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漆酶活化碱木质素的磺甲基化反应活性研究
  • ISSN号:1000-3304
  • 期刊名称:Acta Polymerica Sinica
  • 时间:2013.2.2
  • 页码:232-240
  • 分类:TQ323.1[化学工程—合成树脂塑料工业]
  • 作者机构:[1]华南理工大学化学与化工学院制浆造纸国家重点实验室,广州510640
  • 相关基金:国家重点基础研究发展计划(973计划,项目号2012CB215302,2010CB732205)、国家杰出青年科学基金(基金号20925622)和国家自然科学基金(基金号21176096)资助项目.
  • 相关项目:木质素两亲聚合物的化工理论和技术
中文摘要:

采用漆酶对碱木质素进行活化预处理,并对活化碱木质素进行磺甲基化改性,揭示了漆酶活化对碱木质素磺甲基化反应活性影响的作用机理.采用顶空气相色谱、红外光谱、凝胶渗透色谱、核磁共振等研究了漆酶活化碱木质素的结构特征,结果表明,漆酶对碱木质素既有聚合作用又有解聚作用,分子量变化不大,多分散性增加;漆酶活化使得碱木质素发生脱甲基作用,酚羟基含量增大,紫丁香基含量减低;另外,漆酶可氧化酚羟基变成苯氧自由基使碱木质素聚合.采用分子模拟对漆酶活化碱木质素的电子云密度进行了计算,结果表明脱甲基作用增大了木质素苯环上的电子云密度,有利于磺甲基化反应的进行.采用电位滴定测试磺甲基化产物的磺化度来表征其反应活性的大小,结果表明漆酶活化磺甲基化碱木质素的磺化度提高了35%,且对二氧化钛悬浮体系的分散性能得到明显提高.

英文摘要:

The alkali lignin was modified by laccase,followed by sulfomethylation. To study the mechanism of laccase modification on the influence of sulfomethylation reactivity, the control and laccase modified alkali lignins were characterized by chemical, spectroscopic and chromatographic methods. The molecular weight of sulfomethylated lignins was measured by gel permeation chromatography (GPC) , and the structural changes in laccase modified lignins were characterized by functional groups measurements,headspace gas chromatography (GC) ,infrared spectroscopy (IR) and nuclear magnetic resonance (NMR). It is proposed that laccase was able to promote both polymerization and depolymerisation. The molecular weight (Mw) changed a little, but the polydispersity was larger than that of the control. The demethylation by laccase oxidation made the increase of the content of phenolic group,while the content of syringyl decreased. At the same time, laccase could oxidise the phenolic end-groups into stabilized radicals that subsequently undergo radical-radical coupling. The charge density of lignin model compounds was calculated by molecular simulation. It was indicated that why demethylation benefited the sulfomethylation. According to structural changes in lignin, the mechanism of the influence laccase modification on the sulfomethylation reactivity was deduced. The sulfomethylation reactivity, measured by the content of sulfonie groups,was increased by 35% after laccase modification. It was mainly due to the increase of the content of phenolic groups and the decrease of steric hindrance. In addition, the dispersion efficiency of sulfomethlated alkali lignin with laccase modification on the TiO2 slurry improved significantly.

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期刊信息
  • 《高分子学报》
  • 中国科技核心期刊
  • 主管单位:中国科学院
  • 主办单位:中国化学会 中国科学院化学研究所
  • 主编:张希
  • 地址:北京市海淀区中关村北一街2号
  • 邮编:100190
  • 邮箱:gfzxb@iccas.ac.cn
  • 电话:010-62588927
  • 国际标准刊号:ISSN:1000-3304
  • 国内统一刊号:ISSN:11-1857/O6
  • 邮发代号:2-498
  • 获奖情况:
  • 国家优秀期刊二等奖,中科院优秀期刊二等奖,中国科协优秀期刊
  • 国内外数据库收录:
  • 俄罗斯文摘杂志,美国化学文摘(网络版),荷兰文摘与引文数据库,美国科学引文索引(扩展库),英国高分子图书馆,日本日本科学技术振兴机构数据库,中国中国科技核心期刊,中国北大核心期刊(2004版),中国北大核心期刊(2008版),中国北大核心期刊(2011版),中国北大核心期刊(2014版),中国北大核心期刊(2000版)
  • 被引量:19174