Crosslinkable surfactants based on linoleic acid-functionalized block copolymers of ethylene oxide and e-caprolactone for the preparation of stable PMMA latices

B.H. Tan, Dirk W. Grijpma, Tijs Nabuurs, Jan Feijen

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21 Citations (Scopus)


Amphiphilic diblock and triblock copolymers consisting of poly(ethylene oxide) (PEO) as (central) hydrophilic segment and poly(ε-caprolactone) (PCL) as hydrophobic segment(s) were prepared by ring opening polymerization. The length of the PEO segment was kept constant View the MathML source, whereas the length of the PCL block(s) was either 6 or 10 units for diblock copolymers and 3 or 5 units at each end for the triblock copolymers. These block copolymers were end-functionalized by esterification with linoleic acid (LA), which contains reactive double bonds. The autoxidative behavior of PEO45-(CL3-LA)2 functionalized triblock copolymers was investigated by exposure of films to air at ambient conditions. Ninety percent of the double bonds had disappeared in 15 d and a crosslinked structure was obtained after 30 d. Critical micelle concentrations (CMC) of the crosslinkable surfactants were in the range of 0.08–0.19 mmol/l for the diblock copolymer and of 0.19–0.26 mmol/l for the triblock copolymer. The surface tension of aqueous surfactant solutions at the CMC (γCMC) (25 °C) varied from 47.1 to 51.4 mN/m for the diblock and from 45.6 to 48.1 mN/m for the triblock systems. For both systems CMC and γCMC increase with increasing HLB values. These surfactants were used in PMMA latex preparations. The latices of PMMA prepared with LA-functionalized diblock and triblock copolymers yielded narrow particle size distributions and particle sizes of 180 and 370 nm, respectively, whereas latices prepared with SDS had a particle size of 90 nm. After extraction of the latex particles with methanol, the amounts of the unextractable (either buried or copolymerized) LA-functionalized diblock and triblock copolymers found in extracted PMMA latex particles were 10 and 24% of the initial amount of surfactant added respectively. Control experiments with a stearic acid (SA) containing diblock copolymer showed that the amount of buried surfactant in PMMA latices was 6.5%. By comparing the overall latex characteristics and stability (shelf stability, freeze–thaw testing and addition of electrolyte solutions and ethanol) it was concluded that an LA-functionalized diblock copolymer (MPEO45-CL10-LA) gave better stabilization of PMMA latices than an LA-functionalized triblock copolymer of comparable composition and HLB value.
Original languageUndefined
Pages (from-to)1347-1357
Issue number4
Publication statusPublished - 2005


  • METIS-230234
  • IR-71335

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