Doctoral Dissertations


"Colloidal Unimolecular Polymer (CUP) particles were prepared by the process of water reduction on amphiphilic acrylic copolymers prepared via free radical polymerization technique. The formation of CUP particles was driven by the polymer-polymer interaction being greater than the polymer-solvent interaction and entropically favored by release of the water. It was demonstrated by Dynamic Light Scattering technique that CUP particles based on copolymers below 13,000 MW were unstable and the particles aggregated to a higher particle size. For the polymers with molecular weight (MW) above 13,000, a good correlation between the theoretical and experimental CUP particle size was observed. The rheology behavior of CUPs was affected primarily by the tertiary electroviscous effects arising from the surface charged groups. At similar volume fraction, the CUP viscosity increased in the following order: quaternary ammonium > sulfonate > carboxylate which was directly related to the associated surface water fraction. The surface water was denser than bulk water and was the highest for sulfonate followed by carboxylate and quaternary ammonium functional CUP. The surface activity as measured by maximum bubble pressure tensiometer had the following trend: sulfonate > quaternary ammonium > carboxylate, at similar volume fraction which was attributed to the surface energy reduction because of electrostatic-repulsion. CUPs with sulfonate groups on the surface effectively catalyzed the acrylic-melamine crosslinking reactions and the cured films had mechanical properties similar to those obtained by using a commercial blocked p-toluene sulfonic acid catalyst. The CUP catalysts offered distinct advantages such as lower amount required on a molar equivalent basis and non-leachable in water after crosslinking, as compared to the commercial catalyst."--Abstract, page iv.


Van-De-Mark, Michael R.

Committee Member(s)

Sotiriou-Leventis, Lia
Schuman, Thomas P.
Winiarz, Jeffrey G.
Myers, John



Degree Name

Ph. D. in Chemistry


Missouri University of Science and Technology. Department of Chemistry
Missouri University of Science and Technology. Coatings Institute


Missouri University of Science and Technology

Publication Date

Spring 2015

Journal article titles appearing in thesis/dissertation

  • Molecular weight (MN) and functionality effect on CUP formation and stability
  • Synthesis and characterization of an acid catalyst for acrylic-melamine resin systems based on colloidal unimolecular polymer (CUP) particles of MMA-AMPS
  • Synthesis and characterization of cationic colloidal unimolecular polymer particles (CUPS)
  • Rheology and surface tension behavior of sulfonate functional colloidal unimolecular polymer (CUP)


xv, 166 pages

Note about bibliography

Includes bibliographic references.


© 2015 Ameya Manohar Natu, All rights reserved.

Document Type

Dissertation - Open Access

File Type




Subject Headings

Polymer colloids -- Testing
Surface tension -- Measurement
Polymers -- Rheology
Unimolecular reactions

Thesis Number

T 10721

Electronic OCLC #