Reversible addition–fragmentation
chain transfer (RAFT)
emulsion polymerization is a powerful tool for polymer encapsulation
of pigment nanohybrids. Conventional RAFT emulsion polymers, however,
contain sulfur residues that contribute to undesired odor and deleterious
effects on final materials. Our strategy relies on an amphiphilic
macromonomer poly(methacrylic acid-co-methyl methacrylate)
P(MAA-co-MMA) with an ω-unsaturated end group
synthesized in situ via cobalt(II)-mediated catalytic chain transfer
polymerization (CCTP) at the surface of C.I. Pigment Blue 15:3 (PB)
particles. Subsequently, these macromonomers are used as the living
points to mediate the in situ sulfur-free RAFT (SF-RAFT) emulsion
polymerization of monomers (butyl methacrylate (BMA) and butyl acrylate
(BA)). It was found that a well-controlled polymerization process
was achieved by semibatch SF-RAFT emulsion polymerization on the PB
surface, as evidenced by the smooth increase in the molecular weight
of polymer chains as the polymerization progressed and by transmission
electron microscopy (TEM) results. Due to the sealing effect, these
polymer/PB hybrid particles exhibited excellent colloidal stability
in the aqueous phase. More importantly, film-forming hybrid particles
with a soft P(BMA-co-BA) shell were successfully
prepared in this work, which suggested that SF-RAFT-mediated polymerization
may offer a useful alternative approach to traditional RAFT emulsion
polymers for the preparation of organic/inorganic nanohybrids.
A novel, waterborne polydimethylsiloxane (PDMS)-modified polyurethane-acrylic (Si-PUA)/pigment hybrid emulsion was synthesized by one-step miniemulsion polymerization for the pigment printing of polyester fabric. The phase structure, hydrophobicity, and thermal and mechanical properties of the formed films with different PDMS contents from the hybrid emulsion were investigated. The results indicated that the pigment particles were uniformly distributed in the homogeneous phase polymer substrate without phase separation occurring between the PDMS phase and polyurethane-acrylic. The hydrophobicity and toughness of the Si-PUA/pigment hybrid latex films gradually increased with the increase of PDMS content. Moreover, the obtained hybrid emulsion was used as a self-curable hybrid pigment that was applied to polyethylene terephthalate fabric for pigment printing. This showed that the Si-PUA/pigment hybrid latex particles yielded similarly good values in terms of color strength, and dry- and wet-rubbing fastness to the PDMS-free hybrid latex particles. Furthermore, use of the Si-PUA/pigment hybrid latex avoided certain problems related to printed fabric, such as poor air permeability and softness.
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