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STUDY ON THE CATIONIC POLYMERIZATION OF 1, 3-pentadiene INITIATED BY AlCl_3/ALKYL HALIDE SYSTEMS

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Chinese Journal of Polymer Science 1996年第1期14卷 91-96页

作者：彭宇行刘佳林戴汉松寸琳峰 Chengdu Institute of Organic Chemistry Chinese Academy of Sciences Chengdu 610041

The cationic polymerizations of 1, 3-pentadiene were initiated by AlCl_3 in n-hexaneat 30℃ in the presence of alkyl halides, i.e., tert-butyl chloride, tert-butyl bromide andisobutyl chloride. The effects of these halides on the polymer yield, molecular weight,crosslinking reaction, cyclization and polymer microstructure, have been investigated. Twomain side reactions, crosslinking and cyclization, were suppressed and reduced by theaddition of the halides. The proportion of 1, 4 units of polymer chains was increasedby the presence of the halides, which reduced the polymer yield and the molecular weightof polymers.

关键词： 1,3-pentadiene Cationic polymerization Alkyl halide Chain transfer

Initiating system Me_3SiCl/AlCl_3 for cationic polymerization of 1,3-pentadiene in toluene

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Chinese Journal of Chemistry 1998年第5期16卷 452-457页

作者：邓建国彭宇行 Chengdu Institute of Organic Chemistry Chinese Academy of Sciences ChengduSichuan 610041 China

Cationic polymerization of 1,3-pentadiene (PD) initiated by trimethylsilyl chloride/aluminium chloride (TMSCl/AlCl3) was carried out in toluene at 30℃.The polymer yield was increased by the addition of ***,introduction of TMSC1 gave rise to a drop of the polymer molecular *** results demonstrated that the polymerization initiated by TMSCl/AlCl3 was 2.8 times faster than that induced by AlCl3 *** ethers and ketones were used to mediate the initiating system TMSCl/*** polymer yield and molecular weight of the polymer were decreased in the presence of *** and ethers had different effects on the polymerization,and the polymer yield and molecular weight were lower than those initiated by AlCl3 alone or TMSCl/AlCl3 Structural evidence revealed that the polymerization was indeed initiated by AlCl3 and HCl rcsulting from hydrolysis of TMSC1 by adventitious water.

关键词： 1,3-pentadiene cationic polymerization initiation trimethysllvl chloride

(CH_3)_3SiCl/TiCl_4 INITIATING SYSTEM FOR CATIONIC POLYMERIZATION OF 1,3-pentadiene

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Chinese Journal of Polymer Science 1999年第5期17卷 459-464页

作者：彭宇行 Chengdu Institute of Organic Chemistry Chinese Academy of Sciences Chengdu 610041 China

Cationic polymerizations of 1,3-pentadiene (PD) initiated by trimethylsilyl chloride (TMSCl) incombination with TiCl_4 were carried out in n-hexane at 30℃. The yield of polymer was greatly increased bythe addition of TMSCl, indicating that the TMSCl/TiCl_4 combination is an efficient initiating system for PDcationic polymerization. However, the introduction of TMSCl gave rise to a drop in the molecular weight ofthe polymer. Kinetic results demonstrated that the polymerization initiated by TMSCl/TiCl_4 is 4.5 times fasterthan that induced by TiCl_4 alone. Various ethers were used to mediate the TMSCl/TiCl_4 initiating *** diphenyl ether could increase both the yield and molecular weight of the polymer. Structural evidenceillustrates that the polymerization is indeed initiated by TiCl_4 in combination with HCl resulting fromhydrolysis by adventitious water.

关键词： 1,3-pentadiene Cationic polymerization TMSCI TiCl_4

Alkylation of Toluene with 1,3-pentadiene over [bupy]BF4-AlCl3 Ionic Liquid Catalyst

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Chinese Journal of Chemical Engineering 2007年第5期15卷 680-682页

作者：田力曹发海房鼎业郭世卓 Research Institute of Chemical Technology East China University of Science and Technology Shanghai 200237 China Chemical Research Institute Shanghai Petrochemical Company Limited SINOPEC Shanghai 200540 China

The alkylation of toluene with 1,3-pentadiene to produce pentyltoluene was carded out to obtain 2,6-dimethylnaphalene, which is an important intermediate during the production of 2,6-naphthalene dicarboxylic acid. Based on our previous work using anhydrous AlCl3 as catalyst, [bupy]BF4-AlCl3 ionic liquids were employed to catalyze the reaction of 1,3-pentadiene with toluene. The experimental results show that [bupy]BF4-AlCl3 ionic liquids are suitable for the reaction especially when the molar ratio of AlCl3 to [bupy]BF4 is 1.75 ： 1, and the reaction could proceed at the temperature as low as 0℃. It could be as active as pure AlCl3, but much more environmentally friendly.

关键词： [bupy]BF4-AlCl3 ionic liquids toluene 1,3-pentadiene pentenyltoluene

Cationic polymerization of 1,3-pent adiene in the presence of arenes

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Chinese Journal of Chemistry 1996年第2期14卷 180-185页

作者： Peng, YX Liu, JL Cun, LF Dai, HS CHINESE ACAD SCI CHENGDU INST ORGAN CHEMCHENGDU 610041SICHUANPEOPLES R CHINA

The cationic polymerizations of 1,3-pentadiene initiated by AlCl3 inn-hexane at 30 degrees C have been carried out in the presence of various arenes, i.e., benzene, toluene, p-xylene, o-xylene, m-xylene and mesitylene. The presence of all these arenes have reduced in different degrees the formation of crosslinked products. Namely, the crosslinking reaction, a major side-reaction during the cationic polymerization of 1,3-pentadiene, has been suppressed by adding the aromatic compounds. The results showed that a chain transfer to arene took place and this transfer process hindered the generation of the crosslinked polymer. IR and H-1 NMR spectra have confirmed the existence of the corresponding aryl groups in the resulting polymers.

关键词： cationic polymerization 1,3-pentadiene chain transfer crosslinking reaction