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Characterization, Synthesis, and Application of Borate-selective Polymers

硼酸盐选择性聚合物的表征、合成及应用

基本信息

批准号：
06640790
负责人：
YOSHIMURA Kazuhisa
金额：
$ 1.34万
依托单位：
KYUSHU UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1994
资助国家：
日本
起止时间：
1994 至 1996
项目状态：
已结题

项目摘要

Studies were done using commercially available linear dextran and crosslinked polyols such as Sephadex gel, QAE-Sephadex anion-exchange dextran gel, and Amberlite IRA-743, a boron-selective resin which has a functional group of N-methylglucamine. Together with the distribution measurements of borate on the crosslinked polymers, ^<11>B NMR spectroscopy was employed to elucidate the nature of the complex formation of borate with the polyols. The results obtained were as follows : (1) for the adsorption of borate on a crosslinked dextran. DELTAH values were comparable to those for the complex formation ob borate with monosaccharides and the borate concentration dependence of boron adsorption is a characteristic property of the crosslinked dextran. (2) Well-resolved ^<11>B NMR spectra for the solid gel as well as for a dextran solution were observed. In the dextran system, borate complexes both with alpha, beta-diols and alpha, gamma-diols of glucopyranoside residues were present. This cro … More sslinking of dextran caused the effective concentration of alpha, beta-diol moieties in the crosslinked polymer ligand to become higher than the practical concentrarion, so that the 1 : 2 complexation became more fovorable accoding to the increase in the degree of crosslinking. (3) The borate concentration dependence of boron adsorption on crosslinked dextran gel may be caused by the exclusion of borate anions from the gel phase due to electrostatic repulsion between borate and the fixed anion sites of borate complexes in the gel phase. The stability constant of each complex is similar to that for the Sephadex system : the presence of the fixed cation group in the QAE-Sephadex gel phase did not promote the boron adsorption. (4) The pH of the N-methylglucamine resin phase remains constant in the range of 10 to 11 when the equilibrated bulk solution is pH 6-11. The strong adsorbability of borate on the resin in a wide pH range is due to this phenomenon. From the ^<11>B MAS-NMR measurements, the active species in the resin were proved to be borate complexes of alpha, beta-diols in the functional groups.On the basis of the results obtained, a novel boron-selective polymer was synthesized by introducing tris (hydroxymethyl) groups into chloromethylated polystirene. The properties of this resin are now being investigated. Less

使用市售的线性葡聚糖和交联多元醇如Sephadex凝胶、QAE-Sephadex阴离子交换葡聚糖凝胶和Amberlite IRA-743（一种具有N-甲基葡糖胺官能团的硼选择性树脂）进行研究。结合硼酸盐在交联聚合物上的分布测量，采用~1H B NMR光谱来阐明硼酸盐与多元醇形成络合物的性质。<11>结果表明：（1）交联葡聚糖对硼酸根的吸附。DELTAH值与硼酸盐与单糖形成络合物的值相当，硼吸附的硼酸盐浓度依赖性是交联葡聚糖的特征性质。(2)观察到固体凝胶以及葡聚糖溶液的良好分辨的1H B NMR光谱。<11>在葡聚糖系统中，存在与吡喃葡萄糖苷残基的α，β-二醇和α，γ-二醇的硼酸盐络合物。这个十字架 ...更多信息葡聚糖的交联导致交联聚合物配体中α，β-二醇部分的有效浓度变得高于实际浓度，使得1：2络合变得更有利，这是由于交联度的增加。(3)硼吸附在交联葡聚糖凝胶上的硼酸盐浓度依赖性可能是由于硼酸盐与凝胶相中硼酸盐络合物的固定阴离子位点之间的静电排斥而导致的从凝胶相中排除硼酸盐阴离子。各络合物的稳定常数与Sephadex体系相似：QAE-Sephadex凝胶相中固定阳离子基团的存在并不促进硼的吸附。(4)当平衡的本体溶液的pH为6 - 11时，N-甲基葡糖胺树脂相的pH保持恒定在10 - 11的范围内。硼酸盐在树脂上的强吸附性在很宽的pH范围内是由于这一现象。通过~（12）B MAS-NMR测定，证实了树脂中的活性物种是α，β-二醇的硼酸盐配合物，并在此基础上，通过在氯甲基化聚苯乙烯中引入三羟甲基，合成了一种新型的硼选择性聚合物。<11>目前正在研究这种树脂的性能。少