β-CD基共聚物的合成及其脱色性能研究
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摘要
新型、高效、环保、适用性强的脱色用絮凝剂的设计与合成,对于印染废水污染治理、环境保护来说具有十分重大的意义。β-环糊精(β-CD)作为淀粉的衍生物,具有环境友好、可再生、可降解、价格适中等优点,其改性产物在脱色用絮凝剂领域具有很大的应用前景。
本论文首先采用马来酸酐(MAH)改性β-CD得到可聚合的单体—β-CD-MAH,之后采用过硫酸铵(APS)/亚硫酸氢钠(SBS)氧化还原体系引发β-CD-MAH与阳离子单体甲基丙烯酰氧乙基三甲基氯化铵(TMAEMC)共聚合得到目标产物—β-CD-MAH-TMAEMC。采用红外光谱(FT-IR)、核磁共振谱(1H-NMR)、扫描电子显微镜(SEM)照片以及热重分析(TGA)曲线表征了β-CD-MAH-TMAEMC的化学结构、形貌与热稳定性。并进行了Zeta电位、电导率与粘度的测定分别表征了产物的阳离子度α和特性粘度[η]。此外,以活性艳蓝KN-R为阴离子染料的代表,研究了β-CD-MAH-TMAEMC的絮凝脱色性能以及在絮凝脱色过程中絮凝剂与染料分子之间的作用。
结果表明:β-CD-MAH-TMAEMC的化学结构与预期一致,在絮凝脱色过程中表现出良好的热稳定性。为了获得较高的阳离子度α与特性粘度[η],β-CD-MAH-TMAEMC的最佳合成条件为:单体浓度20 wt%、引发剂浓度0.5 wt% (APS/SBS, 1:1摩尔比)、温度45℃、聚合时间5h、通N2及单体(β-CD-MAH/TMAEMC)质量比6:4。絮凝剂用量、染液pH值和染液温度均对给定染液的脱色效果有影响。对于室温、pH 7、不含盐(0 g/L NaCl)的100 mg/L染液,在搅拌方式为170 r/min×5 min + 60 r/min×10 min的条件下,达到最佳的脱色率—95.45%所对应的絮凝剂浓度为220 mg/L;对于室温、pH 10、含盐(40 g/L NaCl)的100 mg/L染液,在搅拌方式为120 r/min×5 min + 40 r/min×5 min的条件下,达到最佳的脱色率—84.43%所对应的絮凝剂浓度为40 mg/L。
β-CD-MAH-TMAEMC作为絮凝剂在处理活性艳蓝KN-R溶液的过程中,脱色的机理主要是絮凝剂与染料之间的静电吸附作用。此外,共价键、氢键及聚合物架桥对于絮凝剂/染料体系的脱色性能也有贡献。随着絮凝剂所带正电荷密度的增加,脱色率升高,并且所需的絮凝剂用量下降;达到最佳脱色率所需的絮凝剂用量与絮凝剂阳离子度的倒数成线性关系;絮凝剂的相对分子质量对于最终的染液脱色率影响较小,而对形成絮体的形态(如粒径尺寸)有较大的影响。随着絮凝剂相对分子质量的提升,形成絮体的粒径增大,絮凝沉降时间减少。搅拌方式的改变对于最终的脱色率影响不大,但对于絮凝沉降速度有一定的影响。在絮凝剂处理溶液的过程中,使用合适的搅拌方式有助于提高絮凝沉降速度。
flocculants for color removal are meaningful for the wastewater treatments and environmental protections. As a derivative from starches, beta-cyclodextrin (β-CD) has many advantages, such as eco-friendly aspect, renewability, biodegradability and low cost. Therefore, the modified products fromβ-CD have more potential in the area of flocculated decolorization.
In this paper, a polymerizable monomer (β-CD-MAH) was obtained by the esterification between maleic anhydride (MAH) andβ-CD. Thereafter, copolymers ofβ-CD-MAH-TMAEMC as new flocculants for decolorization were synthesized by means of free radical copolymerization betweenβ-CD-MAH and the cationic monomer, N-trimethylaminoethylmethacrylate chloride (TMAEMC). The chemical structure, morphology and thermal stability ofβ-CD-MAH-TMAEMC were characterized by means of FT-IR, 1H-NMR, SEM photos and TGA curves. Besides, the cationic degree (α) and intrinsic viscosity ([η]) ofβ-CD-MAH-TMAEMC were determined by the measurements of zetal potenl, conductivity and viscosity. As a representative of anionic dyes, the reactive brilliant blue KN-R was applied for the flocculation experiments. And the decolrization performances ofβ-CD-MAH-TMAEMC and the interactions betweenβ-CD-MAH-TMAEMC and the reactive brilliant blue KN-R were studied in detail.
The experimental results show that the anticipative chemical structure ofβ-CD-MAH-TMAEMC was achieved. Andβ-CD-MAH-TMAEMC was thermal stable during the normal flocculation processes. An increase in the feed composition of TMAEMC was helpful for increasing the copolymer composition of cationic units (α) and the copolymer’s intrinsic viscosity ([η]). The optimum conditions for synthesis ofβ-CD-MAH-TMAEMC were 6/4 of the weight proportion betweenβ-CD-MAH and TMAEMC, 0.5 % of initiator (APS/SBS, 1/1, mol/mol) relative to the monomer weight, 45 ?C of temperature and time of 5 h. For the given flocculant/dye solution system, many conditions including the flocculant concentration, the pH of dye solution, the temperature of dye solution and the stirring modes had effects on decolorization. Under the condition of pH 7, room temperature and 0 g/L of NaCl, the dye solution at the concentration of 100 mg/L would be mostly decolorized (the highest decolrization efficiency of 95.45%) with the stirring mode of 170 r/min×5 min + 60 r/min×10 min. Accordingly, the optimum dosage of flocculant was 220 mg/L. On the other hand, under the condition of pH 10, room temperature and 40 g/L of NaCl, the dye solution at the concentration of 100 mg/L would be mostly decolorized (the highest decolrization efficiency of 84.43%) with the stirring mode of 120 r/min×5 min + 40 r/min×5 min. Accordingly, the optimum dosage of flocculant was 40 mg/L.
The main mechanism for flocculated decolorization when the synthesized copolymer ofβ-CD-MAH-TMAEMC was added into the dye solution of reactive brilliant blue KN-R was electrostatic adsorption. Aside, other interactions such as covalent bond, H-bond and polymer bridging also contributed to the flocculated decolrization. With increasing the cationic degree of copolymer, the highest decolorization efficiency was improved and the corresponded flocculant dosage was reduced. The linear relationship between the reciprocalαand the optimum flocculant dosage was found. The relative molecular mass ofβ-CD-MAH-TMAEMC had a small role on the decolorization efficiency, but it had an important role on the formed focs’particle sizes. Larger flocs would formed whenβ-CD-MAH-TMAEMC with higher molecular mass was used, inducing faster sedimentation.
本论文首先采用马来酸酐(MAH)改性β-CD得到可聚合的单体—β-CD-MAH,之后采用过硫酸铵(APS)/亚硫酸氢钠(SBS)氧化还原体系引发β-CD-MAH与阳离子单体甲基丙烯酰氧乙基三甲基氯化铵(TMAEMC)共聚合得到目标产物—β-CD-MAH-TMAEMC。采用红外光谱(FT-IR)、核磁共振谱(1H-NMR)、扫描电子显微镜(SEM)照片以及热重分析(TGA)曲线表征了β-CD-MAH-TMAEMC的化学结构、形貌与热稳定性。并进行了Zeta电位、电导率与粘度的测定分别表征了产物的阳离子度α和特性粘度[η]。此外,以活性艳蓝KN-R为阴离子染料的代表,研究了β-CD-MAH-TMAEMC的絮凝脱色性能以及在絮凝脱色过程中絮凝剂与染料分子之间的作用。
结果表明:β-CD-MAH-TMAEMC的化学结构与预期一致,在絮凝脱色过程中表现出良好的热稳定性。为了获得较高的阳离子度α与特性粘度[η],β-CD-MAH-TMAEMC的最佳合成条件为:单体浓度20 wt%、引发剂浓度0.5 wt% (APS/SBS, 1:1摩尔比)、温度45℃、聚合时间5h、通N2及单体(β-CD-MAH/TMAEMC)质量比6:4。絮凝剂用量、染液pH值和染液温度均对给定染液的脱色效果有影响。对于室温、pH 7、不含盐(0 g/L NaCl)的100 mg/L染液,在搅拌方式为170 r/min×5 min + 60 r/min×10 min的条件下,达到最佳的脱色率—95.45%所对应的絮凝剂浓度为220 mg/L;对于室温、pH 10、含盐(40 g/L NaCl)的100 mg/L染液,在搅拌方式为120 r/min×5 min + 40 r/min×5 min的条件下,达到最佳的脱色率—84.43%所对应的絮凝剂浓度为40 mg/L。
β-CD-MAH-TMAEMC作为絮凝剂在处理活性艳蓝KN-R溶液的过程中,脱色的机理主要是絮凝剂与染料之间的静电吸附作用。此外,共价键、氢键及聚合物架桥对于絮凝剂/染料体系的脱色性能也有贡献。随着絮凝剂所带正电荷密度的增加,脱色率升高,并且所需的絮凝剂用量下降;达到最佳脱色率所需的絮凝剂用量与絮凝剂阳离子度的倒数成线性关系;絮凝剂的相对分子质量对于最终的染液脱色率影响较小,而对形成絮体的形态(如粒径尺寸)有较大的影响。随着絮凝剂相对分子质量的提升,形成絮体的粒径增大,絮凝沉降时间减少。搅拌方式的改变对于最终的脱色率影响不大,但对于絮凝沉降速度有一定的影响。在絮凝剂处理溶液的过程中,使用合适的搅拌方式有助于提高絮凝沉降速度。
flocculants for color removal are meaningful for the wastewater treatments and environmental protections. As a derivative from starches, beta-cyclodextrin (β-CD) has many advantages, such as eco-friendly aspect, renewability, biodegradability and low cost. Therefore, the modified products fromβ-CD have more potential in the area of flocculated decolorization.
In this paper, a polymerizable monomer (β-CD-MAH) was obtained by the esterification between maleic anhydride (MAH) andβ-CD. Thereafter, copolymers ofβ-CD-MAH-TMAEMC as new flocculants for decolorization were synthesized by means of free radical copolymerization betweenβ-CD-MAH and the cationic monomer, N-trimethylaminoethylmethacrylate chloride (TMAEMC). The chemical structure, morphology and thermal stability ofβ-CD-MAH-TMAEMC were characterized by means of FT-IR, 1H-NMR, SEM photos and TGA curves. Besides, the cationic degree (α) and intrinsic viscosity ([η]) ofβ-CD-MAH-TMAEMC were determined by the measurements of zetal potenl, conductivity and viscosity. As a representative of anionic dyes, the reactive brilliant blue KN-R was applied for the flocculation experiments. And the decolrization performances ofβ-CD-MAH-TMAEMC and the interactions betweenβ-CD-MAH-TMAEMC and the reactive brilliant blue KN-R were studied in detail.
The experimental results show that the anticipative chemical structure ofβ-CD-MAH-TMAEMC was achieved. Andβ-CD-MAH-TMAEMC was thermal stable during the normal flocculation processes. An increase in the feed composition of TMAEMC was helpful for increasing the copolymer composition of cationic units (α) and the copolymer’s intrinsic viscosity ([η]). The optimum conditions for synthesis ofβ-CD-MAH-TMAEMC were 6/4 of the weight proportion betweenβ-CD-MAH and TMAEMC, 0.5 % of initiator (APS/SBS, 1/1, mol/mol) relative to the monomer weight, 45 ?C of temperature and time of 5 h. For the given flocculant/dye solution system, many conditions including the flocculant concentration, the pH of dye solution, the temperature of dye solution and the stirring modes had effects on decolorization. Under the condition of pH 7, room temperature and 0 g/L of NaCl, the dye solution at the concentration of 100 mg/L would be mostly decolorized (the highest decolrization efficiency of 95.45%) with the stirring mode of 170 r/min×5 min + 60 r/min×10 min. Accordingly, the optimum dosage of flocculant was 220 mg/L. On the other hand, under the condition of pH 10, room temperature and 40 g/L of NaCl, the dye solution at the concentration of 100 mg/L would be mostly decolorized (the highest decolrization efficiency of 84.43%) with the stirring mode of 120 r/min×5 min + 40 r/min×5 min. Accordingly, the optimum dosage of flocculant was 40 mg/L.
The main mechanism for flocculated decolorization when the synthesized copolymer ofβ-CD-MAH-TMAEMC was added into the dye solution of reactive brilliant blue KN-R was electrostatic adsorption. Aside, other interactions such as covalent bond, H-bond and polymer bridging also contributed to the flocculated decolrization. With increasing the cationic degree of copolymer, the highest decolorization efficiency was improved and the corresponded flocculant dosage was reduced. The linear relationship between the reciprocalαand the optimum flocculant dosage was found. The relative molecular mass ofβ-CD-MAH-TMAEMC had a small role on the decolorization efficiency, but it had an important role on the formed focs’particle sizes. Larger flocs would formed whenβ-CD-MAH-TMAEMC with higher molecular mass was used, inducing faster sedimentation.
引文
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