摘要
用红外光谱研究了Cu-py、Cu-PVPy和Cu-QPVPy催化漆酚氧化聚合交联过程。漆酚氧化聚合阶段的共同特征是:1.漆酚酿吸收峰1652crn ̄-1先涨后落;2.共轭双烯吸收峰982和945cm ̄-1逐渐减弱,而共轭三烯吸收峰992cm ̄-1和芳醚吸收峰1215cm ̄-1却逐步增强;3.苯环三取代吸收峰830、765cm ̄-1都有所减弱,苯环四取代吸收峰875和805cm ̄-1出现;4.苯环骨架吸收峰1620、1592cm ̄-1之间的界限缩小甚至消失。到了漆膜的实于阶段,漆酚酿吸收峰1652cm ̄-1再度兴起,但992cm ̄-1吸收峰却由涨转落,其他吸收峰也有变化。以上光谱变化表明这3种催化剂都模拟了漆酶的催化作用。在Cu-PVPy催化漆酚氧化聚合阶段,发现孤立双键吸收峰3008cm ̄-1比共轭双烯吸收峰982和945cm ̄-1消失得更早;并且从反应一开始就出现了1715cm`-1羰基吸收峰。还比较了Cu-PVPy与Cu-QPVPy催化的异同。
The oxidative polymerization and cross-linking process of urushiol catalyzed by cupric complex-es with pyridine,poly(4-vinylpyridine),and partially quaternized poly(4-vinylpyridine)by benzyl chloridewere studied by IR analysis. During oxidative polymerization of urushiol, absorption peak of urushi-olquinone at 1652 cm ̄-1 enlarged at the beginning and then diminished. Absorption peaks of conjugated di-enes at 982 and 945 cm ̄-1 weakened gradually,and absorption peaks of conjugated trienes at 992 cm ̄-1 andthat of aromatic ethers at 1215 cm ̄-1 grew by degrees. Absorption peaks of trisubstituted benzene at 830and 765 cm ̄-1 also declined,and those of tetrasubstituted benzene at 875 and 805 cm ̄-1 appeared.Theboundary valley between both absorption peaks at 1620 and at 1592 cm ̄-1 which are attributed to benzeneskeleton reduced or even disappeared. During the solidifying stage,absorption peak of urushiolquinone at1652 cm ̄-1 rose again, and that at 992 cm ̄-1 changed from enlarging to diminishing. These changes in IRspectra showed that above-mentioned three catalysts simulated the catalytical action of laccase.It was found that absorption peak of carbonyl at 1715 cm ̄-1 appeared at the beginning of the reactionand that of isolated double bond at 3008 cm ̄-1 disappeared earlier than absorption peaks of conjugated di-enes at 982 and 945 cm ̄-1. In addition,differences and similarities between Cu-PVPy and Cu-QPVPy werediscussed.
出处
《林产化学与工业》
EI
CAS
CSCD
北大核心
1994年第2期51-56,共6页
Chemistry and Industry of Forest Products
基金
湖北省自然科学基金
关键词
铜
吡啶
络合物
漆酚
模拟漆酶
Cupric complex with pyridine(Cu-Py )
Cupric complex with poly( 4-vinylpyridine)(Cu-PVPy)
Cupric complex with partially quaternized poly(4-vinylpyridine)by benzyl chloride(Cu-QPVPy)
Urushiol
Models of laccase
IR analysis