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纸质出版日期:2003-8-20,
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杨丹, 钟杰平, 李思东, 贾德民. 天然胶乳氯化反应历程研究[J]. 高分子学报, 2003,(4):489-494.
YANG Dan, ZHONG Jieping, LI Sidong, JIA Demin. STUDY OF CHLORINATION REACTION MECHANISM OF LATEX[J]. Acta Polymerica Sinica, 2003,(4):489-494.
采用红外光谱和化学分析方法
对天然胶乳的氯化反应进行了跟踪分析
其反应历程应与溶液法工艺氯化历程相似 :1)取代氯化和环化
由Cl+ 进攻天然橡胶分子
产生的最初取代
伴随环化
导致二个异戊二烯单元中一个CC双键转化为C—C单键;2)加成 消除
伴随C—C基团的转移;3)纯粹取代 .但胶乳法在第三步“纯粹取代”的同时
生成了一定量的叔碳C—Cl键 ;红外光谱还跟踪纪录了胶乳法CNR中ClCCO和ClC—COOH基团的生成
此二点为胶乳法CNR和溶液法CNR结构上最大的不同之处
也是导致胶乳法CNR稳定性差于溶液法CNR的主要因素 .从13C-NMR对胶乳法CNR分析得出样品中含有的伯、仲、叔碳C—Cl键的比例
结合IR光谱和裂解色谱 质谱分析
得出胶乳法CNR氯化反应的历程
氯原子的取代与加成顺序 ;并由结果分析可知
胶乳法CNR的结构不如溶液法CNR规整
其主要原因为氯化起始阶段有HOCl加成、生成了较多的叔碳C—Cl键以及氯化后期有一定量的ClCCO和ClC—COOH基团生成 .此外
还得出结论 :胶乳法制备CNR的氯化反应在所有的NR分子上均匀发生.
Fourier transform infrared spectroscopy and chemical analysis were applied to study the chlorination reaction mechanism of latex.The results showed that the chlorination mechanism of latex is similar to that from solution:(1) substituted chlorination and cyclization (The initial substitution was created by that chlorine attacked natural rubber molecules with concomitant cyclization reaction)
(2) addition-elimination accompanied by a shiftiog of the C=C group and (3) pure substitution.Furthermore
the production of ClC—C=O and RClC—COOH groups was recorded by Fourier transform infrared spectroscopy.This is the largest difference between CNR prepared from latex and from solution.From the ratio of primary
secondary and tertiary C—Cl bands analyzed by 13C—NMR
combined with IR spectrometry and high resolution pyrolysis gas chromatography-mass spectrometry.the chlorination mechanism of CNR from latex and the sequence of —Cl substitution and addition could be introduced.The structure of CNR from latex is not as regular as CNR from solution.The main reason was that HOCl formed at the initial stage of chlorination
and RClC—COOH produced at the later stage of chlorination.Furthermore
a conclusion could be deduced that the chlorination reaction takes place evenly on all NR molecules in the chlorination process in latex.
氯化天然橡胶氯化历程红外光谱分析13CNMR
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