Commodity and specialty-grade rubbers, such as styrene-butadiene (SBR) or nitrile-butadiene (NBR), are industrially produced in large trains of continuous reactors using an emulsion polymerization process. Both SBR and NBR systems are largely unstudied. Furthermore, the studies that have been published on NBR have been typically limited to issues concerning the characteristics of the product behaviour (i.e. oil/fuel resistance, tensile strength, hardness, compression set). In this work a detailed mathematical model has been developed in order to simulate the industrial production of NBR via emulsion copolymerization of acrylonitrile (AN) and butadiene (Bd) in batch, continuous and trains of continuous reactors. Model predictions include monomer conversion, polymerization rate, copolymer composition, number- and weight-average molecular weights, tri- and tetra-functional branching frequencies, and the number and average size of polymer latex particles. NBR is typically produced at low temperatures (5 to 10 degrees C) using a redox initiation system to generate free radicals. The system is typically composed of three phases, water, polymer particles, and monomer. Surfactants and electrolytes are used to stabilize the particle and monomer phases as polymerization proceeds. Of particular industrial importance, in today's world of tailor-made products, is detailed control over the polymerization reaction. Such control requires a deep understanding of the influence of various reactant feed rates and reactor operating conditions on the process response. In particular, policies to minimize copolymer composition drift and to control molecular weight, polydispersity and chain branching at desirable levels. The model is cast in a dynamic form using ordinary differential equations to describe the change of each species, the average number of particles, total average polymer volume, and the first three leading moments of the molecular weight distribution. With a multiphase system it is necessary to determine the concentration of each component in each phase. For this, a constant partition coefficient approach was adopted, as opposed to a purely thermodynamic approach. Particle generation was modelled considering both micellar and homogeneous mechanisms. Model parameters were obtained from the open literature or arrived at after sensitivity analysis. Simulations starting the reactors full of water, feeding all ingredients to the first reactor and using an average residence time of 60 minutes revealed considerable copolymer drift starting in the forth reactor (33% conversion), and heightened molecular weights and chain branching once the monomer phase disappeared (50% conversion). Further simulations revealed that both copolymer drift and the growth of molecular weight and branching could be controlled through additional feed streams of AN and chain transfer agent to downstream reactors. Furthermore, polymer productivity could be increased by appropriately splitting the total monomer feed between the first couple of reactors in the train.

The goal of this work is to increase the current understanding of Controlled Radical Polymerizations (CRPs) in two areas. Progressing closer towards employing an aqueous system, specifically miniemulsion, to produce poly(vinyl acetate) via reversible addition fragmentation chain transfer (RAFT) chemistry constitutes the first part of this goal. Presented are the results of miniemulsion polymerizations using both water and oil-soluble initiators. Limiting conversions in both are examined and explained in terms of radical loss. The second part of the goal is to further the understanding of the nature of the RAFT/miniemulsion system when employed in continuous tubular reactors. The development of the recipe using mixed surfactants, the results of styrene homopolymerizations in batch and tube, and the results of a chain extension experiment demonstrating the living nature of the chains formed in the tubular reactor are presented. Kinetic anomalies are addressed, as well as polydispersity (PDI) differences between batch and tube. Flow phenomenon and their influence on residence time distribution and by implication the polydispersity of the polymer formed are offered as explanations for the variance in PDI and are subsequently quantified. A model of RAFT in laminar flow is presented and the results and implications are discussed in general terms. The flow profile of the reactor is examined using a tracer technique developed specifically for this system. Experiments are presented directly relating the residence time distribution to the polydispersity of the polymer. Transient behavior of the reactor in isolated plug flow is explained in terms of initiator loss. Both experimental data and a model are used to support this hypothesis. Finally, conclusions and implications are presented and unanswered questions and the ideas for future work that they generated are addressed.

Acrylonitrile based engineering random copolymers were prepared via one step emulsion polymerization using ammonium persulfate (initiator), 1-dodecanthiol (chain transfer agent) and DOWFAX 8390 (surfactant) in the presence of water at approximately 65 0C. Three copolymer compositions were studied for novel polyacrylonitrile, (PAN)-polyhydroxyethyl acrylate (PHEA), PAN-polybutyl acrylate (PBA), novel PAN-polyt-butyl acrylate (PtBA), PAN-polyethyl acrylate (PEA) and PAN-polymethyl acrylate (PMA) with acrylate content varying from 8, 12 and 16 molar percent. Infrared spectroscopy, proton and carbon NMR were successfully utilized to confirm the chemical structure of copolymers. In order to determine the comonomer compositions in the copolymer structure, proton nuclear magnetic resonance, 1H NMR studies were carried out. Thermal (TGA, DSC) and mechanical properties of homo and copolymers were also investigated. Intrinsic viscosity (IV) measurements in dimethyl formamide (DMF) solution revealed that the molecular weight of the copolymers were quite enough to form ductile films. In this study, hydrogels and their copolymers of acrylonitrile (PAN-PHEA) were also studied. Some properties of the free standing copolymer films such as / swelling behaviors and densities were evaluated. It was also demonstrated that the nanocomposites of these copolymers could be utilized in filtration technology. Hence, novel PAN(88)-co-PMA(12) and polyaniline (PANI) nanocomposites were prepared at various PANI loadings to remove toxic chromium(VI) solution from water. Chemical structure, swelling and fracture morphology of the nanocomposites membranes were studied. It was observed that PANI had a great impact on the chromium removal. Permeate flux and rejection of chromium(VI) were demonstrated for various pHs and chromium(VI) concentrations. Finally, influences of comonomer composition on the thermal properties of the copolymers were investigated to input their structure property relation.

Acrylonitrile were copolymerized with 2-ethylhexyl acrylate and hexyl acrylate via one step emulsion polymerization using ammonium persulfate (initiator), 1-dodecanthiol (chain transfer agent) and DOWFAX 8390 (surfactant) in the presence of water at about 68 0C. Poly (acrylonitrile-2ethylhexyl acrylate) and poly (acrylonitrile-hexyl acrylate) copolymers with three different comonomer composition (8, 12 and 16 molar percent) were prepared. FTIR and 1H-NMR were used in order to clarify the chemical structure of copolymers. The comonomer amount incorporated into copolymers was determined by using 1H-NMR spectra. The thermal behavior of copolymers was determined by DSC and TGA. Molecular weights of copolymers were determined by intrinsic viscosity (IV) measurements. IV measurements revealed that both poly (acrylonitrile-2ethylhexyl acrylate) and poly (acrylonitrile-hexyl acrylate) have sufficient molecular weight to form nanoporous filtration membranes. Nanoporous filtration membranes were prepared and tested for chromium (IV) removal. It was observed that chromium (VI) rejections of nanoporous filtration membrane were highly dependent on the concentration and the pH of the solutions. Almost complete removal (99, 9 percent Cr (VI)) rejection was achieved at pHs 2, 5 and 7 for solution containing 50 ppm, chromium (VI) with permeate flux within a range from 177 to 150 L/m2h at 689.5 kPa. Also, chemical structure, swelling ratios, sheet resistivity and fracture morphologies of the nanoporous filtration membrane were studied. It should be noted that the nanoporous filtration membranes were fouling resistant.

This thesis aims to improve the performance of latex-based pressure-sensitive adhesives (PSAs). PSA performance is usually evaluated by tack, peel strength and shear strength. Tack and peel strength characterize a PSA’s bonding strength to a substrate while shear strength reflects a PSA’s capability to resist shear deformation. In general, increasing shear strength leads to a decrease in tack and peel strength. While there are several commercial PSA synthesis methods, the two most important methods consist of either solvent-based or latex-based techniques. While latex-based PSAs are more environmentally compliant than solvent-based PSAs, they tend to have much lower shear strength, at similar tack and peel strength levels. Therefore, the goal in this thesis was to greatly improve the shear strength of latex-based PSAs at little to no sacrifice to tack and peel strength. In this study, controlling the polymer microstructure of latexes or their corresponding PSA films was used as the main method for improving the PSA performance. The research was sub-divided into four parts. First, the influence of chain transfer agent (CTA) and cross-linker on latex polymer microstructure was studied via seeded semi-batch emulsion polymerization of butyl acrylate (BA) and methyl methacrylate (MMA). Three techniques were used to produce the latexes: (1) adding CTA only, (2) adding cross-linker only, and (3) adding both CTA and cross-linker. It was found that using CTA and cross-linker simultaneously allows one to expand the range of latex microstructural possibilities. For example, latexes with similar gel contents but different Mc (molecular weight between cross-links) and Mw (molecular weight of sol polymers) could be produced if CTA and cross-linker concentration are both increased. However, for the corresponding PSAs with similar gel contents, the relationship between their polymer microstructure and performance was difficult to establish as almost all of the medium and high gel content PSAs showed very low tack and peel strength as well as extremely large shear strength readings. In the second part of this thesis, in order to improve the tack and peel strength of medium and high gel content PSAs, the monomer composition and emulsifier concentration were varied. It was found that changing the monomer mixture from BA/MMA to BA/acrylic acid (AA)/2-hydroxyethyl methacrylate (HEMA) while simultaneously decreasing emulsifier concentration dramatically improved the corresponding PSAs’ shear strength as well as tack and peel strength. The addition of polar groups to the PSA increased its cohesive strength due to the presence of strong hydrogen bonding; meanwhile, PSA films’ surface tension increased. In the third part, two series of BA/AA/HEMA latexes were generated by varying the amounts of CTA either in the absence or presence of cross-linker. The latexes produced in the absence of cross-linker exhibited significantly larger Mc and Mw compared to their counterparts with similar gel contents prepared with cross-linker. The PSAs with the larger Mc and Mw showed much larger shear strengths due to improved entanglements between the polymer chains. In the final part of the thesis, the performance of the BA/AA/HEMA PSAs was further improved by post-heating. Compared with original latex-based PSAs with similar gel contents, heat-treated PSAs showed not only significantly improved shear strengths, but also much larger tack and peel strengths. The different shear strengths were related to the PSAs’ gel structures, which were discrete in the original PSAs but continuous in the heat-treated PSAs. The improved tack and peel strengths were related to the PSA films’ surface smoothness. During the post-heating process, the PSA polymer flowed, resulting in much smoother surfaces than the original PSA films. In addition, the effect of post-heating was related to the polymer microstructure of the untreated PSAs. Decreasing the amount of very small or very big polymers or simultaneously increasing Mc and Mw could lead to post-treated PSAs with significantly better performance. Moreover, it was found that by optimizing the polymer microstructure of the original latex-based PSAs, it was possible to obtain a treated PSA with similar or even better performance than a solvent-based PSA with similar polymer microstructure. Our original objective was surpassed: in two cases, not only was shear strength greatly improved, but so were tack and peel strength due to the simultaneous modification of PSA bulk and surface properties.

In this study, waterborne silicone-acrylic resin was produced by incorporating silane coupling agent onto the acrylic main chain by emulsion polymerization. After applying different emulsion polymerization processes, batch polymerization was selected to obtain the resultant resin. Thus finding the optimum conditions by investigating the parameters of monomer ratios, initiators, concentrations of initiators, temperature and time, the novel resin was synthesized. Water-dispersed silicone-acrylic resin was produced using butyl acrylate, butyl methacrylate, methyl methacrylate, 3-methacryloxypropyltrimethoxysilane and acrylic acid as a hydrophilic monomer. 2,2&#039 / -azobis[2-(2-imidazolin-2yl)propane]dihydrogen chloride as thermal initiator and t-butyl hydroperoxide / sodiummetabisulfite as redox couple initiator were selected as the best effective initiators for the production of silicone-acrylic resin. The reaction temperature of the preparation of silicone-acrylic resin was taken as 50&amp / #61616 / C maximum to prevent gelation and agglomeration. To understand the effect of silane coupling agent on the properties of the resin, a new resin was synthesized which did not contain any silane coupling agent and the properties of both resins were determined by FTIR spectroscopy, thermal analysis and mechanical tests. Their physical properties were also determined. The addition of 3-methacryloxypropyltrimethoxysilane to the main chain increased the hardness and the gloss values but slightly decreased the abrasion resistance value of the silicone-acrylic resin. All the samples showed superior flexibility. The produced polymer which contains silane coupling agent showed excellent adhesion properties on glass and metal plates.

Conventional free-radical miniemulsion polymerization has been well studied since early 1970s. Conventional free-radical miniemulsion polymerizations have inherent limitations associated with uncontrolled free-radical polymerization mechanism. The goal of this work is to develop a variety of unconventional miniemulsion polymerization techniques by applying new polymerization techniques (typically in solution or bulk) to miniemulsion systems to overcome their inherent limitations and extend the application of free-radical miniemulsion polymerization. This work focused on the exploration of kinetic and mechanistic aspects of unconventional miniemulsion polymerizations. First, enzyme initiated free-radical miniemulsion polymerization, in contrast with those conventional chemical initiated miniemulsion polymerization, is demonstrated for the first time as an answer to the challenges associated with using the hydrophobic of vinyl monomers in aqueous enzymatic reactions. A procedure for enzyme initiated free-radical miniemulsion polymerization was formulated and stable poly(styrene) latexes were successfully synthesized. The kinetics of enzyme initiated free-radical miniemulsion polymerization and the effect of reaction conditions on the polymerization was elucidated. Second, RAFT miniemulsion polymerization of hydrophobic monomers was performed in CSTR trains and the transient states, previously identified by others in our group, were elucidated. Next, RAFT miniemulsion polymerization of a partially water soluble monomer was studied. RAFT miniemulsion polymerizations of gamma-methyl-alpha-methylene-gamma-butyrolactone, a partially water soluble lactone monomer derived from renewable sources, was successfully formulated. Homogeneous nucleation was found to play an important role in the free-radical "miniemulsion" homopolymerization of MeMBL. By using styrene as a comonomer, the RAFT miniemulsion polymerizations of MeMBL and styrene were well controlled and narrowly distributed copolymers of MeMBL/styrene were produced. Following the study of the partially water monomer, RAFT inverse miniemulsion polymerization was proposed for the polymerization of hydrophilic monomers. The kinetics of RAFT inverse miniemulsion polymerization of acrylamide exhibited the typical behavior of controlled polymerizations up to high conversions. The effects of reaction parameters on the polymerization rate and particle size were investigated. The dominant locus of radical generation for particle nucleation and the fate of desorbed monomeric radicals in inverse miniemulsion polymerizations were evaluated. Finally in this work, conclusions and implications are presented and ideas for future work are suggested.

The synthesis of well-defined polymer nanoparticles will have immediate applications in the biomedical industry as nanocontainers for the controlled delivery and release of water insoluble drugs. The ability to control molecular weight, particle morphology and chemical functionality and to obtain polymeric nanoparticles with narrow molecular weight and particle size distributions is paramount for their application-specific design. Two synthetic approaches were investigated in the synthesis of well-defined polymer nanoparticles, emulsion polymerization and self assembly. The successful implementation of Reversible Addition-Fragmentation Chain Transfer (RAFT) in emulsion polymerization was the first challenge faced when controlling nanoparticle molecular weight and size. Initially we showed that successful ‘living’ emulsion polymerizations of styrene could be carried out using a non-ionic surfactant. The success was achieved when preparing polymers of low molecular weight (5 and 9 K targeted Mn’s with polydispersities (PDIs) below 1.2). Deviation from ideal ‘living’ behavior occurred when targeting Mn’s greater than 20 K (at 100 % conversion). The ‘degassing technique’ was then investigated as an avenue to generate stable polystyrene nanoparticles by emulsion polymerization without the addition of surfactant (residual surfactant can result in detrimental effects on product quality). The polymerization of this emulsion system in the presence of a low reactive RAFT agent was ‘living’ in nature. In the presence of a high reactive RAFT agent the emulsion system showed ‘living’ nature, however, secondary nucleation occurred, which resulted in broad molecular weight distribution (MWD). Thus, the emulsion polymerization approach to preparing well-defined polymer nanoparticles was giving less than desirable results. An alternative method to prepare polymer nanoparticles with controlled chemical composition and morphology is to self assemble pre-synthesized block copolymers in water. This approach has several significant advantages over the emulsion systems: (i) all polymer chains are of near uniform chain length and chemical composition, (ii) the ratio between the hydrophobic and hydrophilic polymers can easily be controlled, (iii) chemical functionality can be located in different morphological regions, (iv) a wide range of 3-dimensional structures apart from spheres can be prepared (i.e. rods and vesicles), and (v) additives such as surfactant, stabilizers and residual monomer usually found after an emulsion polymerization are not required in the self assembly methodology. These advantages justify our shift in strategy. The only disadvantage of the self assembly process is that one cannot reach high weight fractions of polymer in water and is usually limited to below 2 wt-%, where as emulsion polymerizations can allow weight fractions of polymer close to 50 wt-%. Well-defined amphiphilic 4-arm star polyacrylic acid-block-polystyrene (PAA-b-PSTY) copolymers, prepared by RAFT solution polymerization, were dispersed in water to form core-shell micelles, in which the shell consisted of tethered PAA loops. The entropic penalty for having such loops resulted in a less densely packed PSTY core when compared to linear diblock copolymers of the same arm length. The surface of the shell was irregular due to the tethering points, but when cleaved the PAA chains extended to form a regular and relatively uniform corona. Controlling the polymer architecture enabled the synthesis of polymer micelles with tethered PAA loops, which could be opened to form uniform corona when desired. Three-miktoarm star and dendrimers with miktoarms consisting of PSTY, polytert-butyl acrylate (PtBA), polymethyl acrylate (PMA) and PAA were then synthesized using a combination of Atom Transfer Radical Polymerization (ATRP) and Huisgen 1,3-dipolar cycloaddition ‘click’ reactions. In all reactions, the stars and dendrimers were well-defined with PDIs lower than 1.09. This was the first step in the synthesis of well-defined highly ordered polymer structures. The synthesis of such structures demands high level of purity at each synthetic step eliminating the possibility of side reactions, which as of consequence lowers product yields. The synthesis and use of reactive solid supports to remove excess linear polymer to increase the yields of polymeric 3-arm stars and dendrimers was employed. These supports are a cheap approach to scavenge polymeric species with either azido or alkynyl functionality, after which the solid support can be filtered away from the product. These supports aided the synthesis of 3rd generation polymeric dendrons and dendrimers consisting of homopolymer PSTY with either solketals or alcohols at the periphery, diblock PSTY and PtBA, and amphiphilic diblock. The methodology used to construct these structures was a combination of ATRP to produce linear polymers with telechelic functionality, with the subsequent use of this functionality to join the polymers together via ‘click’ reactions. Micellization of the amphiphilic structures in water produced polymer nanoparticles of uniform size. The dendrimer nanoparticles were 18 nm in diameter, consisting of 19 individual dendrimers. The dendrimers most probably have no mutual interpenetration and thus pack uniformly to form the micelles. The dendron nanoparticles were 21 nm with an aggregation number of 43 dendrons per micelle, which suggests they form cone-like structures and self-assemble to form crew-cut micelles. Using a convergent approach polymer structures with unprecedented chemical diversity (hydrophobic or amphiphilic) and complexity (G2 miktoarm dendrimers with a degradable core) consisting of PSTY, PMA, PtBA and PAA were then synthesized with high purity using copper wire as the ‘click’ catalyst.

Doctor of Philosophy / The kinetics of electrosterically stabilized emulsion systems was studied. The aim of this was to understand the impact that steric and electrosteric stabilizers have on the kinetics of particle growth and particle formation in the area of emulsion polymerization. The well-established mechanisms that govern these processes for emulsions stabilized by conventional low molecular weight surfactants were used as a reference point for comparative purposes. Model latexes were synthesized that comprised of a poly(styrene) core stabilized by a corona of poly(acrylic acid). The advent of successful controlled radical polymerization techniques in heterogeneous media (via RAFT polymerization) allowed for latexes to be synthesized under molecular weight control. For the first time, the degree of polymerization of the stabilizing block on the particle surface was able to be controlled and verified experimentally using mass spectrometry techniques. Three latexes were made with different average degrees of polymerization of the stabilizing block; five, ten and twenty monomer units respectively. A methodology was developed to remove the RAFT functionality from the polymer chains present in the emulsion while retaining the desired particle morphology. Oxidation with tertbutylhydroperoxide (TBHP) was proven to be successful at eliminating the living character provided by the thiocarbonyl end-group. Extensive dialysis and cleaning of the latex was performed to ensure no residual TBHP or reaction by-products remained. Latexes with poly(styrene) cores were chosen for this work as poly(n-butyl acrylate) latexes were shown to be influenced by chain transfer to polymer, providing an additional kinetic complication. The three electrosterically stabilized emulsions were used as seed latexes in carefully designed kinetic experiments to measure the rate of polymerization as a function of time. Two independent techniques (chemically initiated dilatometry and γ-relaxation dilatometry) were used to measure the rate coefficients of radical entry (ρ) and exit (k) in these systems – the two parameters that essentially govern the rate of particle growth. The latexes were chosen such that they satisfied ‘zero-one’ conditions (i.e. that any given latex particle contains at most one growing radical at any given time) in order to simplify data analysis. Three different chemical initiators were used, each yielding a radical with a different electric charge. Results from γ-relaxation experiments demonstrated that the three electrosterically stabilized latexes gave very long relaxation times when removed from the radiation source, ultimately yielding very small k values. These values were up to a factor of 10 smaller than that predicted by the ‘transfer-diffusion’ model for exit for particles of that size. This reduction was attributed to a ‘restricted diffusion’ effect, where the exiting monomeric radical has to diffuse through a dense layer of polymer on the particle surface, where its mobility will be restricted. Modification of the Smoluchowski equation for diffusion-controlled adsorption/desorption to account for this postulate led to the development of a model that gave excellent semi-quantitative agreement with experiment. Chemically initiated dilatometric experiments (using three different types of initiator) gave the unusual result of very low reaction rates and low steady-state values of 'nbar', the average number of radicals per particle. Using the standard kinetic equations for styrene-based systems (where it is assumed that an exited monomeric radical undergoes re-entry), this led to the calculation of impossibly small values of the entry rate coefficient ρ (far below any background or ‘thermal’polymerization rate). However upon removing the assumption of re-entry and assuming that exited radicals undergo termination, the obtained values of ρ were in almost perfect agreement with the values predicted from the ‘control by aqueous phase growth’ entry mechanism. This unexpected result was attributed to chemical reaction with the poly(acrylic acid) stabilizers through chain transfer to polymer (via hydrogen-atom abstraction). This postulate was verified by separate experiments that demonstrated that poly(acrylic acid) could act as a reasonably efficient chain transfer agent for styrene polymerization. The addition of poly(acrylic acid) to the aqueous phase of a conventionally stabilized emulsion also led to the rate reduction seen previously. NMR experiments demonstrated the existence of poly(acrylic acid-graft-styrene), which could only be formed through termination of a poly(styrene) chain with a poly(acrylic acid) chain bearing a mid-chain radical (as the product of a chain transfer reaction). These additional terms of transfer and termination were included in the governing kinetic equations of emulsion systems (the Smith-Ewart equations) to develop a model to account for the behaviour of electrosterically stabilized latexes. The ultimate fate of an exiting radical was now shown to be a competition between fates; successful desorption into the aqueous phase, or chemical reaction (through transfer or termination) within the hairy layer. These additional terms were shown to significantly reduce the theoretical value of nbar, and were in excellent agreement with experiment. For small electrosterically stabilized particles with a densely packed ‘hairy layer,’ it was seen that transfer/termination is the dominant loss mechanism as opposed to desorption. The developed model showed that as the particle size was increased, the dominant loss mechanism once again became successful desorption into the aqueous phase. The model was shown to give excellent agreement with experimental data from ‘uncontrolled’ emulsion systems. To explain the highly unusual secondary nucleation behaviour seen in systems such as these, it was postulated that beta-scission of a poly(acrylic acid) chain bearing a mid-chain radical is an important mechanistic step in the nucleation mechanisms of these systems. Modelling (both steady-state and time-dependent) gave good agreement with experiment with a minimal number of adjustable parameters. Theory (and supporting experimental evidence) demonstrated that this nucleation mechanism is only significant at high particle numbers; under other conditions the well-known ‘homogeneous nucleation’ mechanism is once again dominant.

Alkali-soluble resins (ASRs) were prepared by (i) solution and (ii) emulsion polymerization. All ASRs were synthesized with number-average molar masses < 20,000 g mol-1 and all had 15 wt% methacrylic acid 5 wt% styrene, the remaining 80 wt% was composed of either methyl methacrylate or a combination of methyl methacrylate and ethyl acrylate. All emulsion ASRs were made to 20% solids, with volume-average particle diameters (dv) in the region 30 – 50 nm, with a glass transition temperature of 80 – 120 °C. Emulsion polymerization was the preferred route for ASR synthesis, to allow further studies on their dissolution behaviour. Before their use as colloidal stabilizers, the dissolution behaviour of the ASRs needed to beinvestigated e.g. effect of temperature, molar mass, and composition. Particle size and absorbance measurements were taken during dissolution of ASRs to achieve 100%neutralization and these were shown to have two stages, an apparent particle swelling (whichwas rapid), and a slower, decrease in particle size as water-soluble polymeric material wasdiffusing out of the ASR particles. From this, further interpretation allowed for calculating the diffusion coefficient of the ASR polymer using the Stokes-Einstein equation. Time-domain nuclear magnetic resonance (TD-NMR) was employed to enhance understanding of what is occurring in the ASR particles, and in the aqueous, continuous phase. The final aspect of this project was to use the ASRs prepared as colloidal stabilizers in emulsion polymerizations of butyl acrylate (BA) and butyl methacrylate (BMA) using varying levels and also the effect of adding additional surfactant. The results show that the effect of ASR molar mass, the concentration of stabilizer, and also the impact of the EA-containing ASR greatly influence stability, whereby lower ASR molar mass, higher levels of stabilizer and including EA greatly benefit colloidal stability in PBA latexes. In PBMA latexes, a similar trend was also observed, but, the presence of ethyl acrylate (EA) in the ASR backbone has a detrimental effect on the colloidal stability, caused by the inability of grafting to occur between the ASR and PBMA.