Synthesis, characterization and application of acrylic colloidal unimolecular polymer (CUP)

182 Pages·2016·3.92 MB·English

by  Ameya Manohar Natu

SScchhoollaarrss'' MMiinnee
Doctoral Dissertations Student Theses and Dissertations
Spring 2015
SSyynntthheessiiss,, cchhaarraacctteerriizzaattiioonn aanndd aapppplliiccaattiioonn ooff aaccrryylliicc ccoollllooiiddaall
uunniimmoolleeccuullaarr ppoollyymmeerr ((CCUUPP))
Ameya Manohar Natu
Follow this and additional works at: https://scholarsmine.mst.edu/doctoral_dissertations
Part of the Polymer Chemistry Commons
DDeeppaarrttmmeenntt:: CChheemmiissttrryy
RReeccoommmmeennddeedd CCiittaattiioonn
Natu, Ameya Manohar, "Synthesis, characterization and application of acrylic colloidal unimolecular
polymer (CUP)" (2015). Doctoral Dissertations. 2391.
https://scholarsmine.mst.edu/doctoral_dissertations/2391
This thesis is brought to you by Scholars' Mine, a service of the Missouri S&T Library and Learning Resources. This
work is protected by U. S. Copyright Law. Unauthorized use including reproduction for redistribution requires the
permission of the copyright holder. For more information, please contact [email protected].
SYNTHESIS, CHARACTERIZATION AND APPLICATION OF ACRYLIC
COLLOIDAL UNIMOLECULAR POLYMER (CUP)

by

AMEYA MANOHAR NATU

A DISSERTATION
Presented to the Faculty of the Graduate School of the
MISSOURI UNIVERSITY OF SCIENCE AND TECHNOLOGY
In Partial Fulfilment of the Requirements for the Degree

DOCTOR OF PHILOSOPHY
in
CHEMISTRY
2015
Approved by
Dr. Michael R. Van De Mark, Advisor
Dr. Chariklia Sotiriou-Leventis
Dr. Thomas Schuman
Dr. Jeffrey Winiarz
Dr. John Myers
 2015
AMEYA MANOHAR NATU
All Rights Reserved
iii
PUBLICATION DISSERTATION OPTION
The dissertation is divided into five chapters and has been prepared in the form of
four manuscripts for publication. Papers included are prepared as per the requirements of
the journal in which they are published or are submitted.
Paper I found on pages 12-42 is published Journal of Coatings Technology and
Research.
Paper II found on pages 43-85 has been submitted to Progress in Organic Coatings.
Paper III found on pages 86-121 has been submitted to Colloid and Polymer
Science.
Paper IV found on pages 122-160 will be submitted to a peer-reviewed journal.
iv
ABSTRACT
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.
v
ACKNOWLEDGMENTS
First and foremost, I would like to thank my advisor, Dr. Michael R. Van De Mark
for his continuous guidance and support during my pursuit of graduate studies at Missouri
S&T. His technical, professional and personal guidance has helped me to not only be
successful academically but also to be a better human being. I admire his compassion and
discipline which taught me to be passionate and hard-working.
I want to thank my advising committee members, Dr. Chariklia Sotiriou-Leventis,
Dr. Thomas Schuman, Dr. Jeffrey Winiarz and Dr. John Myers for their support and
guidance throughout the completion of my Ph.D. program. I thank the Department of
Chemistry and the Missouri S&T Coatings Institute for financial support and other
resources. I acknowledge fellow researchers: Dr. Minghang Chen, Dr. Jigar Mistry, Sagar
Gade, and Yousef Dawib for their help and support at various occasions.
I am grateful to my friends; Abhishek, Pratik, Viswanaath and Sushrut who
believed in me and my endeavors.
Last but not the least, I am truly indebted to my Family: my parents; Mr. Manohar
Natu and Mrs. Veena Natu; grandmother: Mrs. Girija Vishwanath Natu; sister: Amala Natu
and my wife Ar. Vrushali Lele, as well as my cousins and family for their unconditional
love and support.
vi
TABLE OF CONTENTS
Page
PUBLICATION DISSERTATION OPTION ................................................................... iii
ABSTRACT ...................................................................................................................... iv
ACKNOWLEDGMENTS ...................................................................................................v
LIST OF ILLUSTRATIONS ...............................................................................................x
LIST OF TABLES ........................................................................................................... xiv
SECTION
1. INTRODUCTION ...................................................................................................... 1
1.1. POLYMER NANOPARTICLES ........................................................................1
1.2. POLYMERIC MICELLES .................................................................................2
1.3. COLLOIDAL UNIMOLECULAR POLYMER (CUP) .....................................5
1.3.1. Water-reduction Process For CUP Synthesis.............................................7
1.3.2. Water-reduction Protocol ...........................................................................7
1.3.3. Determination Of Effective Charge ...........................................................7
1.4. OBJECTIVE OF THIS RESEARCH ................................................................10
PAPER
I MOLECULAR WEIGHT (MN) AND FUNCTIONALITY EFFECT ON CUP
FORMATION AND STABILITY .......................................................................... 12
ABSTRACT ................................................................................................................. 12
INTRODUCTION ........................................................................................................ 13
EXPERIMENTAL ....................................................................................................... 16
Materials .............................................................................................................16
Polymer synthesis ...............................................................................................16
Synthesis for 12K polymer .................................................................................17
Characterization of polymers synthesized ..........................................................17
Water-Reduction of MMA-MAA based copolymers to form CUPs .................18
Characterization of CUPs ...................................................................................20
RESULTS AND DISCUSSION .................................................................................. 21
Acid Number ......................................................................................................21
Molecular weight determination ........................................................................22
vii
Water-reduction of the polymers to prepare CUPs ............................................23
Viscosity measurements of CUP solutions ........................................................27
Particle size analysis ...........................................................................................31
CONCLUSIONS .......................................................................................................... 39
ACKNOWLEDGEMENTS ......................................................................................... 40
REFERENCES ............................................................................................................. 41
II. SYNTHESIS AND CHARACTERIZATION OF AN ACID CATALYST FOR
ACRYLIC-MELAMINE RESIN SYSTEMS BASED ON COLLOIDAL
UNIMOLECULAR POLYMER (CUP) PARTICLES OF MMA-AMPS .............. 43
ABSTRACT ................................................................................................................. 43
1. INTRODUCTION .................................................................................................... 44
2. MATERIALS AND METHODS ............................................................................. 48
2.1. Characterization of Commercial Acrylic Resins ...............................................49
2.2. Synthesis of Random Copolymer of MMA and AMPS ....................................49
2.3. Water-Reduction of MMA-AMPS Based Copolymer To Form CUPs .............50
2.4. CO2H-CUP Synthesis ........................................................................................50
2.5. Characterization of Synthesized MMA-AMPS Copolymer ..............................51
2.6. Characterization of CUPs ..................................................................................51
2.7. Coating Formulations and Testing ....................................................................52
3. RESULTS AND DISCUSSION .............................................................................. 57
3.1. Process of Water-reduction ...............................................................................57
3.2. Rheological Behavior ........................................................................................59
3.3. Role of Solvent and Divalent Cations ...............................................................60
3.4. Particle Size Analysis Using DLS .....................................................................62
3.5. Thermogravimetric Analysis and Differential Scanning Calorimetry (DSC) ...63
3.6. Effectiveness of CUP Catalyst In Curing OH-latex With Melamine Resin .....65
3.7. Efficiency of CUP Catalyst In Curing OH-latex With Melamine Resin ..........71
3.8. Effectiveness of CUP Catalyst In Curing CO H -latex and CO H-CUP resin
2 2
With Melamine Resin .......................................................................................72
3.9. Leaching Experiment ........................................................................................79
4. CONCLUSIONS ...................................................................................................... 82
5. ACKNOWLEDGEMENTS ..................................................................................... 83
viii
6. REFERENCES ......................................................................................................... 83
III.SYNTHESIS AND CHARACTERIZATION OF CATIONIC COLLOIDAL
UNIMOLECULAR POLYMER PARTICLES (CUPS) ......................................... 86
ABSTRACT ................................................................................................................. 86
1. INTRODUCTION .................................................................................................... 87
2. THEORETICAL BASIS FOR RHEOLOGY BEHAVIOR ..................................... 91
2.1. Primary Electroviscous Effect ...........................................................................91
2.2. Secondary Electroviscous Effect .......................................................................91
2.3. Tertiary Electroviscous Effect ...........................................................................92
2.4. Determination of Intrinsic Viscosity of CUPs ..................................................92
3. MATERIALS AND METHODS ............................................................................. 93
3.1. Materials ............................................................................................................93
3.2. Polymer Synthesis and Characterization ...........................................................93
3.3. Water-reduction .................................................................................................95
3.4. Particle Size and Distribution of CUPs .............................................................95
3.5. Absolute Viscosity of CUPs ..............................................................................96
3.6. Surface Tension .................................................................................................96
4. RESULTS AND DISCUSSION .............................................................................. 97
4.1. Characterization of Polymer and CUPs ............................................................97
4.2. Water-reduction Process ...................................................................................99
4.3. Rheological Behavior ......................................................................................100
4.4. Particle Size Analysis Using DLS ...................................................................101
4.5. Specific Viscosity Comparison .......................................................................102
4.6. Density of Surface Water ................................................................................108
4.7. Equilibrium Surface Tension Behavior ...........................................................111
4.8. Dynamic Surface Tension Behavior................................................................114
5. CONCLUSIONS .................................................................................................... 118
6. ACKNOWLEDGEMENTS ................................................................................... 119
7. REFERENCES ....................................................................................................... 120
IV.RHEOLOGY AND SURFACE TENSION BEHAVIOR OF SULFONATE
FUNCTIONAL COLLOIDAL UNIMOLECULAR POLYMER (CUP) ............. 122
ABSTRACT ............................................................................................................... 122
ix
1. INTRODUCTION .................................................................................................. 123
2. THEORETICAL BASIS ........................................................................................ 126
2.1. Determination of Effective Charge .................................................................126
2.1.1. Nernst-Einstein model ............................................................................126
2.1.2. Hessinger’s model ..................................................................................127
2.1.3. Charge renormalization ..........................................................................127
2.2. Theories Related With Rheology ....................................................................129
2.3. Determination of Intrinsic Viscosity of CUPs ................................................132
3. EXPERIMENTAL ................................................................................................. 133
3.1. Materials ..........................................................................................................133
3.2. Synthesis and Characterization of Copolymers ..............................................133
3.3. Preparation of CUPs ........................................................................................134
3.4. Characterization of CUPs ................................................................................136
3.4.1. Shearing viscosity ..................................................................................136
3.4.2. Absolute viscosity of CUP solutions .....................................................136
3.4.3. Particle size of CUPs..............................................................................136
3.4.4. Surface tension measurement.. ...............................................................137
4. RESULTS AND DISCUSSION ............................................................................ 137
4.1. Acid Number and Density ...............................................................................137
4.2. Particle Size Analysis ......................................................................................138
4.3. Specific Viscosity of CUP Suspension ...........................................................139
4.4. Surface Water Density ....................................................................................144
4.5. Rheological Model Fitting ..............................................................................146
4.6. Surface Tension Measurement ........................................................................150
5. CONCLUSIONS .................................................................................................... 157
6. ACKNOWLEDGEMENTS ................................................................................... 158
7. REFERENCES ....................................................................................................... 158
SECTION
2. SUMMARY ........................................................................................................... 161
BIBLIOGRAPHY ...................................................................................................... 164
VITA ........................................................................................................................ 166