A Catalyst Platform for Unique Cationic (Co)Polymerization in Aqueous Emulsion

Abstract

Sodium dodecyl benzene sulfonate (DBSNa) surfactants, with a polydisperse and hyperbranched structure, combined with different rare earth metal salts generate highly water‐dispersible Lewis acid surfactant combined catalysts (LASCs). This platform of new complexes promotes fast, efficient cationic polymerization of industrially relevant monomers in direct emulsion at moderate temperature. The process described here does not require high shearing, long polymerization time, or large catalyst content. It allows the reproducible generation of high‐molar‐mass homopolymers of pMOS, styrene, and isoprene, as well as random or multiblock copolymers of the latter two, in a simple and straightforward one‐pot reaction.

Cationic polymerization of styrene using iron-containing ionic liquid catalysts in an aqueous dispersed medium

“…However, the molar mass obtained in these studies ( n M ≤ 4.5 kg mol -1 ) were much lower than those reported here. There are reports in the literature of styrene-derived polymers with higher number-average molar mass, 40 [11] , 117 [12] , and 550 kg mol -1 [40] , in which, the distributions are relatively high, from 2.0 to 3.8, because it is very difficult to control these polymerization mechanism as large polymer chains are formed.…”

“…However, conventional ionic polymerizations are often performed under anhydrous conditions and traces of water should be avoided as catalysts react with water and become inactive [2] . In recent decades several efforts have been made in order to develop new catalysts very attractive to the ionic polymerization of different monomers in aqueous dispersed medium [3][4][5][6][7][8][9][10][11][12] . However, these works use an excessive catalyst load (3 to 10 mol%) and, except for the work of Vasilenko et al [12] , there was the formation of polymers with low molar masses (less than 40 kg mol -1 ), similar to that obtained via free radical bulk polymerization.…”

“…In recent decades several efforts have been made in order to develop new catalysts very attractive to the ionic polymerization of different monomers in aqueous dispersed medium [3][4][5][6][7][8][9][10][11][12] . However, these works use an excessive catalyst load (3 to 10 mol%) and, except for the work of Vasilenko et al [12] , there was the formation of polymers with low molar masses (less than 40 kg mol -1 ), similar to that obtained via free radical bulk polymerization. In the literature, there are few reports on cationic polymerization using the miniemulsion technique.…”

A novel synthetic strategy for styrene–butadiene–styrene tri-block copolymer with high cis -1,4 units via changing catalytic active centres

“…Advanced polymer materials are widely concerned by people because of their light weight, high strength and multiple functions [1][2][3][4][5]. Styrene-butadiene-styrene tri-block copolymer (SBS), as one of the most important thermoplastic elastomers with excellent mechanical properties and processability, is an attractive material that has drawn significant attention in industry and academia [6][7][8][9][10]. Anionic polymerization is presently used in the industrial synthesis of SBS, and the obtained copolymers have narrow molecular weight distributions, but anionic polymerization cannot effectively control the stereoregularity of butadiene.…”

New insight into the cold crystallization of natural rubber: The role of linked and free fatty chains

“…In this study, it was investigated the synthesis of new hybrid polymers formed from the functionalization of a pure 1,4‐ cis PI (molar mass of ~10 000 g/mol) with one or two fatty chains at one chain‐end as a closer model of NR and their cold crystallization properties. Even if isoprene polymerization was already studied by many techniques (cationic, anionic, radical, metathesis, and coordination polymerization), none of them allowed to reach a pure 1,4‐ cis microstructure with controlled chain‐ends.…”