CN106622153B - 一种胶原/壳聚糖印迹材料的制备方法 - Google Patents

一种胶原/壳聚糖印迹材料的制备方法 Download PDF

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CN106622153B
CN106622153B CN201611038643.0A CN201611038643A CN106622153B CN 106622153 B CN106622153 B CN 106622153B CN 201611038643 A CN201611038643 A CN 201611038643A CN 106622153 B CN106622153 B CN 106622153B
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邓慧
阿依非热
王晓宁
郑智远
王雪
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Abstract

本发明涉及一种胶原与壳聚糖的共混物为功能单体,EDTA为交联剂,Cu(Ⅱ)为模板的印迹材料的制备及应用。该材料首先将胶原与壳聚糖以一定比例溶解于醋酸溶液中,缓慢向该溶液中加入一定量的EDTA,室温搅拌一定时间后加入适量戊二醛,加入一定浓度的硫酸铜溶液搅拌一定时间后将混合物低温烘干。用盐酸和氢氧化钠溶液交替洗去混合物中的模板Cu2+后蒸馏水反复洗涤低温烘干便可得到Cu(Ⅱ)印迹材料。该材料对Cu2+具有良好的去除能力,胶原与壳聚糖的共混和EDTA的交联可以加强壳聚糖的机械强度,同时还可以增强壳聚糖对Cu2+的去除能力。

Description

一种胶原/壳聚糖印迹材料的制备方法
技术领域
本发明涉及一种Cu(Ⅱ)的印迹材料,尤其涉及一种胶原/壳聚糖印迹材料的制备方法。
背景技术
壳聚糖是一种性能优良的天然高分子材料,因分子中有大量的羟基和氨基,对许多金属离子具有良好的螯合作用,能有效地吸附或捕集水体中的金属离子。但壳聚糖为弱碱性高分子聚合物,在酸性条件下会软化流失甚至溶解,不利于回收再利用,因而限制了其实际应用。交联剂与壳聚糖作用可以改善其酸溶性,但由于交联占用了大量的羟基和氨基等活性基团,导致交联后的壳聚糖吸附性能大大降低。
发明内容
本发明针对上述现有技术中存在的问题,提供一种胶原/壳聚糖印迹材料的制备方法,为了克服壳聚糖作为功能单体易酸溶,强度低,对金属离子的螯合能力有限的缺点,添加胶原与壳聚糖共同作为功能单体。为了克服过量交联剂有可能引起的吸附容量降低的问题,改用EDTA这种金属离子螯合剂作为主要的交联剂,辅以少量戊二醛进行交联。
该吸附剂制备方法包括如下步骤:
步骤1、将适量胶原和壳聚糖用醋酸溶液溶解搅拌一定时间;
步骤2、向胶原和壳聚糖的混合物中加入一定量的EDTA,室温搅拌一定时间后加入适量戊二醛继续搅拌一定时间;
步骤3、向上述混合物中加入一定浓度的硫酸铜溶液搅拌一段时间后,将得到的蓝色凝胶于低温下烘干后用0.1mol/L的盐酸和0.1mol/L的氢氧化钠溶液反复洗涤至凝胶无色后蒸馏水洗涤,低温烘干便可得到胶原/壳聚糖印迹材料。
所述的步骤1中,胶原为商品胶原纤维。
所述的步骤1中,胶原和壳聚糖要完全溶解混合。
所述的步骤1中,胶原与壳聚糖的质量比例范围为3:1—1:1。
所述的步骤1中,醋酸溶液质量浓度为2%-5%,搅拌时间2h。
所述的步骤2中,EDTA与壳聚糖的质量比例范围为1:2—1:20,戊二醛的添加量为1:15—1:30(V/V)。
所述的步骤2中,搅拌时间为1-2h。
所述的步骤3中,硫酸铜溶液的浓度为0.8g/L-1g/L,搅拌时间为1-4h,硫酸铜溶液与混合物溶液的体积比为2:1-3:1。
本发明的优点和特点:
胶原纤维是一种外观白色、透明的天然纤维,是直链结构性蛋白,在胶原纤维分子中含有大量羧基、氨基、羟基等活性基团,具有很高的化学活性,能和水分子以氢键结合,亲水能力强。壳聚糖与胶原纤维共混可以改善壳聚糖的机械强度和在酸性介质中的稳定性,并且胶原纤维属于天然高分子产物,易与壳聚糖混合。EDTA是一种含有羧基和氨基的螯合剂, 具有广泛的配位能力,可以有效提高壳聚糖对金属离子的吸附能力。金属离子印迹技术是以金属离子为模板分子印迹技术原理制备对模板金属离子有选择吸附性能的高分子功能材料的一种方法。金属离子为模板制备的壳聚糖树脂对多元金属离子溶液的吸附,与未印迹的壳聚糖相比,其对目标离子的选择吸附性会大大提高。利用EDTA作为交联剂,不仅可以增强壳聚糖的物理强度,而且可以增强壳聚糖对金属离子的络合能力。本发明以壳聚糖和胶原的共混物作为功能单体,EDTA作为交联剂,采用离子印迹的方法合成对Cu2+具有良好吸附性能的材料。
附图说明
图1为胶原/壳聚糖印迹材料的电镜扫描图片。
图2为实施例1中的胶原/壳聚糖印迹材料不同的接触时间条件下对50ml初始浓度100mg/L的Cu(Ⅱ)的吸附效果图。
具体实施方式
实施例1
0.5g壳聚糖,0.5g胶原纤维溶解于20ml醋酸溶液中搅拌2h 至溶液透明,向溶液中缓慢加入0.05g EDTA,tiji室温下搅拌2小时,逐滴加入2ml戊二醛/甲醛溶液搅拌1h,加入0.8g/L的硫酸铜溶液12.5ml搅拌1h后形成蓝色凝胶,50℃低温烘干后,用0.1mol/L盐酸溶液和0.1mol/L氢氧化钠溶液分别浸泡洗去蓝色后,50℃低温烘干则得到胶原/壳聚糖印迹材料。
取0.01g胶原/壳聚糖印迹材料加入到50ml初始浓度为100mg/L的Cu(Ⅱ)溶液中震荡24小时后过滤分离,取上清液采用铜离子电极法测定溶液残余Cu(Ⅱ)浓度,计算去除率为99%。
实施例2
0.5g壳聚糖,0.8g胶原纤维溶解于20ml醋酸溶液中搅拌2h 至溶液透明,向溶液中缓慢加入0.1g EDTA,,室温下搅拌2小时,逐滴加入2ml戊二醛/甲醛溶液搅拌2h,加入0.8g/L的硫酸铜溶液12.5ml搅拌2h后形成蓝色凝胶,50℃低温烘干后,用0.1mol/L盐酸溶液和0.1mol/L氢氧化钠溶液分别浸泡洗去蓝色后,50℃低温烘干则得到胶原/壳聚糖印迹材料
取0.01g胶原/壳聚糖印迹材料加入到50ml初始浓度为100mg/L的Cu(Ⅱ)溶液中震荡24小时后过滤分离,取上清液采用铜离子电极法测定溶液残余Cu(Ⅱ)浓度,计算去除率为99%。
实施例3
0.5g壳聚糖,1.0g胶原纤维溶解于20ml醋酸溶液中搅拌2h 至溶液透明,向溶液中缓慢加入0.2g EDTA,,室温下搅拌2小时,逐滴加入2ml戊二醛/甲醛溶液搅拌2h,加入1g/L的硫酸铜溶液10ml搅拌2h后形成蓝色凝胶,50℃低温烘干后,用0.1mol/L盐酸溶液和0.1mol/L氢氧化钠溶液分别浸泡洗去蓝色后,50℃低温烘干则得到胶原/壳聚糖印迹材料
取0.01g胶原/壳聚糖印迹材料加入到50ml初始浓度为200mg/L的Cu(Ⅱ)溶液中震荡24小时后过滤分离,取上清液采用铜离子电极法测定溶液残余Cu(Ⅱ)浓度,计算去除率为99%。
实施例4
0.5g壳聚糖,1.0g胶原纤维溶解于20ml醋酸溶液中搅拌2h 至溶液透明,向溶液中缓慢加入0.5g EDTA,,室温下搅拌2小时,逐滴加入2ml戊二醛/甲醛溶液搅拌2h,加入1g/L的硫酸铜溶液10ml搅拌2h后形成蓝色凝胶,50℃低温烘干后,用0.1mol/L盐酸溶液和0.1mol/L氢氧化钠溶液分别浸泡洗去蓝色后,50℃低温烘干则得到胶原/壳聚糖印迹材料
取0.01g胶原/壳聚糖印迹材料加入到50ml初始浓度为400mg/L的Cu(Ⅱ)溶液中震荡24小时后过滤分离,取上清液采用铜离子电极法测定溶液残余Cu(Ⅱ)浓度,计算去除率为99%。
实施例5
取一系列0.01g实施例1中的胶原/壳聚糖印迹材料加入到50ml初始浓度为100mg/L的Cu(Ⅱ)溶液中,震荡不同时间后离心过滤取上清液采用铜离子电极法测定溶液残余的染料浓度,计算其去除率,如图2所示。

Claims (6)

1.一种胶原/壳聚糖印迹材料的制备方法,其特征在于包括下述步骤:
步骤1、将适量胶原和壳聚糖用醋酸溶液溶解搅拌一定时间;
步骤2、向胶原和壳聚糖的混合物中加入一定量的EDTA,室温搅拌一定时间后加入适量戊二醛继续搅拌一定时间;
步骤3、向上述混合物中加入一定浓度的硫酸铜溶液搅拌一段时间后,将得到的蓝色凝胶于低温下烘干后用0.1mol/L的盐酸和0.1mol/L的氢氧化钠溶液反复洗涤至凝胶无色后蒸馏水洗涤,低温烘干便可得到胶原/壳聚糖印迹材料;
所述的步骤1中,胶原与壳聚糖的质量比例范围为3:1—1:1;
所述的步骤2中,EDTA与壳聚糖的质量比例范围为1:2—1:20,戊二醛的添加量为1:15—1:30(V/V)。
2.根据权利要求1所述的一种胶原/壳聚糖印迹材料的制备方法,其特征在于所述的步骤1中,胶原为商品胶原纤维。
3.根据权利要求1所述的一种胶原/壳聚糖印迹材料的制备方法,其特征在于所述的步骤1中,胶原和壳聚糖要完全溶解混合。
4.根据权利要求1所述的一种胶原/壳聚糖印迹材料的制备方法,其特征在于所述的步骤1中,醋酸溶液质量浓度为2%-5%,搅拌时间2h。
5.根据权利要求1所述的一种胶原/壳聚糖印迹材料的制备方法,其特征在于所述的步骤2中,搅拌时间为1-2h。
6.根据权利要求1所述的一种胶原/壳聚糖印迹材料的制备方法,其特征在于所述的步骤3中,硫酸铜溶液的浓度为0.8g/L-1g/L,搅拌时间为1-4h,硫酸铜溶液与混合物溶液的体积比为2:1-3:1。
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