CN111636145A - 一种吸附重金属的聚酯纤维膜及其制备方法 - Google Patents

一种吸附重金属的聚酯纤维膜及其制备方法 Download PDF

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CN111636145A
CN111636145A CN202010544275.7A CN202010544275A CN111636145A CN 111636145 A CN111636145 A CN 111636145A CN 202010544275 A CN202010544275 A CN 202010544275A CN 111636145 A CN111636145 A CN 111636145A
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Abstract

本发明公开了一种吸附重金属的聚酯纤维膜及其制备方法,包括:在DCC/DMAP体系下,5‑(2‑吡啶)间苯二甲酸和乙二醇进行酯化反应制备功能性第三组分,与对苯二甲酸乙二醇酯进行酯交换反应合成共聚酯,再进行静电纺丝制备聚酯纤维膜;吡啶氮具有孤对电子,与Cd(II)和Cr(VI)能够快速形成稳定的配合物,通过化学接枝于PET分子链上,使得纤维膜具有良好的再生性,可多次循环利用,可应用于废水处理领域。

Description

一种吸附重金属的聚酯纤维膜及其制备方法
技术领域
本发明属于膜技术领域,具体涉及一种吸附重金属的聚酯纤维膜及其制备方法。
背景技术
近年来,随着工业化进程加快,大量含有重金属的工业废水和城市生活污水排放到环境中,对大气、土壤和水环境,尤其是人类健康带来了严重危害,对人体产生危害的主要有铅、镉、铬、汞、砷。目前处理重金属离子的方法很多,比如化学沉淀法、离子交换法等,但由于会产生大量的污泥和导致二次污染,应用受到限制,而膜吸附法操作简便、成本低廉,是一种极具潜力的吸附净化工业废水中重金属离子的手段。
聚酯(PET)具有良好的成纤性,并且具有良好的力学强度、耐溶剂、耐酸腐的优点,近年来有关于PET纤维应用于废水处理、重金属吸附领域的报道越来越多。刘小钊报道了一种聚酯纺织品表面接枝丙烯酸、丙烯酰胺的Cu2+吸附膜,属于表面接枝改性。(刘小钊等,等离子体接枝法制备PET-g-AM纤维的铜离子吸附性能研究,印染助剂,2019,36(05),15-19.)王闻宇报道了一种采用静电纺丝法制备的聚酯/角蛋白共混纳米纤维膜,对水溶液中的Cr(VI)具有良好的吸附性,属于共混改性。(王闻宇,靳许,史长曲,金欣,李刘倩,林童.聚酯/角蛋白纳米纤维膜的制备及其铬离子吸附性能.天津工业大学学报,2019,38(03):15-21.),而对于合成阶段改性的聚酯纤维膜用于金属吸附领域的未见有报道。
发明内容
本发明通过加入功能性第三组分与对苯二甲酸和乙二醇进行酯交换反应合成聚酯,所得聚酯通过静电纺丝制备纳米纤维膜,该纤维膜对Cd(II)和Cr(VI)有良好的吸附功能,并且具有再生性。
本发明的目的在于提供一种吸附重金属的聚酯纤维膜。
本发明的另一目在于是提供上述吸附重金属的聚酯纤维膜的制备方法。
本发明上述目的通过以下技术方案实现:
一种吸附重金属的聚酯纤维膜,其结构式如下:
Figure BDA0002539995550000021
式中m:n=1:5~20。
上述吸附重金属的聚酯纤维膜的反应流程及制备方法如下:
1.5-(2-吡啶)间苯二甲酸乙二醇酯(M1)的制备
在圆底烧瓶中加入5-(2-吡啶)间苯二甲酸、乙二醇(EG)、N,N'-二环己基碳酰亚胺(DCC)、N,N-对二甲氨基吡啶(DMAP),用等体积干燥二氯甲烷溶解,在室温下反应24h后过滤除去不溶物,50~80℃下蒸发滤液溶剂,以二氯甲烷为洗脱剂,通过硅胶柱色谱分离得到浅黄色液体M1。
所述5-(2-吡啶)间苯二甲酸、EG、DCC、DMAP的投料摩尔比为1:3:5:0.2。
M1的结构式如下:
Figure BDA0002539995550000031
式中,x的取值为1~3。
2.对苯二甲酸乙二醇酯(M2)的制备
在圆底烧瓶中加入对苯二甲酸二甲酯(DMT)、乙二醇(EG)、催化剂醋酸锰,通入N2,在240~260℃下进行酯交换反应。当冷凝回收的甲醇的体积不低于理论体积的90%时,酯交换反应结束,制得M2。
所述DMT、EG的投料摩尔比为1:2,醋酸锰的投料量为DMT质量的0.05%。
M2的结构式如下:
Figure BDA0002539995550000032
3.共聚酯的制备
按一定的比例将M1和M2投入圆底烧瓶中,通入N2,温度升高至240~260℃时,启动真空泵,真空度控制在800~1000Pa内0.5~1h进行预缩聚,将温度升高至250~280℃,真空度低于50Pa,开始终缩聚反应1~2h,用氮气解除真空并出料,得到共聚酯。
所述M1、M2的投料摩尔比为1:5~20。
4.静电纺丝制备聚酯纤维膜
以三氯甲烷:三氟乙酸体积比为3:1的比例作为纺丝溶剂,将共聚酯投入纺丝溶剂中充分溶解后,静置24h以消除气泡,制得纺丝液注入静电纺丝装置的溶液通道进行纺丝。纺丝得到的聚酯纤维膜用丙酮浸泡1~2h,以出去残留的溶剂,然后放入50℃真空烘箱中干燥24h。
所述纺丝液的质量浓度为20%。
静电纺丝参数为:纺丝电压24kV,接收距离10~15cm,纺丝溶液流速为0.3-1mL/h,纺丝速度为40μm/min。
本发明具有如下优点和有益效果:
本发明提供一种吸附重金属的聚酯纤维膜及其制备方法,通过加入功能性第三组分5-(2-吡啶)间苯二甲酸乙二醇酯与对苯二甲酸乙二醇酯进行酯交换合成PET,再采用静电纺丝的方式制备得到纳米聚酯纤维膜。共聚酯分子链中的吡啶单元的N原子带有孤对电子,与大部分过渡金属和稀土金属具有稳固迅速的配位作用,能够吸附生态水环境中有害的重金属物质,如Cd(II)和Cr(VI)。具有重金属吸附作用的吡啶化学接枝至PET分子链上,使得纤维膜具有良好的再生性,可多次循环利用。
附图说明
图1为M1和M2的1H-NMR谱图。
图2为不同溶液酸度下聚酯纤维膜对Cd(II)静态饱和吸附量Q的影响。
图3为不同溶液酸度下聚酯纤维膜对Cr(VI)静态饱和吸附量Q的影响。
图4为聚酯纤维膜吸附Cd(II)的静态饱和吸附量Q随时间的变化曲线。
图5为聚酯纤维膜吸附Cr(VI)的静态饱和吸附量Q随时间的变化曲线。
具体实施方式
下面结合具体实施例对本发明做进一步详细说明,但实施例并不对本发明做任何形式的限定。除非特别说明,本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
(1)5-(2-吡啶)间苯二甲酸乙二醇酯(M1)的制备
按摩尔投料比5-(2-吡啶)间苯二甲酸:EG:DCC:DMAP=1:3:5:0.2称取各原料,加入圆底烧瓶,并用等体积干燥二氯甲烷溶解,在室温下反应24h后过滤除去不溶物,60℃下蒸发滤液溶剂,以二氯甲烷为洗脱剂,通过硅胶柱色谱分离得到浅黄色液体M1。
根据1H-NMR,如图1所示,计算M1缩合度为2。
(2)对苯二甲酸乙二醇酯(M2)的制备
按摩尔投料比为1:2称取对苯二甲酸二甲酯(DMT)和乙二醇(EG)加入圆底烧瓶,加入DMT 0.05wt%的醋酸锰,通入N2,在240℃下进行酯交换反应。当冷凝回收的甲醇的体积不低于理论体积的90%时,酯交换反应结束,制得M2。
根据1H-NMR,如图1所示,计算M2缩合度为1。
(3)共聚酯的制备
按一定的质量比例将M1和M2投入圆底烧瓶中,通入N2,温度升高至240℃时,启动真空泵,真空度控制在800Pa内1h进行预缩聚,将温度升高至270℃,真空度控制在50Pa,关闭N2,开始终缩聚反应2h,用氮气解除真空并出料,得到共聚酯。
(4)静电纺丝制备聚酯纤维膜
以三氯甲烷:三氟乙酸体积比为3:1的比例作为纺丝溶剂,将共聚酯投入纺丝溶剂中充分溶解后,静置24h以消除气泡,制得纺丝液注入静电纺丝装置的溶液通道进行纺丝。纺丝得到的聚酯纤维膜用丙酮浸泡1h,以出去残留的溶剂,然后放入50℃真空烘箱中干燥24h。
所述纺丝液的质量浓度为20%。
静电纺丝参数为:纺丝电压24kV,接收距离115cm,纺丝溶液流速为0.3mL/h,纺丝速度为40μm/min。
实施例1~4和对比例1除M1与M2除投料比例不同,其余制备步骤和条件相同,即按照上述步骤(1)~(4)制备得到纤维膜,各例的投料比例及对应的其各项测试列于表1。
表1
Figure BDA0002539995550000071
本发明测试:
(1)特性粘度:根据标准GB/T 14190-2008测试特性粘度。配制苯酚和四氯乙烷的混合溶剂(w/w=1/1),制成浓度为0.005g/mL的共聚酯溶液。按Mark-Houwink方程(IV)根据[η]计算样品的粘均分子量M,对PET而言,K=6.7×10-3,α=0.47。
[η]=KMα (IV)
(2)元素分析:采用德国Elmentar Vario EL元素分析仪测试样品的N元素含量。
从表中可知,纤维膜的含N量与对Cd(II)、Cr(VI)吸附量成正相关,与共聚酯的特性粘度成负相关,说明5-(2-吡啶)间苯二甲酸乙二醇酯的缩聚活性较对苯二甲酸二甲酯低。
(3)金属离子静态饱和吸附量测试:称量50mg样品膜置于具塞锥形瓶中,加入10mL的HAc-NaAc缓冲溶液(pH=2~6)浸泡12h,分别加入10mL的2mmol/L的重铬酸钾水溶液和四氯合镉水溶液,在45℃下恒温振荡一定时间,取上层清液稀释50倍。溶液中铬酸根阴离子质量浓度的测定按GB/T 7466-1987测量,四氯合镉配阴离子的质量浓度采用电感耦合等离子体质谱仪直接测量。静态饱和吸附量Q按以下公式(V)计算:
Figure BDA0002539995550000081
式中,C0为溶液初始浓度(mg/L),Ct为吸附平衡时的溶液浓度(mg/L),V为待测溶液体积(L),m为纤维膜的质量(g)。
从图1和图2可以看出,溶液pH值为3.5左右时,纤维膜对Cd(II)的吸附容量最大,溶液pH值为5左右时,纤维膜对Cr(VI)的吸附容量最大。表1中聚酯纤维膜吸附Cd(II)和Cr(VI)的静态饱和吸附量Q,测试溶液pH分别为3.5和5。
(4)再生性测试:将饱和吸附的纤维膜置于50mL浓度为0.1mol/L氢氧化钠水溶液以120r/min的频率振荡解吸20min,然后取出用蒸馏水冲洗2遍,再用25mL浓度为0.02mol/L盐酸溶液浸泡5min,取出后并用蒸馏水洗净后再进行静态饱和吸附量测试。

Claims (3)

1.一种吸附重金属的聚酯纤维膜及其制备方法,其特征在于,所述吸附重金属的聚酯纤维膜具有式(I)结构:
Figure FDA0002539995540000011
式中m:n=1:5~20。
2.一种吸附重金属的聚酯纤维膜及其制备方法,其特征在于,包括以下步骤:
(1)5-(2-吡啶)间苯二甲酸乙二醇酯(M1)的制备
以N,N'-二环己基碳酰亚胺(DCC)为脱水剂、N,N-对二甲氨基吡啶(DMAP)为催化剂、二氯甲烷为反应溶剂,5-(2-吡啶)间苯二甲酸、乙二醇(EG)为原料进行酯化反应,蒸发得到的粗产物以二氯甲烷为洗脱剂,通过硅胶柱色谱分离得到浅黄色液体M1,结构式如式(Ⅱ)所示:
Figure FDA0002539995540000012
式中,x的取值为1~3;
(2)对苯二甲酸乙二醇酯(M2)的制备
以醋酸锰为催化剂,苯二甲酸二甲酯(DMT)与乙二醇(EG)进行酯交换反应,制得M2,结构式如式(III)所示:
Figure FDA0002539995540000021
(3)共聚酯的制备
M1和M2进行酯交换反应,制备共聚酯(I)。预缩聚反应温度在240~260℃,真空度800~1000Pa,反应时间为0.5~1h;终缩聚反应温度在250~280℃,真空度低于50Pa,反应时间1~2h;
(4)静电纺丝制备聚酯纤维膜。
3.根据权利要求2所述一种吸附重金属的聚酯纤维膜及其制备方法,其特征在于:
所述步骤(1)的5-(2-吡啶)间苯二甲酸、EG、DCC、DMAP的投料摩尔比为1:3:5:0.2;
所述步骤(2)的DMT、EG的投料摩尔比为1:2,醋酸锰的投料量为DMT质量的0.05%;
所述步骤(3)的M1、M2的投料摩尔比为1:5~20。
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