h后,加入两性离子单体(阳离子基团为三甲基丙基溴化铵,阴离子基团为羧甲基,两种基团的摩尔比为1:1,两种基团由亚甲基相连,亚甲基的个数为3)和引发剂(过硫酸铵),保温搅拌3h,得两性离子变性淀粉的水溶液;
2)向步骤1)所得的水溶液中加入聚乙烯醇,在90℃下冷凝回流2h,所得反应物趁热倒入模具中,立即放入-15℃条件下冷冻10h,得白色或浅褐色坚硬固体物,即为变性淀粉复合凝胶的水合物,称重为22.7g;其中
所述淀粉的质量为2g,所述淀粉、纯水、两性离子单体、引发剂和聚乙烯醇的质量比为1:10:0.1:0.003:2。
实验例1:变性淀粉复合凝胶粉末在盐水中的溶胀性能测定
称取变性淀粉复合凝胶粉末(按实施例1所述方法制得)1g,在20℃环境下,放入纯水中或质量浓度5%的氯化钠盐水中,测定不同浸泡时间下的凝胶吸水率(SR),结果如图1所示。
由图1可知,浸泡时间超过50分钟后吸水率趋于稳定;在5%的氯化钠盐水中,此凝胶的吸水率高于在纯水中的数值,说明按本发明所述方法制得的产品在盐水中有良好的吸水效果,具有优异的吸收盐水的性能。
实验例2:变性淀粉复合凝胶粉末吸收铜离子性能测定
称取变性淀粉复合凝胶粉末(按实施例1所述方法制得)1g,在20℃环境下,分别放入硫酸铜摩尔浓度5mmol/L的纯水溶液或硫酸铜摩尔浓度5mmol/L的盐水(氯化钠质量浓度5%)中,测定凝胶对铜离子的吸收性能,如图2所示。
由图2可知,吸收量随浸泡时间延长而增加;在5%的氯化钠盐水中,此凝胶对铜离子的的吸收效果高于在纯水中的数值,说明按本发明所述方法制得的产品在盐水中具有良好的吸收重金属离子的性能。
实验例3:变性淀粉复合凝胶的水合物自然降解过程
取变性淀粉复合凝胶的水合物(按实施例1所述方法制得),在20℃环境下放置7天,观察其自然霉变的效果,结果如图3所示。
由图3可知,在空气中放置7天以后出现大量霉变斑,说明本发明所述方法制得的产品具有较好的降解性能。
Claims (8)
1.一种变性淀粉复合凝胶,其结构如下式(I)所示:
其中,x=0.1~0.3,y=0.03~0.1,n=0~3;
所述变性淀粉复合凝胶的制备方法主要包括以下步骤:
1)将淀粉置于水中糊化,向所得混合物中加入两性离子单体和引发剂,搅拌反应0.5~2h,得到两性离子变性淀粉水溶液;其中,所述的两性离子单体为一种化合物,其同一结构单元中同时含有阳离子基团和阴离子基团,两种基团的摩尔比为1:1,两种基团由亚甲基相连,亚甲基个数在0~3之间;两性离子单体中的阳离子基团为选自铵基和铵基衍生物中的一种,阴离子基团为选自羧基、磺酸基和磷酸基中的一种;所述的铵基衍生物为可接受质子的叔胺、季铵盐或烷基季铵盐;
2)向两性离子变性淀粉水溶液中加入聚乙烯醇,回流反应2h~4h,反应物趁热倒入模具中,冷冻成型,得到变性淀粉复合凝胶的水合物;其中,
所述淀粉、两性离子单体、引发剂和聚乙烯醇的质量比为1:0.1~1:0.001~0.01:2~10。
2.权利要求1所述变性淀粉复合凝胶的制备方法,主要包括以下步骤:
1)将淀粉置于水中糊化,向所得混合物中加入两性离子单体和引发剂,搅拌反应0.5~2h,得到两性离子变性淀粉水溶液;其中,所述的两性离子单体为一种化合物,其同一结构单元中同时含有阳离子基团和阴离子基团,两种基团的摩尔比为1:1,两种基团由亚甲基相连,亚甲基个数在0~3之间;两性离子单体中的阳离子基团为选自铵基和铵基衍生物中的一种,阴离子基团为选自羧基、磺酸基和磷酸基中的一种;所述的铵基衍生物为可接受质子的叔胺、季铵盐或烷基季铵盐;
2)向两性离子变性淀粉水溶液中加入聚乙烯醇,回流反应2h~4h,反应物趁热倒入模具中,冷冻成型,得到变性淀粉复合凝胶的水合物;其中,
所述淀粉、两性离子单体、引发剂和聚乙烯醇的质量比为1:0.1~1:0.001~0.01:2~10。
3.根据权利要求2所述的制备方法,其特征在于:还包括干燥步骤,具体为:将所得变性淀粉复合凝胶的水合物解冻,干燥,得到变性淀粉复合凝胶粉末。
4.根据权利要求2或3所述的制备方法,其特征在于:步骤1)中,所述的淀粉为选自薯类淀粉、谷物淀粉、玉米淀粉和豆类淀粉中的一种或两种以上的组合。
5.根据权利要求2或3所述的制备方法,其特征在于:步骤1)中,所述淀粉和水的质量比为1:10~100。
6.根据权利要求2或3所述的制备方法,其特征在于:步骤1)中,所述的引发剂为选自过硫酸铵、过硫酸钾、硝酸铈铵和硫酸高铈中的一种或两种以上的组合。
7.根据权利要求2或3所述的制备方法,其特征在于:步骤2)中,冷冻的温度为-20~-15℃。
8.权利要求1所述变性淀粉复合凝胶作为重金属吸附剂中的应用。
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