Amphiphilic cycloterpolymers of diallyldimethylammonium chloride, diallyloctadecylammonium chloride, and sulfur dioxide

Abstract

ABSTRACT:A hydrophilic monomer (diallyldimethylammonium chloride), a hydrophobic monomer (diallyloctadecylammonium chloride), and sulfur dioxide are cycloterpolymerized in dimethylsulfoxide using azobisisobutyronitrile as the initiator to afford water-soluble cationic polyelectrolytes having a five-membered cyclic structure on the polymeric backbone. The molecular weights of the polymers containing varying amounts of the hydrophobic monomer (0 -7.5 mol %) are determined by light-scattering experiments. The solution properties of the series of cationic polyelectrolytes are investigated by viscometric techniques. A polymer concentration (C* HA ) of Ͻ1 g/dL is required for the manifestation of hydrophobic associations in these terpolymers containing C 18 hydrophobic pendents. This is a notable improvement over the C* HA values (ca. 15-17 g/dL) for the associating cyclopolymers having a pendant length of C10 to C14. The polymer solutions exhibit a sharp increase in viscosity with increasing polymer concentrations in salt-free as well as salt-added solutions. The presence of sodium chloride is shown to enhance the hydrophobic association tremendously.

Synthesis and solution properties of amphiphilic cyclopolymers and terpolymers of 4‐methoxycarbonyl‐1,1‐diallylpiperidinium chloride, diallyloctadecylammonium chloride, and sulfur dioxide

“…The [η]'s in 0.1 N NaCl were found to be low in comparison with many other polymers synthesized in our earlier studies 8–10, 15–17. A 2‐g/dL solution of polymers 3 –M 2 ‐2.8 or 3 –M 2 ‐3.7 failed to give any indication of hydrophobic associations, as revealed by viscosity measurements.…”

“…The incorporation of the hydrophobic monomers was calculated with 1 H-NMR analysis. 23 The hydrophobic repeating unit had a total of 47 H atoms (excluding NH þ , which was exchanged to ND þ ); the integrated area (A) in the range d ¼ 0.6-1.65 belonged to 35 H atoms of the hydrophobic tail (CH 2 ) 16…”

“…[5][6][7][8][9][10] Polyampholytes and PZs, unlike polyelectrolytes, exhibit antipolyelectrolyte behavior, 6,[11][12][13] that is, an enhancement in the viscosity and solubility in the presence of added electrolytes (e.g., NaCl), because of the neutralization of the ionically crosslinked network in a collapsed coil conformation of the polymers. There have been some reports [14][15][16][17][18][19] that described the synthesis of associating ionic copolymers prepared by Butler's cyclopolymerization technique. Above a hydrophobic association concentration (C HA *), interchain associations of the hydrophobic groups led to a more pronounced increase in the viscosity by a reversible formation of the three-dimensional physical crosslinks of the polymer chains.…”

Synthesis and viscosity of hydrophobically modified polymers containing dendritic segments

“…The resulting polymer architecture, having cyclic units embedded in the backbone, has been recognized as the eighth major structural type of synthetic polymers 16. There are, however, only a few reports17–23 that describe the synthesis of associating ionic copolymers prepared by Butler's cyclopolymerization technique. Previous kinetic studies24 have indicated that monomer concentrations of 50–65 wt % are required to obtain polymers with high conversions, high molecular weights, and low residual double bonds.…”

Synthesis, viscosity behavior, and interactions with a surfactant of some amphiphilic copolymers of diallyldimethylammonium chloride and diallyldodecyl‐ or diallyloctadecyl‐ammonium chloride

“…The discovery of the polymerization of N,N ‐diallyl quaternary ammonium salts 1 by Butler and Ingley21, 22 via an intra‐ and intermolecular chain propagation through a five‐membered cyclic structure and subsequently, their copolymerization with sulfur dioxide23 led to the synthesis of an array of linear water‐soluble cationic polyelectrolytes (CPE)24 2 and 3 of tremendous scientific and technological interest. There are reports25–31 that describe the synthesis of associating ionic copolymers prepared by Butler's polymerization technique. Previous kinetic studies32 have indicated that a monomer concentration of 50–65 wt % is required to obtain polymers with high conversion, high molecular weight, and low residual double bonds.…”