Product Analysis and Reaction Mechanism of High-Pressure Synthesis of Sulfurized Isobutylene by One-Step Method

doi:10.11944/j.issn.1000-0518.2015.07.140397

Chinese Journal of Applied Chemistry ›› 2015, Vol. 32 ›› Issue (7): 771-776.DOI: 10.11944/j.issn.1000-0518.2015.07.140397

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Product Analysis and Reaction Mechanism of High-Pressure Synthesis of Sulfurized Isobutylene by One-Step Method

LI Fei, JIANG Heng, ZHAO Shanlin^*, LI Ping

School of Chemistry and Materials Science,Liaoning Shihua University,Fushun,Liaoning 113001,China

Received:2014-11-18 Accepted:2015-03-25 Published:2015-06-30 Online:2015-06-30
Contact: Shanlin ZHAO
Supported by:
Supported by the National Natural Science Foundation of China (No.21171083)

Abstract

Abstract:

Sulfurized isobutylene was prepared from sulfur and isobutylene via high pressure one-step method at 160~190 ℃ with n-octylamine as catalyst. GC, FT-IR and ¹H NMR analyses of the final products show that it contains chain-like and cyclic polysulfides, chain-like polysulfides are main products, accompanied with the byproducts 4-methyl-3H-1,2-dithiole-3-thione (MDTT), tert-butyl mercaptan, and a small amount of exhaust gas such as H₂S. The formation of MDTT and H₂S is the result of the hydrogen abstraction reaction from isobutylene catalyzed by alkali in the sulfurization process. H₂S then reacts with isobutylene by Markovnikov addition to the formation of tert-butyl mercaptan which is converted to linear polysulfides by reaction with sulfur.

Key words: sulfurized isobutylene, methyl-3H-dithiole-thione, chain-like tert-butyl polysulfides, reaction mechanism

CLC Number:

LI Fei, JIANG Heng, ZHAO Shanlin, LI Ping. Product Analysis and Reaction Mechanism of High-Pressure Synthesis of Sulfurized Isobutylene by One-Step Method[J]. Chinese Journal of Applied Chemistry, 2015, 32(7): 771-776.

References

[1]	YANG Jingpei,TIAN Hongjia,ZHANG Sulian,et al. Process for Production of Vulcanized Isobuktene by Closed and Non-contaminated Circulation Method:CN,97109899.9[P],1998-12-02(in Chinese). 杨景培,田洪加,张素莲,等. 闭路无污染硫化异丁烯的生产工艺:中国,97109899.9[P],1998-12-02.
[2]	MENG Xiangru. Anhydrous Antichloration Technique of Isobutene Sulfide Super Pressure Anti-scuff Agent:CN,200610045908.X[P],2006-09-20(in Chinese). 孟祥儒. 硫化异丁烯极压抗磨剂无水脱氯工艺:中国,200610045908.X[P],2006-09-20.
[3]	Arvizzigno J A,Brooklyn N Y,Ashjian H,et al. Sulfurized Olefins:US,US5338468[P],1994-08-16.
[4]	WANG Xianfa,MIAO Fengqin,FU Zhiqiang,et al. Method for Synthesizing Sulfurized Isobutylene:CN,201310387600.3[P],2013-11-27(in Chinese). 王宪法,苗凤琴,付志强,等. 硫化异丁烯的合成方法:中国,201310387600.3[P],2013-11-27.
[5]	DUAN Huiwei,LI Jiwen,LI Dejun,et al. Synthesis Technique of Sulfide Isobutene by One-step Method:CN,201310387600.3[P],2013-11-27(in Chinese). 段会伟,李继文,李德军,等. 一步法硫化异丁烯的合成工艺:中国,200610045249.X[P],2008-01-02.
[6]	JIANG Binbo,CHEN Nan,ZHENG Laichang,et al.Research on Reaction Kinetics of Sulfurized Isobutylene by One-step Synthesis[J]. Acta Pet Sin(Pet Process Sect),2014,30(3):501-508(in Chinese). 蒋斌波,陈楠,郑来昌,等. 硫化异丁烯的一步法合成反应动力学研究[J]. 石油学报(石油加工),2014,30(3):501-508.
[7]	KE Yunlong. Research on Reaction Kinetics and the Synthesis of Sulfurized Isobutylene by One-step Synthesis[D]. Hangzhou:Zhejiang University,2011(in Chinese). 柯云龙. 硫化异丁烯的一步法合成及其反应动力学研究[D]. 杭州:浙江大学,2011.
[8]	ZHENG Laichang,FENG Yi,ZHENG Wenjun,et al.Pilot Plant Research about Synthesis of High Pressure Sulfurized Isobutene[J]. Spec Petrochem,2002,19(4):29-32(in Chinese). 郑来昌,冯铱,郑文君,等. 高压硫化异丁烯的中试合成研究[J]. 精细石油化工,2002,19(4):29-32.
[9]	Braid M,Kokotailo G T,Landis P S,et al.Synthesis and Structure of a Novel Macrocyclic Polydisulfide[J]. J Am Chem Soc,1978,100(19):6160-6162.
[10]	Davis R E,Nakshbendi H F. Sulfur in Amine Solvents[J]. J Am Chem Soc,1962,84(11):2085-2090.
[11]	FENG Yi,ZHANG Bailing,SU Gang. Development of High Pressure Sulfurized Isobutene[J]. Lubr Oil,2001,16(1):37-40(in Chinese). 冯铱,张白玲,苏刚. 高压硫化异丁烯的研制[J]. 润滑油,2001,16(1):37-40.
[12]	XU Jing,ZHANG Longhua,FU Xisheng. Tribological Characteristics of Sulfurized Olefins Synthetized by Different Techniques[J]. Tribology,2002,22(4):311-313(in Chinese). 续景,张龙华,伏喜胜. 不同工艺制备的硫化烯烃的摩擦学特性研究[J]. 摩擦学学报,2002,22(4):311-313.
[13]	Harris J,Li X P,Chaka A M. Copper Corrosion Mechanisms of Organopolysulfides[J]. Oil Gas Sci Technol,1996,51(1):171-181.
[14]	Tsuchiya N,Suto Y,Kabuta T,et al.Sustainable Hydrogen Production System with Sulfur-water-organicmaterials by Hydrothermal Reaction[J]. J Mater Sci,2008,43(7):2115-2122.
[15]	Jencks W P,Regenstein J. Ionization Constants of Acids and Bases[M]//Roger L L,Fiona M M. Handbook of Biochemistry and Molecular Biology. 4th ed. Boca Raton:CRC Press,2010:595-596.
[16]	Cremlyn R J. An Introduction to Organosulfur Chemistry[M]. Chichester:John Wiley & Sons Ltd,1996:8-17.
[17]	Landis P S. The Chemistry of 1,2-Dithiole-3-thiones[J]. Chem Rev,1965,65(2):237-245
[18]	Johnson D E,Horodysky P A G,Olszewski W F,et al. Sulfurized Olefin Extreme Pressure/Antiwear Additives and Compositions Thereof:US,US5135670[P],1992-08-04.
[19]	Qian E W,Hirabayashi K,Hirasawa S,et al.Synthesis of Di-t-butyl Polysulfide from Isobutene, Hydrogen Sulfide, and Sulfur(Part 2) Catalytic Behavior of MFI Zeolites[J]. J Jpn Pet Inst,2009,52(3):128-138.
[20]	Sobik P,Grunenberg J,B r czky K,et al. Identification, Synthesis, and Conformation of Tri- and Tetrathiacycloalkanes from Marine Bacteria[J]. J Org Chem,2007,72(10):3776-3782.
[21]	Thomson J W,Nagashima K,Macdonald P M,et al.From Sulfur-amine Solutions to Metal Sulfide Nanocrystals:Peering into the Oleylamine-sulfur Black Box[J]. J Am Chem Soc,2011,133(13):5036-5041.

Product Analysis and Reaction Mechanism of High-Pressure Synthesis of Sulfurized Isobutylene by One-Step Method

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