壳聚糖三元接枝马来酸酐衣康酸共聚物的制备及其阻垢性能研究
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摘要
本论文主要研究了以壳聚糖为主体,马来酸酐、衣康酸为单体的共聚物的制备及其阻垢性能研究。壳聚糖(Chitosan)是一种含有羟基、氨基等活性基团的天然高分子化合物,具有无毒,生物降解性好和反应中不产生二次污染等优点,被作为绿色原料越来越广泛的应用在水处理中药剂的制备。马来酸酐(Maleic anhydride)又名顺丁烯二酸酐,经常用作为一种高效绿色的水处理剂原料。衣康酸(Itaconic acid)又名亚甲基丁二酸,分子中含有不饱和双键,因此具有活泼的化学性质,可进行自身间的聚合也能与其他单体聚合。本论文主要采取这样一种思路,以壳聚糖为主体,接枝共聚马来酸酐和衣康酸单体,合成一种新型、高效、绿色以及成本低廉的阻垢剂,并通过静态阻垢实验研究该阻垢剂的阻垢性能。
首先,以壳聚糖为主体,以过硫酸铵和亚硫酸氢钠为引发剂,在氮气的保护下,通过溶液聚合反应,将壳聚糖、马来酸酐、衣康酸进行接枝共聚,合成一种含有-OH、-NH2、-COOH的三元接枝共聚物。以接枝率为考察指标,通过单因素分析得出了该三元接枝共聚物的最佳合成条件为:引发剂浓度为3.2×10-2mol/L、反应温度50℃、反应时间为5h、单体摩尔比n(MA):n(IA) =1:1.5、m(壳聚糖):m(马来酸酐+衣康酸)=1:3。
其次,用红外光谱分析、XRD分析、元素分析、热重分析和扫描电镜分析对这壳聚糖三元接枝共聚物进行表征定性分析,得出壳聚糖三元接枝马来酸酐衣康酸共聚物的表征与壳聚糖的表征有较大改变,且马来酸酐、衣康酸单体已接枝到壳聚糖上。
再次,通过静态阻垢实验,探讨了壳聚糖三元接枝马来酸酐衣康酸共聚物阻垢剂的阻垢情况。考察了阻垢性能的影响因素,如阻垢剂浓度,水样PH值,恒温时间,恒温温度,水样中Ca2+浓度。所得结论如下:当阻垢剂浓度为60mg/L, PH=8,恒温时间8h,恒温温度为(60士1)℃,Ca2+浓度为500 mg/L时,可获得最佳阻垢效果,阻垢率达90%以上。并初步探讨了壳聚糖三元接枝马来酸酐衣康酸共聚物阻垢剂的阻垢机理,比较符合晶格畸变理论。
最后,将壳聚糖三元接枝共聚物(CTS-MA-IA)与水解聚马来酸酐(HPMA)、2-丙烯酸胺-2-甲基丙基磺酸(AMPS)相比较,得出结论当阻垢剂投加量为30mg/L时,三者阻垢率逐渐接近。除此之外,水样PH、温度、水质硬度对阻垢率均有不同程度的影响。
This paper was mainly about the preparation of three grafted compound, which contains chitosan, maleic anhydride and itaconic acid. Chitosan is a kind of nature high molecular polymer with -OH、-NH2 groups. Because of the low toxic, readily biodegradable advantages, many researchers pay attention to the application of chitosan in water treatment field. Maleic anhydride is another kind of raw material in water treatment, which is effective and low toxic. Itaconic acid has active chemical property. Chitosan was selected as the subject grafted with maleic anhydride and itaconic acid to prepare a novel effective and green scale inhibitor. The inhibition performance of the grafted compound is studied.
Firstly, taking chitosan as the main material, taking ammonium per sulfate as initiator, under the protection of N2, the grafted reaction to get the three grafted compound was carried on. Considering the grafted rate, the best conditions were: concentration of initiator =3.2×10-2 mol/L;reaction temperature =50℃; reaction time =5h; n(MA):n(IA) =1:1.5; m(chitosan):m(maleic+itaconic)=1:3.
Secondly, infrared spectrometer,X-Ray diffraction,thermo gravimetric analysis, element analysis, scanning electron microscope methods were used to characterize three grafted compound. The characterization with several difference showed that maleic anhydride and itaconic acid are grafted on chitosan subject.
Thirdly, the inhibition performance of the grafted compound was studied by the static anti-scaling method. The conditions were: concentration of scale inhibitor =60mg/L; PH =8; constant temperature =(60士1)℃; constant time =8h; concentration of Ca2+ =500mg/L. The inhibition rate can reach 90% and above. And the inhibition mechanism was studied, the theory of lattice disformation was possible.
Finally, the inhibition performance with other scale inhibitors, such as HPMA and AMPS were compared.
首先,以壳聚糖为主体,以过硫酸铵和亚硫酸氢钠为引发剂,在氮气的保护下,通过溶液聚合反应,将壳聚糖、马来酸酐、衣康酸进行接枝共聚,合成一种含有-OH、-NH2、-COOH的三元接枝共聚物。以接枝率为考察指标,通过单因素分析得出了该三元接枝共聚物的最佳合成条件为:引发剂浓度为3.2×10-2mol/L、反应温度50℃、反应时间为5h、单体摩尔比n(MA):n(IA) =1:1.5、m(壳聚糖):m(马来酸酐+衣康酸)=1:3。
其次,用红外光谱分析、XRD分析、元素分析、热重分析和扫描电镜分析对这壳聚糖三元接枝共聚物进行表征定性分析,得出壳聚糖三元接枝马来酸酐衣康酸共聚物的表征与壳聚糖的表征有较大改变,且马来酸酐、衣康酸单体已接枝到壳聚糖上。
再次,通过静态阻垢实验,探讨了壳聚糖三元接枝马来酸酐衣康酸共聚物阻垢剂的阻垢情况。考察了阻垢性能的影响因素,如阻垢剂浓度,水样PH值,恒温时间,恒温温度,水样中Ca2+浓度。所得结论如下:当阻垢剂浓度为60mg/L, PH=8,恒温时间8h,恒温温度为(60士1)℃,Ca2+浓度为500 mg/L时,可获得最佳阻垢效果,阻垢率达90%以上。并初步探讨了壳聚糖三元接枝马来酸酐衣康酸共聚物阻垢剂的阻垢机理,比较符合晶格畸变理论。
最后,将壳聚糖三元接枝共聚物(CTS-MA-IA)与水解聚马来酸酐(HPMA)、2-丙烯酸胺-2-甲基丙基磺酸(AMPS)相比较,得出结论当阻垢剂投加量为30mg/L时,三者阻垢率逐渐接近。除此之外,水样PH、温度、水质硬度对阻垢率均有不同程度的影响。
This paper was mainly about the preparation of three grafted compound, which contains chitosan, maleic anhydride and itaconic acid. Chitosan is a kind of nature high molecular polymer with -OH、-NH2 groups. Because of the low toxic, readily biodegradable advantages, many researchers pay attention to the application of chitosan in water treatment field. Maleic anhydride is another kind of raw material in water treatment, which is effective and low toxic. Itaconic acid has active chemical property. Chitosan was selected as the subject grafted with maleic anhydride and itaconic acid to prepare a novel effective and green scale inhibitor. The inhibition performance of the grafted compound is studied.
Firstly, taking chitosan as the main material, taking ammonium per sulfate as initiator, under the protection of N2, the grafted reaction to get the three grafted compound was carried on. Considering the grafted rate, the best conditions were: concentration of initiator =3.2×10-2 mol/L;reaction temperature =50℃; reaction time =5h; n(MA):n(IA) =1:1.5; m(chitosan):m(maleic+itaconic)=1:3.
Secondly, infrared spectrometer,X-Ray diffraction,thermo gravimetric analysis, element analysis, scanning electron microscope methods were used to characterize three grafted compound. The characterization with several difference showed that maleic anhydride and itaconic acid are grafted on chitosan subject.
Thirdly, the inhibition performance of the grafted compound was studied by the static anti-scaling method. The conditions were: concentration of scale inhibitor =60mg/L; PH =8; constant temperature =(60士1)℃; constant time =8h; concentration of Ca2+ =500mg/L. The inhibition rate can reach 90% and above. And the inhibition mechanism was studied, the theory of lattice disformation was possible.
Finally, the inhibition performance with other scale inhibitors, such as HPMA and AMPS were compared.
引文
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