聚乙烯醇纤维金属配合物的合成和表征

以聚乙烯醇纤维(PVA)为配体原料,分别与FeCl3、NiCl2、CuCl2和Pb(Ac)2反应,制备了宏观上仍保持原纤维形态的PVA Fe(Ⅲ)、PVA Ni(Ⅱ)、PVA Cu(Ⅱ)、PVA Pb(Ⅱ)纤维配合物(用PVA M表示).用红外光谱仪分别对PVA和4种配合物在4000～400cm-1范围进行傅立叶变换红外光谱测量,对各PVA M的FTIR主要吸收峰做了经验归属,并与PVA的相应吸收峰做对比分析,结果表明,与金属离子形成配合物后,PVA分子中O—H氢键缔合状态被破坏,向高波数位移了65～86cm-1,PVA中的羟基氧与金属离子发生配位作用.PVA Fe(Ⅲ)的XPS显示,PVA中O1s只出现532.5eV单峰,而PVA Fe(Ⅲ)中O1s分裂为531.4eV和532.3eV两个峰,且Fe2p只有一个峰710.9eV,比FeCl3的结合能值711.2eV下降,说明OH氧与Fe3+形成配位键.

SYNTHESIS AND SPECTRA OF COMPLEXES INVOLVING POLYVINYL ALCOHOL FIBER LIGANDS

By reactions of FeCl-3,NiCl-2,CuCl-2 and Pb(Ac)-2 with polyvinyl alcohol fiber,the complexes of (A) PVA-Fe(Ⅲ),(B) PVA-Ni(Ⅱ),(c) PVA-Cu(Ⅱ),and (D)PVA-Pb(Ⅱ) have been synthesized.The complexes still keep the shape of fiber.They were characterized by IR and XPS measurements.The IR band ν_ O—H shifts to higher wavenumber by 65～86 cm -1,from 3300 cm -1(PVA) to 3365 cm -1(A),3388 cm -1(B),3386 cm -1(C) and 3383 cm -1(D),respectively.And band ν_ C—O shifts to higher wavenumber by 3～5 cm -1:from 1087 cm -1(PVA) to 1091 cm -1(A),1090 cm -1(B),1092 cm -1(C) and 1090 cm -1(D),respectively.The binding energy of O_ 1s and Fe_ 2p was changed during the formation of the PVA-Fe(Ⅲ) complex.XPS studies indicated that the single peak of O_ 1s in PVA splitted into double peaks for O_ 1s in PVA-Fe(Ⅲ);and the Fe_ 2p peak shifted from 711.2 eV to 710.9 eV.All these results implied the bonding of OH oxygen with metal ion in the complexes.