Robin A. Hutchinson's research while affiliated with Queen's University and other places

Publications (192)

Article
The radical homopolymerization of N‐tert‐butyl acrylamide (t‐BuAAm) and its copolymerization with methyl acrylate (MA) is studied in ethanol/water solutions. In‐situ NMR experiments, supported by bench‐scale lab batch experiments, are conducted over a range of initial monomer and initiator levels between 50−70 °C. While short chain branching for po...
Article
Three process variations are developed to synthesize dextran-bovine serum albumin (BSA) model conjugate through the Maillard reaction and a Schiff base-Amadori solid phase rearrangement mechanism at 90 °C. The influences of lyophilization pH and dextran:BSA molar ratio on the reaction are investigated, with the highest yields achieved by absorbing...
Article
We present an updated and expanded dataset of benchmark propagation rate coefficient ( k p ) data obtained from pulsed laser polymerization (PLP) of 13 vinyl monomers (styrene, methyl methacrylate, ethyl methacrylate, butyl...
Article
The effect of solvent on the radical copolymerization propagation kinetics of methyl acrylate (MA) with N- tert -butyl acrylamide (tBuAAm) is studied using the pulsed laser polymerization size exclusion chromatography technique (PLP-SEC),...
Article
When applying the pulsed laser polymerization–size exclusion chromatography (PLP-SEC) method to determine the propagation rate coefficient ( k p ) for bulk methyl acrylate at 25 °C, the characteristic ratio L 1 / L 2 of chain...
Article
A process for the well-controlled growth of acrylates by Cu-mediated polymerization has been developed, with macroinitiator synthesized continuously in a copper tubular reactor and subsequently chain-extended in a semi-batch reactor system without additional copper species. Extending this process to methacrylates and styrene monomers, however, has...
Article
Full-text available
Poly(lactic acid) choline iodide ester methacrylate, poly(PLA4ChMA), is a cationic degradable polymer that can flocculate particles and dewater oil sands from tailings ponds. This novel material has yet to be characterized in terms of environmental and human health. If ingested, this substance may become bioaccessible. The bioaccessibility (bioacce...
Article
The introduction of functional groups through radical copolymerization under starved‐feed conditions is a cost‐effective means to produce acrylate resins for coatings applications. The semi‐batch recipes often include a large fraction of nonfunctional acrylates and methacrylates, with a low percentage of functional comonomer added to become statist...
Article
The influence of alcohol and alcohol/water solutions on the radical copolymerization kinetics of 2-hydroxyethyl methacrylate (HEMA) with 2-methoxyethyl acrylate (MEA) is studied using pulsed-laser-polymerization coupled with size exclusion chromatography. It is found that MEA incorporation into the copolymer is increased in butanol, methanol (MeOH)...
Article
Me6TREN (tris[2‐(dimethylamino)ethyl]amine) is commonly used in Cu(0)‐mediated polymerization of acrylates due to its ability to promote high reaction rates while maintaining excellent control of chain growth. However, its cost presents a significant barrier to commercialization. Thus, the use of PMDETA (N,N,Nʹ,Nʹʹ,Nʹʹ‐pentamethyldiethylenetriamine...
Article
Among the many contributions that Kenneth “Ken” O'Driscoll made to advance the understanding of radical polymerization kinetics was the implementation of proper statistical procedures for extracting (monomer) reactivity ratios from experimental data for copolymer composition. He emphasized the importance of experimental design, using non‐linear reg...
Article
The effect of retardation exhibited in dithiobenzoate-mediated polymerizations is perhaps the most controversial kinetic phenomenon discussed in polymer chemistry in the last 20 years. However, the Missing Step reaction (MSR), which involves the termination between a propagating radical and a 3-arm star product, has emerged as a hypothesis to expla...
Article
Secondary reactions significantly affect acrylate polymerization rates as well as the architecture of polymer produced by high‐temperature solution radical polymerization. This impact is amplified under the semi‐batch starved‐feed policy used to keep monomer concentration low. Thus, the importance of intramolecular chain transfer (backbiting) is si...
Article
Tertiary Amine Methacrylates (TAMAs), such as 2-(N,N-diethylamino)ethyl methacrylate (DEAEMA) and 2- (N,N-dimethylamino)ethyl methacrylate (DMAEMA), and PEGylated (macro)monomers, such as 2-ethoxy- ethyl methacrylate (EEMA1) and poly(ethylene glycol) methyl ether methacrylates with 9 and 23 units (PEGMA9 and PEGMA23, respectively), are two families...
Article
An online database created and curated by an IUPAC subcommittee is introduced. It is designed to act as central access point for finding reliable kinetic data on radical polymerizations. The...
Article
Knowledge of the average composition and molecular weights of copolymers containing functional groups is often not enough to ensure product quality, as the distribution of the reactive moieties among the chains affects performance. This work couples a kinetic Monte Carlo model, previously verified as providing an accurate description of the semi-ba...
Article
Full-text available
The radical homopolymerization kinetics of 3-(methacryloylaminopropyl) trimethylammonium chloride (MAPTAC) and its batch copolymerization with nonionized acrylic acid (AA) in aqueous solution are investigated and modeled. The drift in monomer composition is measured during copolymerization by in situ NMR over a range of initial AA molar fractions a...
Article
There is limited knowledge of the radical polymerization kinetics of partially water-miscible monomers, often used as comonomers in emulsion or solution polymerizations. Herein, the propagation kinetics of 2-methoxyethyl acrylate (MEA) and methyl acrylate (MA) are compared to that of the fully water-miscible monomer acrylic acid (AA) in alcohol/wat...
Article
Solution radical homopolymerization of isobornyl acrylate (iBoA) under starved‐feed higher temperature conditions unexpectedly leads to polymer product with low dispersity (<1.3) compared to the polymerization of butyl acrylate (BA) under identical conditions. Both backbiting and β‐scission reactions occur, as the poly(iBoA) product contains close...
Article
Functional acrylic resins for the coatings and adhesives industry are often synthesized by radical solution copolymerization at high temperatures (>120 °C) using starved-feed semibatch operation. The kinetic Monte Carlo (KMC) stochastic modeling technique has emerged as a method to represent the placement of the functional comonomer units across th...
Article
Full-text available
The novel cationic flocculant, poly(lactic acid) choline iodide ester methacrylate (poly(PLA4ChMA)), has been shown to provide improved flocculation of 5.0 wt.% mature fine tailings (MFT) diluted in deionized water compared to commercial anionic polymers, with continued dewatering of the sediment occurring as the polymer undergoes partial hydrolyti...
Article
The cationic flocculant poly(lactic acid) choline iodide ester methacrylate, poly (PLA4ChMA), is a promising candidate for dewatering oil sands mature fines tailings (MFT) that enhances solids consolidation as it undergoes partial hydrolysis. However, the degradation products have yet to be fully characterized. In the present work, proton nuclear m...
Article
Full-text available
Butyl acrylate and butyl methacrylate high-temperature starved-feed solution semi-batch copolymerizations with varying monomer feed composition, final polymer content, and reaction temperature were carried out to investigate the impact of operating conditions and secondary reactions on product molecular weight (MW) and terminal double bond (TDB) co...
Article
The kinetics of batch aqueous-phase solution radical copolymerization of an ionizable monomer acrylic acid (AA) with a cationic monomer 2-(methacryloyloxyethyl)trimethylammonium chloride (TMAEMC) to produce polyelectrolytes are investigated using in-situ NMR to follow both overall monomer conversion and comonomer composition. The rate of monomer co...
Article
The radical homopolymerization kinetics of 2‐(methacryloyloxyethyl) trimethylammonium chloride (TMAEMC) in aqueous solution is investigated across a wide range of initial monomer contents (5–35 wt%), ionic strengths, and pH levels using an in‐situ NMR technique to track monomer consumption over the complete conversion range. Molar mass distribution...
Article
Arrhenius parameters capturing the temperature dependence of radical polymerization propagation rate coefficients, kp , for methyl acrylate, butyl acrylate, and vinyl acetate in bulk are reported, based on the fitting of benchmark data sets compiled from independent laboratories using the pulsed-laser polymerization/size exclusion chromatography me...
Article
Low dispersity poly(methyl acrylate) with a target degree of polymerization of 10 (poly(MA)10) was produced in both batch and a continuous tubular reactor at room temperature using Cu(0) catalysis. The resulting polymer solution could be stored for over a week while maintaining excellent activity as a macroinitiator for the further growth of poly(a...
Article
Acrylic resins for automotive coatings are produced in non‐aqueous dispersions (NAD) of nanometer size. These must be sterically stabilized by oligomeric dispersants, which are complex reactive oligomers possessing vinyl and hydroxyl functionalities, controlling the size of the nanocolloid. Hence, we have developed a kinetic Monte Carlo (kMC) model...
Article
Full-text available
2-Hydroxyethyl methacrylate (HEMA) is an important component of many acrylic resins used in coatings formulations, as the functionality ensures that the chains participate in the cross-linking reactions required to form the final product. Hence, the knowledge of their radical copolymerization kinetic coefficients is vital for both process and recip...
Article
The factors influencing the periodic structure in molar mass distributions (MMDs) generated in pulsed-laser polymerization (PLP) experiments are investigated to extend the range of operating conditions under which radical polymerization propagation rate coefficients (kp) can be reliably estimated. Specifically, it is shown how kp may be determined...
Article
Full-text available
The atom transfer radical polymerization of butyl methacrylate mediated by Cu(I)Br/N,N,N′,N″,N″‐pentamethyldiethylenetriamine in anisole at 70 °C with the subsequent addition of bis(difluoroboryldiphenylglyoximato)cobalt(II) after 2 h is modeled using Predici software, to gain additional insight to the system used experimentally to produce macromon...
Article
The effect of dispersity on the stabilization performance of poly(butyl methacrylate) (P(BMA)) ω-unsaturated macromonomer used as a reactive dispersant in nonaqueous acrylic dispersion (NAD) polymerization is investigated for the first time. Macromonomer with low dispersity (1.3) is synthesized in a one-pot process by the addition of bis(difluorobo...
Article
Variants of the partially hydrolytically-degradable cationic macromonomer polycaprolactone choline iodide ester methacrylate (PCL2ChMA) have been synthesized to assess the effects of structure on the performance of the resulting polymers in the flocculation of mature fine tailings (MFT) that are a byproduct of bitumen extraction from oil sands. Nei...
Article
While Kinetic Monte Carlo (KMC) techniques provide a powerful means to model polymer microstructure, the associated computational cost has been a barrier to its wide-spread adoption. The case of radical semi-batch polymerization under starved-feed policy is a particularly challenging application: at the initial stage, a large simulation volume is r...
Article
Poly(acrylic) nanoparticles produced by nonaqueous dispersion (NAD) radical polymerization are important components in many automotive coating formulations. A series of experiments show that the properties of final dispersions (particle size distribution, viscosity, and stability) correlate to the thermodynamics of the NAD system, as characterized...
Article
Solvent effects on reactivity ratios (ri) and overall composition-averaged copolymer propagation rate coefficients (kp,cop) are generally not observed during methacrylic ester radical copolymerization. However, hydroxyl-bearing comonomers, such as 2-hydroxyethyl methacrylate (HEMA), lead to significant deviations from expectation for both ri and kp...
Article
Full-text available
The radical copolymerization kinetics of acrylamide (AM) and the water-soluble monomer sodium 4-hydroxy-4-methyl-2-methylene butanoate (SHMeMB), formed by saponification of the bio-sourced monomer γ -methyl-α-methylene- -butyrolactone (MeMBL), are investigated to explain the previously reported slow rates of reaction during synthesis of superabsorb...
Article
We synthesized hydrolytically-degradable cationic polymers by micellar radical polymerization of a short-chain polyester macromonomer, polycaprolactone choline iodide ester methacrylate (PCL2ChMA) with two polyester units, and used them to flocculate oil sands mature fine tailings (MFT). We evaluated the flocculation performance of the homopolymer...
Article
A new water-soluble monomer, sodium 4-hydroxy-4-methyl-2-methylene butanoate (SHMeMB), formed by saponification of the bio-derived monomer γ-methyl-α-methylene-γ-butyrolactone (MeMBL), was copolymerized with acrylamide (AM) in aqueous solution to make superabsorbent hydrogels with equilibrium degree of swelling in the range of 6 700 – 59 000 %, dep...
Article
Pulsed laser polymerization coupled with size exclusion chromatography (PLP-SEC) was implemented to study the micellar radical homopropagation kinetics of cationic surfmer, polycaprolactone choline iodide ester methacrylate (PCLnChMA with n = 2 average polyester units), at concentrations of 5, 10, and 20 wt% in aqueous solutions at 25, 50, 70, and...
Article
Full-text available
The radical copolymerization of butyl acrylate (BA) and 2-hydroxyethyl acrylate (HEA) was investigated under batch and semi-batch operations, with a focus on the influence of hydrogenbonding on acrylate backbiting. The effect of hydrogen bonding on HEA to BA relative incorporation rates during copolymerization, previously seen in low-conversion kin...
Article
Pulsed-laser polymerization combined with polymer analysis by NMR and size-exclusion chromatography is used to study the radical copolymerization kinetics of isoprene (IP) with glycidyl methacrylate (GMA). The copolymer is characterized by a close-to-alternating microstructure, with the addition of IP leading to a significant decrease in the compos...
Article
Polylactic acid ethyl ester methacrylate (PLANEMA) macromonomers are synthesized with N = 1, 5, 7, and 9 average number of polyester units. While propagation rate coefficients (kp) determined by pulsed laser polymerization experiments for bulk PLA1EMA and PLA5EMA are not significantly different over the 40–100 °C temperature range, they are elevate...
Article
The pulsed-laser polymerization technique in combination with size exclusion chromatography and nuclear magnetic resonance is used to study the influences of solvent choice and monomer structure on the copolymerization propagation kinetics of 2-hydroxyethyl acrylate (HEA) and 2-methoxyethyl acrylate (MEA). The similarity in the monomer structures p...
Article
Short-chain polyester methacrylate macromonomers with alkyl, tertiary amine, carboxyl, and hydroxyl end-group functionalities are synthesized by ring-opening polymerization and subsequent modification. Monomer conversion and composition drift during batch radical copolymerizations of (macro)monomer with styrene are tracked using the in situ NMR tec...
Article
Short-chain polyester methacrylate macromonomers with alkyl, tertiary amine, carboxyl, and hydroxyl end-group functionalities are synthesized by ring-opening polymerization and subsequent modification. Monomer conversion and composition drift during batch radical copolymerizations of (macro)monomer with styrene are tracked using the in situ NMR tec...
Article
Nano-sized polyacrylate colloids (< 200 nm) at high solids level (~ 60 wt%) are prepared via non-aqueous dispersion (NAD) semibatch polymerization using n-butyl methacrylate (BMA)-based macromer dispersants of varying chain lengths and levels of functionality provided by incorporation of 2-hydroxyethyl methacrylate (HEMA) comonomer. The effect of b...
Article
A numerical approach has been developed to capture the inhomogeneous and nonstationary processes of pulsed laser polymerization (PLP). The new simulation tool has been applied to systematically investigate how temperature gradients that develop in the sample cell influence the accuracy of propagation rate coefficients, kp, determined by the PLP-SEC...
Article
Propagation rate coefficient values, kp, reported by several groups for radical polymerization of bulk vinyl acetate are critically evaluated. All data are obtained by the combination of pulsed-laser polymerization and subsequent polymer analysis by size exclusion chromatography, as recommended by the IUPAC Working Party on Modeling of Polymerizati...
Article
2-Hydroxyethyl acrylate (HEA), commonly introduced to control resin properties and introduce crosslinking sites, affects radical copolymerization kinetics through hydrogen-bonding, with the extent of the influence dependent upon solvent choice. The pulsed-laser polymerization technique has been applied to systematically investigate the influence of...
Article
An in situ NMR technique is used to measure the relative monomer consumption rates of acrylamide (AM) and acrylic acid (AA) over a broad range of initial comonomer compositions, initial monomer concentrations (5-40 wt % in aqueous solution), and the complete range of AA ionization. The composition drift with conversion was found not only to be a st...
Article
The application of specialized pulsed-laser techniques has led to a vastly improved understanding of the kinetics of aqueous phase solution radical polymerization of water-soluble monomers. Propagation rate coefficients vary significantly with monomer concentration, an effect unique to the aqueous environment. In addition, the formation and reactio...
Article
Micellar radical polymerization of a short-chain polyester macromonomer, polycaprolactone choline iodide ester methacrylate (PCLnChMA), is used to produce a new cationic flocculant that becomes more hydrophobic in response to hydrolytic degradation. The cationic tips of the comb-like poly(PCL3ChMA) accelerate the settling rate of oil sands tailings...
Article
Acrylamide (AAm) is an important water-soluble monomer. Pulsed-laser polymerization in conjunction with size-exclusion chromatography (PLP-SEC) has been employed to measure the propagation rate coefficient, k(p), in aqueous solution at monomer concentrations from 1 to 30 wt % and temperatures between 5 and 70 degrees C. Laser pulse repetition rate...
Article
A kinetic model for the radical homopolymerization of acrylamide in aqueous solution is developed, incorporating propagation and termination rate coefficients as functions of monomer concentration and including the formation and reaction of midchain radicals based on the insights and measured rate coefficients from recent pulsed-laser studies. The...
Article
In this work the molecular weight distribution (MWD) of several ATRP techniques has been derived and solved using the Reduced Stiffness by Quasi Steady State Approximation (RSQSSA) methodology. The QSSA has been validated on the living radicals for normal, Simultaneous Reversible and Normal Initiation (SRNI) and Activators Regenerated by Electron T...
Article
Nitroxide-mediated polymerization (NMP) is conducted in batch and in a continuous stirred-tank reactor (CSTR) at temperatures up to 200 °C using a thermally stable nitroxide. A kinetic model was developed using the Predici® software package to further understand the experimental trends under batch and continuous operation. Using the estimated activ...
Article
Radical propagation kinetics of the bulk homopolymerizations of vinyl pivalate (VPi) and vinyl benzoate (VBz) have been studied using pulsed-laser polymerization (PLP) combined with size exclusion chromatography (SEC). As part of the study, the Mark-Houwink para-meters of poly(VPi) and poly(VBz) in tetrahydrofuran are determined using a triple dete...
Article
Non-aqueous dispersion (NAD) radical polymerization is used to produce poly(acrylic) nanoparticles (<200 nm) at 60 wt% solids content by a starved-feed semibatch process, with steric stabilization provided by a low molecular weight vinyl-functionalized polymeric dispersant. The performance of a vinyl-terminated BMA macromer is compared to that of a...
Article
Full-text available
Reversible deactivation radical polymerization (RDRP) of 2-hydroxyethyl acrylate in D2O with Cu(0) wire mediation and with two-step Cu(0) in situ mediation was investigated. The concentration of active species on the Cu(0) surface, which was influenced by Cu(0) type (wire or particle), polymer chain length, and activator and deactivator concentrati...
Article
Batch radical polymerization of 5–40 wt% non-ionized acrylic acid (AA) in aqueous solution has been studied between 35 and 90 °C under variation of initiator concentration and type as well as upon addition of different levels of 2-mercaptoethanol as chain-transfer agent (CTA). Chain-length-dependent termination was taken into account in a model dev...
Article
A new alkoxyamine based on a highly thermally stable nitroxide is used for the controlled polymerization of styrene and butyl acrylate at temperatures up to 200 °C. High monomer conversions are reached in a few minutes with a linear increase in polymer chain-length with conversion, a final dispersity (Đ) of ∼1.2, and successful chain-extension of t...
Article
The free-radical polymerization (FRP) kinetics for n-butyl cyanoacrylate (BCA) and methyl methacrylate (MMA) copolymerization are studied in bulk at 30–70 °C using both a pulsed-laser polymerization technique and Quantum Mechanics (QM). Through the addition of 1 v% dichloroacetic acid, the notoriously rapid anionic polymerization of alkyl-cyanoacry...
Article
The validity of the Mayo-Lewis (ML) terminal model for copolymer composition in nitroxide mediated copolymerization is systematically tested by simulation. Significant deviations in copolymer composition from ML behavior occur under various parameter combinations before the nitroxide quasi-equilibrium condition (QEC) is reached. Maximum deviations...
Article
Pulsed‐laser polymerization with subsequent analysis of the polymer molar mass distribution by size‐exclusion chromatography, PLP–SEC, is used to measure the propagation rate coefficient, k p, of N‐vinylpyrrolidone (NVP) in a series of organic solvents, varying the NVP concentration from 5 to 100 wt% and varying the temperature between –5 and +80 °...
Article
The radical propagation kinetics of vinyl acetate (VAc) has been studied by pulsed-laser polymerization coupled with analysis of the resulting polymer molar mass distributions. The significant increase in the apparent propagation rate coefficient observed with increasing pulse repetition rate is explained by the influence of the head-to-head defect...
Article
The copolymerization of butyl methacrylate (BMA) and butyl acrylate (BA) initiated by CuBr2/TPMA/EBiB (TPMA: tris[(2-pyridyl)methyl]amine; EBiB: ethyl 2-bromoisobutyrate), with tin(II) 2-ethylhexanoate (Sn(EH)2) as reducing agent, is studied experimentally and by kinetic Monte Carlo simulations at 70 and 90 °C under batch ARGET ATRP conditions in a...
Article
The validity of the Mayo-Lewis (ML) terminal model for copolymer composition in nitroxide mediated copolymerization is systematically tested by simulation. Significant deviations in copolymer composition from ML behavior occur under various parameter combinations before the nitroxide quasi-equilibrium condition (QEC) is reached. Maximum deviations...
Article
The distribution of functional groups in polymer chains produced in radical copolymerization by starved-feed semibatch operation is simulated using three different methodologies. Even under perfect control of the overall copolymer composition, a significant fraction of the polymer chains produced contain no functionality. A deterministic model is f...
Article
The pulsed laser polymerization-high termination rate limit-size-exclusion chromatography (PLP-HTRL-SEC) technique is used to estimate the mode of termination () for n-butyl methacrylate (n-BMA) polymerization at 30 degrees C. It is found that molecular mass distributions measured in these experiments are influenced by an unknown side reaction such...
Article
Full-text available
Propagation rate coefficient (kp) data for radical polymerization of methyl acrylate (MA) in the bulk are critically evaluated and a benchmark dataset is put forward by a task-group of the IUPAC Subcommittee on Modeling of Polymerization Kinetics and Processes. This dataset comprises previously published results from three laboratories as well as n...
Article
Radical copolymerizations of 2-hydroxyethyl methacrylate (HEMA) with n-butyl methacrylate (BMA) and n-butyl acrylate (BA) were carried out in xylene, DMF, and n-butanol solutions. Solvent effects on copolymerization propagation kinetics were investigated using pulsed laser polymerization (PLP) combined with size exclusion chromatography (SEC) as we...
Article
An in-situ NMR technique has been developed to study the aqueous phase copolymerization of non-ionized acrylic acid (AA) and acrylamide (AM) under near-isothermal conditions at much higher monomer contents than previously reported in the literature. The composition data obtained over the entire conversion range provides a precise estimate of monome...
Poster
Acrylic resins used as polymeric binders in automotive coatings or matrices for contact lenses are complex copolymers containing reactive functional (often hyroxyl) groups. A better understanding of the copolymerization kinetics of these monomers is required in order to ensure uniform distribution of the functionl groups among the polymer chains ov...