Living Oligomerization of Isobutylene Using Di- and Triisobutylene Hydrochlorides as Initiators

Abstract

The living isobutylene oligomerization initiated by diisobutylene hydrochloride (1) or triisobutylene hydrochloride (2) in the presence of BCl3 and benzyltriethylammonium tetrachloroborate has been studied by gas chromatography which allowed the detection of the individual oligomers 2, 3, 4, etc. The reactions followed second-order kinetics, first-order with respect to initiator (1 or 2), first-order with respect to BCl3, and zeroth-order with respect to isobutylene. A kinetic model has been derived which explains these phenomena.

LIVING CARBOCATIONIC OLIGOMERIZATION OF ISOBUTYLENE BY TERTIARY ALCOHOL/BCl3/1-METHYL- 2-PYRROLIDINONE INITIATING SYSTEMS. KINETIC STUDY

“…These results are corroborated by recent works reported by Mayr et al [20,27] who studied the living isobutylene oligomerization initiated by CumCl or TMPCl/BCl 3 system in the presence of benzyltriethylammonium tetraborate, particularly the kinetics of the initiation and the early propagation steps. These results are corroborated by recent works reported by Mayr et al [20,27] who studied the living isobutylene oligomerization initiated by CumCl or TMPCl/BCl 3 system in the presence of benzyltriethylammonium tetraborate, particularly the kinetics of the initiation and the early propagation steps.…”

Direct synthesis of highly reactive polyisobutylenes via cationic polymerization of isobutylene co‐initiated with TiCl4 in nonpolar hydrocarbon media

“…It is necessary to further investigate the possibility of incorporation of other olefins (n-butane and 2-butene) or butadiene into PIB polymer chains during IB polymerization from the mixed C 4 fractions with H 2 O/TiCl 4 /iAmOH initiating system at 230 C even though IB was more highly reactive than other C 4 isomers (butadiene, n-butene, and cis22-butene) in the cationic polymerization co-initiated by TiCl 4 . 87 In order to get further insight into the chemical structure of resulting polymer chains, 13 C NMR characterization was performed on the representative polymer sample obtained from selective cationic polymerization of IB in the mixed C 4 fraction feed with H 2 O/TiCl 4 /iAmOH ini-tiating system at iAmOH/TiCl 4 5 0.3 at 230 C, and the comparative commercial HRPIB (BASF, Glissopal 1000, exo-double bond 5 90.1 mol %) obtained from IB polymerization in hexane. The DEPT-135 technique was also used to analyze the chemical structure of this resulting polymer since only the lines of carbons bonded to hydrogen are detected and lines of methine and methylene carbons exhibit a different phase in DEPT-135 spectra.…”

“…[63][64][65][66][67][68][69] Strong electron donors, such as dimethylsulfoxide, N,N-dimethylacetyamide, amines, and pyridine, were normally introduced to these above polymerization systems co-initiated by BCl 3 or TiCl 4 to increase initiation efficiency, stabilize propagating species, and suppress chain transfer reaction and termination. [9][10][11][12][13][14][15][16][17][18][19] Highly reactive polyisobutylenes (HRPIBs) with low molecular weight and preferably more than 80 mol % have high reactivity for further functionalization and could be used as intermediates in the preparation of additives for fuels and lubricants. [4][5][6][7][8][20][21][22][23][24][25][26][27][28][29][30][31][32][33] HRPIB can be mainly prepared by two major techniques: (A) single-step process and (B) two-step process.…”

Synthesis, characterization and biological activity of C60 derivative

“…Many great efforts have been made to achieve living cationic polymerization since the first living polymerization was discovered in 1956 1. Living cationic polymerizations of isobutylene (IB) coinitiated by BCl 3 , TiCl 4 , and organoaluminum chlorides, such as Et 2 AlCl and Me 2 AlCl, have been achieved 2–11. The key of living cationic polymerization system is to match the reactivity of monomer to the strength of Lewis acid coinitiator.…”

“…The key of living cationic polymerization system is to match the reactivity of monomer to the strength of Lewis acid coinitiator. Initiator was selected from organic tertiary esters, ethers, alcohols, halides, and substituted epoxides 2–11. Strong electron donors (EDs), such as dimethylsulfoxide, N,N ‐dimethylacetyamide, amines, and pyridine, were introduced to these above polymerization systems coinitiated by BCl 3 or TiCl 4 to increase initiation efficiency, stabilize propagating species, and suppress chain transfer reaction and termination.…”