CN107326650A - 一种涤纶非织造织物的改性方法 - Google Patents

一种涤纶非织造织物的改性方法 Download PDF

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CN107326650A
CN107326650A CN201710613408.XA CN201710613408A CN107326650A CN 107326650 A CN107326650 A CN 107326650A CN 201710613408 A CN201710613408 A CN 201710613408A CN 107326650 A CN107326650 A CN 107326650A
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CN107326650B (zh
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张辉
薛海军
韩白冰
徐军
孙润军
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Xian Polytechnic University
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Abstract

本发明公开了一种涤纶非织造织物的改性方法,具体为:首先对涤纶非织造织物前处理,除去涤纶非织造布表面粘附的杂质;然后在涤纶非织造布填充壳聚糖柠檬酸凝胶整理液:最后在填充整理后的涤纶非织造织物表面负载纳米二氧化钛,即得到具有光催化活性,且能够吸附重金属离子的织物。本发明采用化学接枝方法将壳聚糖柠檬酸凝胶填充整理到涤纶非织造布内部,同时在织物表面负载二氧化钛颗粒薄膜,开发出了一种既可以光催化降解有机污染物,又能够吸附重金属离子的材料。制备出的涤纶非织造布机械和化学稳定性好,光催化活强,吸附具有选择性,环境友好。且通过洗脱附能够去除重金属离子,对光催化降解不会造成影响,可以多次重复使用,节约了成本。

Description

一种涤纶非织造织物的改性方法
技术领域
本发明属于纺织工程技术领域,涉及一种涤纶非织造织物的改性方法。
背景技术
密度大于4.5g·cm-3的金属如铜、锰、铅、金和银等一般称为重金属。当水体中重金属离子含量过高时,便会造成水体污染,重金属离子污染持续时间长,很难自行降解,而且会通过食物链富集放大其毒性,危害到水生动植物以及人类的健康,已引起人们的高度关注。目前,水体中重金属离子处理方法主要有化学沉淀法、离子交换法、薄膜法、电化学法和吸附法等,其中吸附法具有高效,成本低廉,操作简便和安全等优点。
纺织印染废水中不仅含有重金属离子,而且还残留有大量的有机染料成分,特别是苯、萘和蒽醌类有机物,芳香族硝基化合物,芳香族胺类化合物,以及联苯等多苯环的取代化合物,其毒性都比较大,且很难自然降解。壳聚糖是甲壳动物外壳中的甲壳素经过碱性水解去除部分乙酰基后的衍生物,化学名称为β-(1-4)-2-氨基-2-脱氧-D-葡萄糖(脱乙酰甲壳素)。壳聚糖的相对分子质量变化范围比较广,溶解度会随着脱乙酰度和分子量的不同发生变化,脱乙酰度越大分子量越小,其溶解度也就越大。壳聚糖能够溶解于浓的无机酸、稀的有机酸,一般不溶于水、碱性液体和普通有机溶剂。壳聚糖含有大量的活性基团-NH2和-OH,可作为天然阳离子絮凝剂,与重金属离子会生成稳定的五环鳌合物。壳聚糖没有毒性,可生物降解,处理水中的重金属离子不会引发二次污染,而且来源丰富,价格低廉,是一种环保优良的水处理材料。使用交联改性可以提高壳聚糖的稳定性、吸附选择性和环境友好性,三维网状结构交联高分子和溶剂彼此作用产生溶胀,交联网状结构能够限定溶胀活动,交联程度决定了溶胀水平,交联密度越高,溶胀度越小。但缺点是壳聚糖比较软,机械强度差,与其他硬质原料相比容易挥发,凝胶性质不稳定,而且交联改性后氨基数目会变少,降低了壳聚糖凝胶吸附重金属离子的容量。研究表明,交联剂对壳聚糖水凝胶吸附重金属离子影响很大,以往人们多使用柠檬酸交联壳聚糖接枝改性涤纶织物,用来制备吸附重金属离子的功能性材料,但是吸附较慢,去除重金属能力不是很高,且功能比较单一。目前具有光催化活性和吸附重金属能力的涤纶非织造布改性方法还未见报道。
发明内容
本发明的目的是提供一种涤纶非织造织物的改性方法,用以制备一种既可以光催化降解水中有机污染物,又能够吸附重金属离子的功能性织物。
本发明所采用的技术方案是,一种涤纶非织造织物的改性方法,具体按照以下步骤实施:
步骤1,涤纶非织造织物前处理,除去涤纶非织造布表面粘附的杂质;
步骤2,涤纶非织造布填充壳聚糖柠檬酸凝胶整理液:
将步骤1前处理后的涤纶非织造织物浸泡在壳聚糖柠檬酸凝胶整理液,进行填充整理;
步骤3,对步骤2填充整理后的涤纶非织造织物表面负载纳米二氧化钛,即得到具有光催化活性,且能够吸附重金属离子的织物。
本发明的特点还在于,
步骤1前处理具体为:将涤纶非织造布浸泡在氢氧化钠溶液中,在80℃~100℃条件下处理50~70min,随后用去离子水反复清洗直至洗液为中性,最后40℃~60℃烘干。
步骤1中涤纶非织造布与氢氧化钠溶液的质量比为1:10~30,氢氧化钠溶液的浓度为25~45g/L。
步骤2中壳聚糖柠檬酸凝胶整理液制备的具体过程为:
在乙酸水溶液中添加壳聚糖,20℃~40℃条件下磁力搅拌2~4h使其充分降解,然后依次加入柠檬酸、次亚磷酸钠、戊二醛和聚乙二醇,20℃~40℃条件下搅拌5~10min,即得到壳聚糖柠檬酸凝胶整理液。
壳聚糖与乙酸水溶液的质量比为1:30~50,乙酸水溶液的质量百分比浓度为5%~10%,壳聚糖的脱乙酰度为85%~95%,柠檬酸、次亚磷酸钠、戊二醛和聚乙二醇加入量分别为反应体系质量百分比浓度的1~3%、1~3%、0.1~0.3%和0.5~1.5%。
步骤2中填充整理过程具体为:将步骤1前处理后的涤纶非织造布浸泡在壳聚糖柠檬酸凝胶整理液中,放置到真空干燥箱中抽真空20~40min,真空度低于-0.1Mpa,然后在75℃~95℃条件下预烘10~20min。
涤纶非织造布与壳聚糖柠檬酸凝胶整理液的质量比为1:10~30。
步骤3中,涤纶非织造布表面负载纳米二氧化钛具体过程为:
在步骤2填充好的涤纶非织造布表面喷涂钛酸四丁酯无水乙醇溶液,然后在140℃~160℃条件下焙烘10~30min,随后将喷涂后的涤纶非织造布浸泡在去离子水中,90℃~110℃条件下处理20~40min,最后在40~60℃烘干。
钛酸四丁酯无水乙醇溶液的质量百分比浓度为8%~12%,喷涂用量为0.01~0.05mL/cm2
涤纶非织造布与去离子水的质量比为1:30~50。
本发明的有益效果是,
(1)本发明采用化学接枝方法将壳聚糖柠檬酸凝胶填充整理到涤纶非织造布内部,同时在织物表面负载锐钛矿型纳米二氧化钛颗粒薄膜,开发出一种既可以光催化降解有机污染物,又能够吸附重金属离子具有双重功能的材料。利用非织造布内部大小不等的孔隙以及壳聚糖柠檬酸凝胶构成的三维网络结构,以增强对重金属离子的吸附性能,而布面负载的纳米二氧化钛经紫外线或可见光辐照又能够对水中的有机污染物进行光催化降解,实现了纺织印染废水净化处理。
(2)本发明中所使用的涤纶非织造布来源广泛,成本低廉,改性方法简便易操作,安全可靠,制备出的涤纶非织造布机械和化学稳定性好,光催化活强,吸附具有选择性,而且环境友好。壳聚糖柠檬酸凝胶大分子结构中的羟基、氨基与重金属离子会形成稳定的鳌合物,同时又不会去除水中的钾、钠、钙和镁等离子,也不会去除氯、硫酸根、碳酸根和碳酸氢根离子。因此不会改变水体浓度,是处理印染废水、回收贵金属的好方法。
(3)本发明方法所得的涤纶非织造布光催化降解有机染料和吸附重金属离子效率高,通过洗脱附能够去除重金属离子,对光催化降解不会造成影响,非织造布可以多次重复使用,节约了成本。
附图说明
图1为本发明方法所得涤纶非织造布的扫描电镜照片;
图2为本发明方法所得涤纶非织造布的XRD谱图;
图3为本发明方法所得涤纶非织造布的热重-差热曲线;
图4为本发明方法所得涤纶非织造布的红外光谱曲线;
图5为本发明方法所得涤纶非织造布的漫反射光谱曲线;
图6为本发明方法所得涤纶非织造布在温度293K条件下的Langmuir等温吸附模型;
图7为本发明方法所得涤纶非织造布在不同初始铜离子浓度条件下的准二级动力学模型拟合曲线。
具体实施方式
下面结合附图和具体实施方式对本发明进行详细说明。
本发明一种涤纶非织造织物的改性方法,具体按照以下步骤实施:
步骤1:涤纶非织造织物前处理,除去涤纶非织造布表面粘附的杂质:
按照织物质量与溶液质量之比1:10~30称取涤纶非织造织物,将其浸泡在25~45g/L的氢氧化钠溶液中,在80℃~100℃条件下处理50~70min,随后用去离子水反复清洗直至洗液pH值为7.0,最后40℃~60℃烘干。
步骤2:壳聚糖柠檬酸凝胶整理液的制备:
按照壳聚糖质量与溶液质量之比1:30~50,在质量百分比浓度5%~10%的乙酸水溶液中添加脱乙酰度85%~95%的壳聚糖,20℃~40℃条件下磁力搅拌2~4h使其充分降解,然后依次加入一定量的柠檬酸、次亚磷酸钠、戊二醛和聚乙二醇,其中柠檬酸在反应体系中的质量百分比浓度为1~3%,次亚磷酸钠在反应体系中的质量百分比浓度为1~3%,戊二醛在反应体系中的质量百分比浓度为0.1~0.3%,以及聚乙二醇在反应体系中的质量百分比浓度为0.5~1.5%,在20℃~40℃条件下磁力搅拌5~10min,密闭冷藏备用;
步骤3:涤纶非织造布填充壳聚糖柠檬酸凝胶整理液:
按照织物质量与壳聚糖柠檬酸凝胶整理液质量之比1:10~30,将步骤1处理好的涤纶非织造布浸泡在步骤2配制好的壳聚糖柠檬酸凝胶整理液中,然后放置到真空干燥箱中抽真空20~40min,真空度低于-0.1Mpa,接着在75℃~95℃条件下预烘10~20min;
步骤4,涤纶非织造布表面负载纳米二氧化钛:
配制质量百分比浓度8%~12%的钛酸四丁酯无水乙醇溶液,按照0.01~0.05mL/cm2用量,在步骤3填充处理好的涤纶非织造布表面喷涂钛酸四丁酯无水乙醇溶液,在140℃~160℃条件下焙烘10~30min,按照织物质量与去离子水质量之比1:30~50,将喷涂好的涤纶非织造布浸泡在去离子水中,90℃~110℃条件下处理20~40min,最后40~60℃烘干。
吸附重金属离子分析:以铜离子为模型,对利用本发明方法所得的涤纶非织造布对吸附重金属铜离子性能进行测试,具体测试方法为:将0.4g改性后的涤纶非织造布添加到体积50mL、pH值5、质量百分比浓度从10mg/L至110mg/L的硫酸铜水溶液中,静态吸附平衡8h后,用双环己酮草酰二腙BCO对铜离子进行显色,在最大吸收波长545nm处测定吸光度,依据吸光度与浓度标准曲线可以得到铜离子的浓度,并根据公式(1)和公式(2)计算铜离子的去除百分率Re和平衡吸附量qe
式中:C0和Ce分别是铜离子的初始浓度和达到吸附平衡时的浓度(mg/L)。
式中:V是吸附溶液的体积(L);M是涤纶非织造布的质量(g)。
将第一次吸附铜离子的涤纶非织造布在50℃条件下烘干,然后加入到体积100mL、浓度1mol/L的HCl水溶液中脱附60min,接着用去离子水清洗直至pH为7,50℃烘干,再将其添加到体积50mL、pH值5、浓度50mg/L的铜离子溶液中进行第二次吸附,之后重复进行第三次吸附实验。
温度293K条件下吸附等温模型分析:铜离子的初始浓度从10mg/L至110mg/L,待涤纶非织造布达到吸附平衡后测定铜离子溶液的吸光度,然后对吸附等温线进行拟合处理,并依据Langmuir模型,Freundlich模型,Dubinin-Radushkevich模型和Temkin模型对吸附等温线进行拟合分析。
吸附动力学分析:对吸附数据进行准一阶、准二阶和颗粒内扩散动力学模型拟合,以进一步确定负载纳米二氧化钛壳聚糖柠檬酸改性涤纶非织造布的吸附作用机制。
光催化活性分析:以甲基橙染料为模型,将0.4g改性后的涤纶非织造布浸泡在体积50mL、质量百分比浓度10mg/L的甲基橙溶液中,120min达到吸附平衡后,放置在功率60W、主波长254nm的石英紫外线灯下进行辐照,光源距离甲基橙液面10cm,紫外线辐照强度为3.97mw/cm2,辐照5h后抽取5mL溶液,在最大吸收波长463nm处测定吸光度,按照公式(3)计算甲基橙染料降解率D。
式中:A0—甲基橙溶液起始吸光度值;A5h—辐照5h后甲基橙溶液吸光度值。
实施例1
按照织物质量与溶液质量之比1:30称取涤纶非织造布,将其浸泡在质量百分比浓度25g/L的氢氧化钠溶液中,在80℃条件下处理50min,随后用去离子水反复清洗直至洗液pH值为7.0,最后40℃烘干。按照壳聚糖质量与溶液质量之比1:50,在质量百分比浓度5%的乙酸水溶液中添加脱乙酰度85%的壳聚糖,20℃条件下磁力搅拌2h使其充分降解,然后依次加入质量百分比浓度1%的柠檬酸,1%的次亚磷酸钠,0.1%的戊二醛,以及质量百分比浓度0.5%的聚乙二醇,20℃条件下磁力搅拌5min,密闭冷藏备用。按照织物质量与壳聚糖柠檬酸凝胶整理液质量之比1:30,将洗净的涤纶非织造布浸泡在壳聚糖柠檬酸凝胶整理液中,然后放置到真空干燥箱中抽真空20min,真空度低于-0.1Mpa,接着在75℃条件下预烘10min。配制质量百分比浓度8%的钛酸四丁酯无水乙醇溶液,按照0.01mL/cm2用量,在填充了壳聚糖柠檬酸凝胶的涤纶非织造布表面喷涂钛酸四丁酯乙醇溶液,在140℃条件下焙烘10min。按照织物质量与去离子水质量之比1:50,将喷涂后的涤纶非织造布浸泡在去离子水中,90℃处理20min,最后40℃烘干。
将本实施例所得的0.4g涤纶非织造布添加到体积50mL、pH值5、质量百分比浓度50mg/L的硫酸铜水溶液中,静态吸附平衡8h后,用双环己酮草酰二腙BCO对铜离子进行显色,在最大吸收波长545nm处测定吸光度,按照公式(1)计算得到铜离子的去除率为80%,按照公式(2)计算得到平衡吸附量为7.5mg/g。将第一次吸附铜离子的涤纶非织造布50℃烘干,然后加入到体积100mL、浓度1mol/L的HCl水溶液中脱附60min,接着用去离子水清洗直至pH为7,50℃烘干,再将其添加到50mL、pH值5、浓度50mg/L的铜离子溶液中进行第二次吸附,同理进行第三次吸附,其第三次吸附铜离子的去除率可以达到75%以上,平衡吸附量7.0mg/g以上。将0.4g的涤纶非织造布浸泡在体积50mL、质量百分比浓度10mg/L的甲基橙溶液中,吸附平衡120min后放置在功率60W、主波长254nm的石英紫外线灯下辐照,光源距离甲基橙液面10cm,紫外线强度3.97mw/cm2,辐照5h后抽取5mL溶液,在最大吸收波长463nm处测定吸光度,按照公式(3)计算得到甲基橙染料降解率为91%。
实施例2
按照织物质量与溶液质量之比1:10称取涤纶非织造布,将其浸泡在质量百分比浓度45g/L的氢氧化钠溶液中,在100℃条件下处理70min,随后用去离子水反复清洗直至洗液pH值为7.0,60℃烘干。按照壳聚糖质量与溶液质量之比1:30,在质量百分比浓度10%的乙酸水溶液中添加脱乙酰度95%的壳聚糖,40℃条件下磁力搅拌4h使其充分降解,然后依次加入质量百分比浓度3%的柠檬酸,3%的次亚磷酸钠,0.3%的戊二醛,以及质量百分比浓度1.5%的聚乙二醇,40℃条件下磁力搅拌10min,密闭冷藏备用。按照织物质量与壳聚糖柠檬酸凝胶整理液质量之比1:10,将洗净的涤纶非织造布浸泡在壳聚糖柠檬酸凝胶整理液中,然后放置到真空干燥箱中抽真空40min,真空度低于-0.1Mpa,接着在95℃条件下预烘20min。配制质量百分比浓度12%的钛酸四丁酯无水乙醇溶液,按照0.05mL/cm2用量,在填充了壳聚糖柠檬酸凝胶的涤纶非织造布表面喷涂钛酸四丁酯无水乙醇溶液,160℃条件下焙烘30min。按照织物质量与去离子水质量之比1:30,将喷涂后的涤纶非织造布浸泡在去离子水中,110℃条件下处理40min,最后60℃烘干。
将本实施例所得的0.4g涤纶非织造布添加到体积50mL、pH值5、质量百分比浓度50mg/L的硫酸铜水溶液中,静态吸附平衡8h后,用双环己酮草酰二腙BCO对铜进行显色,在最大吸收波长545nm处测定吸光度,按照公式(1)计算得到铜离子的去除率为91%,按照公式(2)计算得到平衡吸附量为8.8mg/g。将第一次吸附铜离子的涤纶非织造布50℃烘干,然后加入到体积100mL、浓度1mol/L的HCl水溶液中脱附60min,接着用去离子水清洗直至pH为7,50℃烘干,再将其添加到50mL、pH值5、浓度50mg/L的铜离子溶液中进行第二次吸附,同理进行第三次吸附,其第三次吸附铜离子的去除率可以达到84%以上,平衡吸附量7.6mg/g以上。将0.4g的涤纶非织造布浸泡在体积50mL、质量百分比浓度10mg/L的甲基橙溶液中,吸附平衡120min后放置在功率60W、主波长254nm的石英紫外线灯下辐照,光源距离甲基橙液面10cm,紫外线强度3.97mw/cm2,辐照5h后抽取5mL溶液,在最大吸收波长463nm处测定吸光度,按照公式(3)计算得到甲基橙染料降解率为94%。
实施例3
按照织物质量与溶液质量之比1:20称取涤纶非织造布,将其浸泡在质量百分比浓度35g/L的氢氧化钠溶液中,在90℃条件下处理60min,随后用去离子水反复清洗直至洗液pH值为7.0,50℃烘干。按照壳聚糖质量与溶液质量之比1:40,在质量百分比浓度8%的乙酸水溶液中添加脱乙酰度90%的壳聚糖,30℃条件下磁力搅拌3h使其充分降解,然后依次加入质量百分比浓度2%的柠檬酸,2%的次亚磷酸钠,0.2%的戊二醛,以及质量百分比1.0%的聚乙二醇,30℃条件下磁力搅拌8min,密闭冷藏备用。按照织物质量与壳聚糖柠檬酸凝胶整理液质量之比1:20,将洗净的涤纶非织造布浸泡在壳聚糖柠檬酸凝胶整理液中,然后放置到真空干燥箱中抽真空30min,真空度低于-0.1Mpa,接着在85℃条件下预烘15min。配制质量百分比浓度10%的钛酸四丁酯无水乙醇溶液,按照0.03mL/cm2用量,在填充了壳聚糖柠檬酸凝胶的涤纶非织造布表面喷涂钛酸四丁酯无水乙醇溶液,150℃条件下焙烘20min。按照织物质量与去离子水质量之比1:40,将喷涂后的涤纶非织造布浸泡在去离子水中,100℃条件下处理30min,最后50℃烘干。
将本实施例所得的0.4g涤纶非织造布添加到体积50mL、pH值5、质量百分比浓度50mg/L的硫酸铜水溶液中,静态吸附平衡8h后,用双环己酮草酰二腙BCO对铜进行显色,在最大吸收波长545nm处测定吸光度,按照公式(1)计算得到铜离子的去除率为98%,按照公式(2)计算得到平衡吸附量为9.5mg/g。将第一次吸附铜离子的涤纶非织造布50℃烘干,然后加入到体积100mL、浓度1mol/L的HCl水溶液中脱附60min,接着用去离子水清洗直至pH呈中性,50℃烘干,再将其添加到50mL、pH值5、浓度50mg/L的铜离子溶液中进行第二次吸附,同理进行第三次吸附,其第三次吸附铜离子的去除率可以达到90%以上,平衡吸附量8.5mg/g以上。将0.4g的涤纶非织造布浸泡在体积50mL、质量百分比浓度10mg/L的甲基橙溶液中,吸附平衡120min后放置在功率60W、主波长254nm的石英紫外线灯下辐照,光源距离甲基橙液面10cm,紫外线强度3.97mw/cm2,辐照5h后抽取5mL溶液,在最大吸收波长463nm处测定吸光度,按照公式(3)计算得到甲基橙染料降解率为99%。
图1是本发明方法所得涤纶非织造布的扫描电镜照片。可以看出,壳聚糖柠檬酸凝胶填充处理后的涤纶非织造布内部填充有浆糊状的物质,应为壳聚糖柠檬酸有机物,仍然保留着大量的孔隙;喷涂钛酸四丁酯之后,布面附着有纳米级的颗粒状团聚物,应为二氧化钛。图2是本发明方法所得涤纶非织造布的XRD谱图。测试结果表明,碱处理后的涤纶非织造布的衍射峰强度均有所增强,特别是(-110)和(110)晶面处的衍射峰变化较为明显,说明涤纶纤维中的无定形区发生一定程度的水解,导致结晶区含量有所增加;壳聚糖柠檬酸填充处理之后,衍射峰强度反而有所减弱,在衍射角8.3°和11.4°出现了两个不十分明显的小衍射峰,应为壳聚糖柠檬酸接枝后所引起;喷涂钛酸四丁酯之后,在衍射角6°出现了一个小衍射峰,同时在48°和54°左右出现了两个不十分明显的衍射峰,与PDF卡片中的No.21-1272相一致,应为锐钛矿型二氧化钛的特征衍射峰,分别对应着(200)、(105)和(211)晶面,由于(105)和(211)晶面处衍射峰非常接近因此合成为一个衍射峰。图3是本发明方法所得涤纶非织造布的热重-差热曲线。测试结果表明,涤纶非织造布碱处理之后,玻璃化转变温度由75℃略微升至76℃,起始熔融温度由228℃升高至233℃,270℃-380℃间熔融吸热峰变化至250℃-400℃,最大分解温度由448℃升高至458℃;壳聚糖柠檬酸凝胶处理之后,玻璃化转变温度降至55℃,起始熔融温度降至150℃,182℃和250℃出现两个熔融吸热峰,最大分解温度降至448℃;而喷涂钛酸四丁酯之后,玻璃化转变温度没有改变,起始熔融温度升高至235℃,250℃处出现一小的熔融吸热峰,最大分解温度升至453℃。图4是本发明方法所得涤纶非织造布的红外光谱曲线。测试结果表明,涤纶非织造布经过壳聚糖柠檬酸处理之后,3463cm-1处吸收峰有所增强,应为壳聚糖的羟基(-OH)伸缩振动吸收峰和N-H伸缩振动吸收峰所引起,1717cm-1处酯羰基C=O伸缩振动吸收峰移至1720cm-1,是由柠檬酸所引起,受壳聚糖酰胺特征吸收峰影响,1610cm-1处酰胺I的C=O伸缩振动吸收峰和1579cm-1处酰胺II的N-H弯曲振动吸收峰明显增强,1311cm-1是酰胺III的特征吸收峰,应为酰胺基团中的C-N键伸展振动和弯曲振动所引起,1371cm-1处的非晶区CH2面外摇摆振动吸收峰和1341cm-1处的晶区CH2面外摇摆振动吸收峰分别移至1385cm-1和1348cm-1,受壳聚糖C-O-C伸缩振动吸收峰的影响,涤纶纤维C-O伸缩振动吸收峰(ν(C-O))由1234cm-1、1085cm-1和1041cm-1分别移至1230cm-1、1089cm-1和1032cm-1,而970cm-1吸收峰消失,同时在898cm-1处出现了β-糖苷键的C-O伸缩振动吸收峰,说明壳聚糖的氨基与柠檬酸的羧基生成酰胺键,在催化剂和高温焙烘作用下,柠檬酸与壳聚糖生成酯键,其残留的羧基生成酐环与涤纶中的羟基发生酯化交联从而接枝到涤纶纤维表面;喷涂钛酸四丁酯之后,1695cm-1处出现了二氧化钛的特征吸收峰,同时在719cm-1处的苯环CH平面外弯曲振动吸收峰显著增强,这是因为受到二氧化钛Ti-O特征吸收峰的影响,说明涤纶非织造布表面负载了二氧化钛。图5是本发明方法所得涤纶非织造布的漫反射光谱曲线。测试结果表明,涤纶非织造布在305、422、608和678nm处有明显的吸收峰,说明涤纶对紫外线具有较强的吸收能力,对可见光也有一定的吸收;壳聚糖柠檬酸处理之后,对紫外线和可见光的吸收进一步得到增强;喷涂钛酸四丁酯之后,由于布面负载有纳米二氧化钛,因此对紫外线的吸收进一步得到增强,而对可见光吸收有所减弱。图6是本发明方法所得涤纶非织造布在温度293K条件下的Langmuir等温吸附模型。测试结果表明,二氧化钛/壳聚糖凝胶改性后的涤纶非织造布满足单分子层均匀吸附理论。图7是本发明方法所得涤纶非织造布在不同初始铜离子浓度条件下的准二级动力学模型拟合曲线。测试结果表明,二氧化钛/壳聚糖改性涤纶非织造布吸附铜离子符合准二级吸附动力学模型。

Claims (10)

1.一种涤纶非织造织物的改性方法,其特征在于,具体按照以下步骤实施:
步骤1,涤纶非织造织物前处理,除去涤纶非织造布表面粘附的杂质;
步骤2,涤纶非织造布填充壳聚糖柠檬酸凝胶整理液:
将步骤1前处理后的涤纶非织造织物浸泡在壳聚糖柠檬酸凝胶整理液,进行填充整理;
步骤3,对步骤2填充整理后的涤纶非织造织物表面负载纳米二氧化钛,即得到具有光催化活性,且能够吸附重金属离子的织物。
2.根据权利要求1所述的一种涤纶非织造织物的改性方法,其特征在于,所述步骤1前处理具体为:将涤纶非织造布浸泡在氢氧化钠溶液中,在80℃~100℃条件下处理50~70min,随后用去离子水反复清洗直至洗液为中性,最后40℃~60℃烘干。
3.根据权利要求2所述的一种涤纶非织造织物的改性方法,其特征在于,所述步骤1中涤纶非织造布与氢氧化钠溶液的质量比为1:10~30,氢氧化钠溶液的浓度为25~45g/L。
4.根据权利要求1所述的一种涤纶非织造织物的改性方法,其特征在于,所述步骤2中壳聚糖柠檬酸凝胶整理液制备的具体过程为:
在乙酸水溶液中添加壳聚糖,20℃~40℃条件下磁力搅拌2~4h使其充分降解,然后依次加入柠檬酸、次亚磷酸钠、戊二醛和聚乙二醇,20℃~40℃条件下搅拌5~10min,即得到壳聚糖柠檬酸凝胶整理液。
5.根据权利要求4所述的一种涤纶非织造织物的改性方法,其特征在于,所述壳聚糖与乙酸水溶液的质量比为1:30~50,乙酸水溶液的质量百分比浓度为5%~10%,壳聚糖的脱乙酰度为85%~95%,柠檬酸、次亚磷酸钠、戊二醛和聚乙二醇加入量分别为反应体系质量百分比浓度的1~3%、1~3%、0.1~0.3%和0.5~1.5%。
6.根据权利要求1所述的一种涤纶非织造织物的改性方法,其特征在于,所述步骤2中填充整理过程具体为:将步骤1前处理后的涤纶非织造布浸泡在壳聚糖柠檬酸凝胶整理液中,放置到真空干燥箱中抽真空20~40min,真空度低于-0.1Mpa,然后在75℃~95℃条件下预烘10~20min。
7.根据权利要求1或6所述的一种涤纶非织造织物的改性方法,其特征在于,所述涤纶非织造布与壳聚糖柠檬酸凝胶整理液的质量比为1:10~30。
8.根据权利要求1所述的一种涤纶非织造织物的改性方法,其特征在于,所述步骤3中,涤纶非织造布表面负载纳米二氧化钛具体过程为:
在步骤2填充好的涤纶非织造布表面喷涂钛酸四丁酯无水乙醇溶液,然后在140℃~160℃条件下焙烘10~30min,随后将喷涂后的涤纶非织造布浸泡在去离子水中,90℃~110℃条件下处理20~40min,最后在40~60℃烘干。
9.根据权利要求8所述的一种涤纶非织造织物的改性方法,其特征在于,所述钛酸四丁酯无水乙醇溶液的质量百分比浓度为8%~12%,喷涂用量为0.01~0.05mL/cm2
10.根据权利要求8所述的一种涤纶非织造织物的改性方法,其特征在于,所述涤纶非织造布与去离子水的质量比为1:30~50。
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