Vinyl
monomers from soybean, sunflower, linseed, and olive oils
were copolymerized with styrene (St), methyl methacrylate (MMA), and
vinyl acetate (VAc) to determine the reactivity of biobased monomers
in radical copolymerization, as well as their feasibility in emulsion
processes for the synthesis of biobased latexes. Radical copolymerization
of plant-oil-based monomers is described with the classical Mayo–Lewis
equation. Using emulsion (or miniemulsion) polymerization with MMA
or VAc, stable aqueous polymer dispersions with latex particles measuring
80–160 nm and containing 3–35 wt % of biobased monomer
units were successfully synthesized. The number-average molecular
weight of the latex copolymers (20 000–150 000)
decreases by increasing the degree of unsaturation in monomers and
their content in the reaction feed. The presence of plant-oil-based
fragments changes the
T
g
of resulting
copolymers from 105 to 79 °C in copolymerization with MMA and
from 30 to 11 °C in copolymerization with Vac. As a result, biobased
units provide considerable flexibility (elongation at break of about
250%) and improve the toughness of the normally rigid and brittle
poly(MMA). Even a small amount (2–5%) of biobased fragments
incorporated into the structure of poly(VAc) significantly improves
water resistance and provides hydrophobicity to the resulting polymer
latex films. The obtained results clearly indicate that the vinyl
monomers from plant oils can be considered as good candidates for
internal plasticization of polymeric materials through reducing intermolecular
interactions in copolymers.
The objective of the present study is development of novel surface-active block, comb-like, and branched copolymers with peroxide-containing chains, as well as derived functional luminescent and magnetic nanoparticles. The main experimental approaches are based on tailored synthesis of the oligoperoxide surfactants of desired structures and derived coordinating complexes of transitional and rare earth elements. Oligoperoxide-based synthesis of luminescent, magnetic, and other functional nanocomposites with controlled size distribution, functionality, reactivity, and biocompatibility is described. Developed methods provide combining the formation of polymeric, metal, and metal-oxide nanoparticles with irreversible modification of their surface by functional fragments capable of radical and other reactions, including binding of physiologically active substances. Novel nanoparticles were studied by chemical, colloidal-chemical, and rheological methods, X-ray diffraction technique, luminescent spectroscopy, and transmission and scanning electronic microscopy. The availability of ditertiary peroxide fragments on the nanoparticle surface provides a possibility of radical grafting functional polymer chains. The developed functional nanoparticles have been used for phagocytosis measurement, as well as markers of pathological cells, antimicrobial remedies, and nanocarriers for targeted drug delivery.
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