The Incorporation of Vinyl Modified Regenerated Starch Nanoparticles in Emulsion Polymerizations
Creators: name: Cummings, Shidan
Publisher: name: Université d'Ottawa / University of Ottawa
Year: 2017
Subjects: Polymer
Starch
Emulsion
Latex
Polymerization
Nanoparticle
SNP
Composite
Waxy
Dent
Functional
Acrylate
Acrylic
Renewable

description: The replacement of synthetic polymers with renewable content in emulsion polymerization latexes has been a focus of research over the past several decades. Emulsion polymerization is a more sustainable way to produce polymers for films and resins. Starch is a sustainably sourced material that has proven to be extremely useful as a filler, comonomer, and property modifier for polymer latexes. In this thesis, we attempt to incorporate high levels of starch materials into emulsion latex using waxy and dent sourced (cheaper) vinyl-functionalized regenerated starch nanoparticles (RSNPs). When fed as a batch charge, incorporation (by reaction as opposed to blending) of a grade of waxy RSNPs with 3 wt.% polymerizable sugar-based monomer (PSBM) and medium hydrophobicity (S-3-M) into the polymer matrix was 0-10 wt.% for a 15 wt.% RSNP loaded, 40 wt.% solids latex. Semi-batch feeding of the S-3-M RSNPs resulted in stable latex with the highest loadings of 40 and 50 wt.% (40 wt.% solids) with 0-10 wt.% RSNP incorporation into the synthetic particles, while 40 wt.% loading (20 wt.% incorporation) was achieved with a grade of waxy RSNPs with 6 wt.% PSBM and medium hydrophobicity (S-6-M). Strategies were developed to prepare synthetic latexes with high RSNP loadings and moderate incorporation. Dent sourced RSNPs proved difficult to use in emulsion formulations due in part to the higher percentage of water-soluble linear amylose in the nanoparticles. To reduce the chances of coagulation and minimize the viscosity of the final latex it was important to ensure monomer starved conditions, that the only initiator feed occurred at the seed stage of the reaction (to degrade the soluble starch and prevent later stage coagulation), and that a hydrophobic tie-layer was used to assist in removal of soluble starch from the water phase. Although a successful procedure was devised for creating a dent sourced RSNP loaded latex with a viscosity of 250 cp, it was significantly longer than the procedures used with waxy RSNPs (6 h polymerization + 1 h RSNP dispersion). An additional treatment of the RSNP dispersion prior to the polymerization can lower the final latex viscosity to 100 cp. Higher incorporation of vinyl-functionalized RSNPs may be achievable if the covalently bonded PSBM functional groups are resistant to hydrolysis, the amylose and other small MW starches are completely removed from the water phase, and monomers with more appropriate reactivity and hydrophobicity are employed. To this end, maleic and methacrylic anhydride modified RSNPs were prepared and tested in emulsion polymerizations. The maleic anhydride modified RSNPs were successfully loaded into an emulsion latex at 15 wt.% (40 wt.% solids content) resulting in 20-30 wt.% incorporation when utilizing 2-ethylhexyl acrylate as the tie-layer monomer with 2-ethylhexyl acrylate or butyl acrylate/methyl methacrylate/acrylic acid as the shell layer. This work presents the only comprehensive attempt to incorporate RSNPs into synthetic latexes at high loadings and solids with persulfate initiation without the need to severely reduce the RSNP molecular weight. The learning generated provides a framework for continuing research into increasing the incorporation of RSNPs into polymer particles.