Styrenic Surfmer in Emulsion Copolymerization of Acrylic Monomers:  I. Synthesis and Characterization of Polymerizable Surfactants

Abstract

Two procedures to prepare styrenic reactive surfactants are described. The first one, close to a procedure of Ito et al., involves the initiation of anionic polymerization of ethylene oxide by an alkyl silanolate. Once the ethylene oxide is fully consumed, the anion is condensed on a styrenic alkyl bromide. Then the hydroxyl is recovered by a reaction of deprotection. The second one, on the contrary, starts from the hydrophobic end group. This anionic polymerization is initiated by vinyl benzyl alcoholate. Successively butylene oxide and ethylene oxide are polymerized. In the last step, the anion can be used to open the ring of propane sultone and we produce an anionic reactive surfactant, or the living chain can be hydrolyzed to obtain a nonionic surfactant. This second procedure gives good control of both hydrophobicity and hydrophilicity. The physicochemical properties of the corresponding surfactants are measured.

Syntheses of Poly(ethylene oxide) Macromonomers Carrying Tertiary Amine and Quaternary Ammonium End Groups

“…p-Vinylbenzyl alcohol (VBA) was prepared from VBC by reaction with sodium acetate followed by alkaline hydrolysis, according to the procedure described, 7 and distilled over calcium hydride (CaH 2 ) under high-vacuum line, and sealed into calibrated tubes with a breakable seal. Commercial 2-dimethylaminoethyl chloride hydrochloride (DMAC-HCl) (Aldrich) was dried by evacuation under vacuum.…”

“…1 As usual, styryl or methacryloyl functions have been introduced as a (co)polymerizable end group, say α-end group, of the macromonomer, while the other ω-end group is also feasible to introduce another functionality. So far to our knowledge, hydroxyl, 2,3 carboxylate, [4][5][6] sulfonate, 7,8 aldehyde, 9,10 and perfluoroalkyl 11 groups have been reported. In most cases [3][4][5][6][7][8][9][10][11] some elaborate procedures have been involved either in anionic polymerization of ethylene oxide (EO) or in end-group transformation, while 2-hydroxyethyl methacrylate was used together with a Lewis acid to initiate cationic EO polymerization to give poly(ethylene glycol) monomethacrylate in one step.…”

“…So far to our knowledge, hydroxyl, 2,3 carboxylate, [4][5][6] sulfonate, 7,8 aldehyde, 9,10 and perfluoroalkyl 11 groups have been reported. In most cases [3][4][5][6][7][8][9][10][11] some elaborate procedures have been involved either in anionic polymerization of ethylene oxide (EO) or in end-group transformation, while 2-hydroxyethyl methacrylate was used together with a Lewis acid to initiate cationic EO polymerization to give poly(ethylene glycol) monomethacrylate in one step. 2 Our recent strategy in PEO macromonomer synthesis includes initiation of anionic EO polymerization with a functional alcohol, F-OH, as suggested by the original work by Rempp et al, who used potassium p-isopropenylbenzylate to have a corresponding macromonomer.…”

“…[4][5][6][7][8] The charges introduced are expected to add stability to the polymeric microspheres and to prepare extended PEO brushes. Therefore we first tried polymerization of EO with DMAE alkoxide followed by reaction with p-vinylbenzyl chloride (VBC).…”

Synthesis, morphology and rheology of core-shell silicone acrylic emulsion stabilized with polymerisable surfactant

“…It has been demonstrated that polymerisable surfactants exhibit an exceptionally high degree of incorporation into the emulsion polymer, protecting the emulsion from flocculation. Furthermore, the limited mobility of polymerisable surfactants avoids surface migration and the formation of hydrophilic domains in the films, resulting in greatly reduced process foaming, enhanced solvent resistance, improved adhesive and mechanical properties, and far less residual levels in effluent streams, as compared with nonreactive surfactants [22][23][24][25][26][27]. Anionic polymerisable maleate surfactants have already gotten extensive attention from a point of view of reactivity/copolymerization behavior [28,29], and hydroxyethyl methacrylate on maleic anhydride is now available commercially [27].…”