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[1]孟伟娟,邱迎昕,马文超,等.异丁烯-对甲基苯乙烯无规共聚物可见光溴化反应的选择性[J].合成橡胶工业,2022,3:173-181.
　MENG Wei-juan,QIU Ying-xin,MA Wen-chao,et al.Photobromination selectivities of isobutylene-p-methyl styrene random copolymer irradiated with visible light[J].China synthetic rubber industy,2022,3:173-181.
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异丁烯-对甲基苯乙烯无规共聚物可见光溴化反应的选择性(PDF)

《合成橡胶工业》[ISSN:1000-1255/CN:62-1036/TQ]

期数:
2022年3期
页码:
173-181
栏目:
出版日期:
2022-05-15

文章信息/Info

Title:
Photobromination selectivities of isobutylene-p-methyl styrene random copolymer irradiated with visible light
文章编号:
1000-1255（2022）03-0173-09
作者:
孟伟娟; 邱迎昕; 马文超; 魏孜博; 张雷
中国石化北京化工研究院燕山分院 橡塑新型材料合成国家工程研究中心， 北京 102500
Author(s):
MENG Wei-juan;  QIU Ying-xin;  MA Wen-chao;  WEI Zi-bo;  ZHANG Lei
National Engineering Research Center for Synthesis of Novel Rubber and Plastic Materials, Yanshan Branch, Beijing Research Institute of Chemical Industry, SINOPEC, Beijing 102500, China
关键词:
异丁烯-对甲基苯乙烯共聚物; 正离子聚合; 光溴化反应; 自由基反应; 溴化反应选择性; 凝胶化反应; 酸蚀剂
Keywords:
isobutylene-p-methyl styrene copolymer;  cationic polymerization;  photobromination reaction;  free radical reaction;  bromination selectivity;  gelation reaction;  acid etching agent
分类号:
TQ 333.99
DOI:
DOI:10.19908/j.cnki.ISSN1000-1255.2022.03.0173
文献标识码:
A
摘要:
使用气相色谱仪对几种不同纯度的正己烷和环己烷进行了组分分析，并对包括2-甲基戊烷、3-甲基戊烷和甲基环戊烷在内的正己烷的主要支链型同分异构体成分，以及异丁烯-对甲基苯乙烯无规共聚物中对甲基苯乙烯结构单元的模型分子对二甲苯和对二异丙苯在波长为365～840 nm的可见光照射下的光溴化反应进行了对比，筛选出可以有效避免溶剂发生光溴化副反应并提高目标光溴化反应选择性的可见光波长。此外，将异丁烯-对甲基苯乙烯无规共聚物在质量分数为85.740 0%～99.960 0%的溶剂正己烷和环己烷中的光溴化反应的选择性进行了对比，并考察了除酸剂碳酸氢钠和反应温度对异丁烯-对甲基苯乙烯无规共聚物在正己烷中光溴化反应的影响。结果表明，波长为595 nm和630 nm的可见光可作为异丁烯-对甲基苯乙烯无规共聚物光溴化反应的光源，在质量分数为85%的工业正己烷中即可实现良好的光溴化反应，溴的有效利用率可达到70%～80%；碳酸氢钠作为酸蚀剂可以有效抑制异丁烯-对甲基苯乙烯无规共聚物的凝胶化反应。此外，反应温度对光溴化反应有一定影响，当反应温度从5 ℃降至-20 ℃时，溴化反应速率降低了58.87%。
Abstract:
Several types of n-hexane and cyclohexane with different purities were analyzed by gas chromatograph, and the photobromination reactions of the major branched isomer compositions of n-he-xane including 2-methylpentane, 3-methylpentane and methylcyclopentane, and model molecules of structural unit of p-methyl styrene in isobutylene-p-methyl styrene random copolymer, p-xylene and 1,4-diisopropylbenzene, were compared with visible light with the wavelengths of 595 nm and 630 nm as light sources. The visible light wavelengths with which photobromination side reaction of the solvent could be effectively avoided, and with which the selectivity of target photobromination reaction was improved were screened. In addition, the selectivities of photobromination reaction of isobutylene-p-methyl styrene random copolymer in the solvent of n-hexane and cyclohexane with the purities between 85.740 0% and 99.960 0% were compared, and the effect of sodium bicarbonate as the acid etching agent and reaction temperature on the photobromination reaction of isobutylene-p-methyl styrene random copolymers in n-hexane were investigated. The results showed that visible light with the wavelengths of 595 nm and 630 nm could be used as the light sources for the photobromination reaction of isobutylene-p-methyl styrene random copolymer, and efficient photobromination reaction could be achieved in industrial grade n-hexane whose purity was 85% with effective avai-lability of bromine of 70%-80%. The gelation reaction of isobutylene-p-methyl styrene random copolymer could be effectively inhibited with sodium bicarbonate as the acid etching agent. Moreover, to a certain extent, the reaction temperature had an effect on the photobromination reaction, and there was a decrease of 58.87% in the bromination rate when the reaction temperature decreased from 5 ℃ to -20 ℃.

参考文献/References

[1] Powers K W， Wang H C， Chung T C， et al. Para-alkylstyrene/isoolefin copolymers and functionalized copolymers thereof: US， 5162445[P]. 1992-11-10.[2] Wang H C， Powers K W. Functionalized PMS/IB copolymers offer wide range of properties[J]. Elastomerics， 1992， 124（1）： 14-19.[3] Mataka S， Liu Guobin. Potothemal side-chain bromination of methyl， dimethyl， and trimethylbenzenes with N-bromosuccimide[J]. Bulletin of the Chemical Society of Japan， 1994， 67（4）： 113-119.[4] 高春香， 张静， 王蕾. 光溴化法合成对溴苄基溴的研究[J]. 当代化工， 2007， 36（2）： 136-138.[5] 白家强， 王葆仁， 郑国琇， 等. 烷烃的取代反应——戊烷、己烷和庚烷的溴化[J]. 中国科学（B辑）， 1984（4）： 303-307. [6] 钱旭红， 高建宝， 焦家俊， 等. 有机化学[M]. 北京： 化学工业出版社， 1999： 156-157.

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更新日期/Last Update: 2022-05-15