Radical polymerization kinetics of water-soluble monomers

Buback, Michael; Hutchinson, Robin A.; Lacı́k, Igor

doi:10.1016/j.progpolymsci.2022.101645

Cited by 20 publications

(23 citation statements)

References 134 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Additionally, the homopolymer of QAS-BN is soluble in water. Therefore, when an aqueous emulsion polymerization reaction with a water-soluble initiator and water-soluble monomers is carried out, it proceeds through the following stages: (a) the initiator and monomers in the aqueous phase combine to produce reactive radicals; (b) the monomers in the aqueous phase undergo solution polymerization due to the presence of water-soluble monomers to produce water-soluble oligomers [ 41 , 42 ]; (c) the molecular chain grows to a certain level and then enters the micelle to participate in the reaction due to the decrease in water solubility. Due to the above process, the quaternary ammonium groups were concentrated on certain molecular chains.…”

Section: Resultsmentioning

confidence: 99%

One-Step Synthesis of Self-Stratification Core-Shell Latex for Antimicrobial Coating

Zhen

Yuan

et al. 2023

Molecules

View full text Add to dashboard Cite

Herein, we describe a one-step method for synthesizing cationic acrylate-based core-shell latex (CACS latex), which is used to prepare architectural coatings with excellent antimicrobial properties. Firstly, a polymerizable water-soluble quaternary ammonium salt (QAS-BN) was synthesized using 2-(Dimethylamine) ethyl methacrylate (DMAEMA) and benzyl bromide by the Hoffman alkylation reaction. Then QAS-BN, butyl acrylate (BA), methyl methacrylate (MMA), and vinyltriethoxysilane (VTES) as reactants and 2,2’-azobis(2-methylpropionamidine) dihydrochloride (AIBA) as a water-soluble initiator were used to synthesize the CACS latex. The effect of the QAS-BN dosage on the properties of the emulsion and latex film was systematically investigated. The TGA results showed that using QAS-BN reduced the latex film’s initial degradation temperature but improved its thermal stability. In the transmission electron microscopy (TEM) photographs, the self-stratification of latex particles with a high dosage of QAS-BN was observed, forming a core-shell structure of latex particles. The DSC, TGA, XPS, SEM, and performance tests confirmed the core-shell structure of the latex particles. The relationship between the formation of the core-shell structure and the content of QAS-BN was proved. The formation of the core-shell structure was due to the preferential reaction of water-soluble monomers in the aqueous phase, which led to the aggregation of hydrophilic groups, resulting in the formation of soft-core and hard-shell latex particles. However, the water resistance of the films formed by CACS latex was greatly reduced. We introduced a p-chloromethyl styrene and n-hexane diamine (p-CMS/EDA) crosslinking system, effectively improving the water resistance in this study. Finally, the antimicrobial coating was prepared with a CACS emulsion of 7 wt.% QAS-BN and 2 wt.% p-CMS/EDA. The antibacterial activity rates of this antimicrobial coating against E. coli and S. aureus were 99.99%. The antiviral activity rates against H3N2, HCoV-229E, and EV71 were 99.4%, 99.2%, and 97.9%, respectively. This study provides a novel idea for the morphological design of latex particles. A new architectural coating with broad-spectrum antimicrobial properties was obtained, which has important public health and safety applications.

show abstract

Section: Resultsmentioning

confidence: 99%

One-Step Synthesis of Self-Stratification Core-Shell Latex for Antimicrobial Coating

Zhen

Yuan

et al. 2023

Molecules

View full text Add to dashboard Cite

show abstract

“…Backbiting and end-capping by the solvent could also take place as well as incorporation of the solvent into the backbone or side groups of the polymer. 35,36 The solvent can also affect the tacticity when polymerizing vinyl monomers. 37,38 Here, we present the results of a study designed to answer this question for PVCap.…”

Section: Introductionmentioning

confidence: 99%

Kinetic Hydrate Inhibitors: The Effect of Pre- or Postpolymerization Solvent Addition on Performance and a Powerful New Glycol Ether Solvent Synergist

et al. 2023

View full text Add to dashboard Cite

Amphiphilic polyamides such as poly(N-vinyl caprolactam) (PVCap) and related copolymers have been used as kinetic hydrate inhibitors (KHIs) for over 25 years to combat gas hydrate formation in the oil and gas field. The solvent in which they are made is often a synergist to boost KHI performance. Using PVCap and a variety of glycol ethers, we investigate whether the polymerization of VCap in the synergist solvent gives a different KHI performance than a PVCap made in a nonsynergistic solvent, which has had the solvent synergist added afterward. The results of high-pressure, slow constant cooling tests (1 °C/h) in multiple rocking cells using a synthetic natural gas blend suggest that there is little difference as long as the molecular weight distribution is similar by both methods. In the process of these studies, we also identified a new synergist solvent, dipropylene glycol butyl ether (DPGBE), which showed superb synergy with PVCap. DPGBE also gave excellent synergy with poly(N-isopropylmethacrylamide) PNIPMAm but not with poly(N-vinylpyrrolidone) (PVP) or VP:VCap copolymer. The ability of the solvent to boost the KHI performance of the polymer may be related to the cloud point of the polymer. A theory is proposed to explain why sparingly soluble solvents, with the correct structural features, give the best synergy with low cloud point KHI polymers such as PVCap or PNIPMAm.

show abstract

“…[ 5 ] Water as a cosolvent has a significant influence on kinetics, with k p doubling from the bulk value for MA diluted to w mon = 0.20 in EtOH (

α_{EtOH} = 1.00

) at 30°C and doubling again (to ~4× the bulk value) in an EtOH/H 2 O mixture with

α_{EtOH} = 0.50

. The same study showed that the tremendous influence of water on the propagation kinetics of water‐miscible monomers such as AA and AAm [ 3 ] also holds for monomers that have limited water solubility. Indeed, the k p value for 5 wt.% MA in water (close to its miscibility limit) is 16 times higher than the bulk value, reaching a value of 160–200 ⋅ 10 3 L · mol −1 · s −1 at 25°C, in the same range as that of AA under the same reaction condition.…”

Section: Introductionmentioning

confidence: 99%

“…[4] The mechanistic representation was then extended to model the copolymerization of MA with t-BuAAm. [6] As both acrylate and AAm monomers undergo backbiting, [3,7] the set of mechanisms and fitting procedures used to develop the MA homopolymerization model were first applied to represent data collected from t-BuAAm homopolymerization experiments. These homopolymerization representations were then combined and extended to develop the model of MA/t-BuAAm copolymerization used to represent both batch [6] and semi-batch operation.…”

Section: Introductionmentioning

confidence: 99%

“…However, solvents capable of forming or disrupting hydrogen bonds cause the polymerization kinetics of acrylate and acrylamide (AAm) monomers to deviate from those observed in bulk or non-polar solvents. [1] Though a good foundation of literature has been developed for the solventbased kinetics of hydrophobic acrylates in organic solvents [1,2] and hydrophilic acrylates and AAms in water, [3] there is limited knowledge as to how the kinetics evolve as the solvent transitions from organic to aqueous mixtures.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

A systematic study of tert‐butylacrylamide‐methyl acrylate‐acrylic acid radical solution terpolymerization

et al. 2023

Self Cite

View full text Add to dashboard Cite

Multi‐functional polymers used for personal care products can be synthesized by radical polymerization of acrylic acid (AA) in alcohol/water solutions with non‐functional monomers such as methyl acrylate (MA) and N‐tert‐butylacrylamide (t‐BuAAm). However, solvents capable of forming or disrupting hydrogen bonds cause the polymerization kinetics of these monomers to deviate from their polymerization behaviour in bulk and non‐polar solvents. In this work, a previous mechanistic model developed for MA/t‐BuAAm copolymerization is extended to represent the terpolymerization system MA/t‐BuAAm/AA. The additional kinetic coefficients required for the system are estimated from fitting to AA homopolymerizations and AA/MA and AA/t‐BuAAm copolymerizations conducted in an ethanol/water solution. In‐situ nuclear magnetic resonance (NMR) spectroscopy is used to follow monomer conversions and composition drift behaviour, with the molar mass distributions of the polymer products characterized by size‐exclusion chromatography. Although AA is more reactive than MA in non‐polar solvents, the reactivities of the two monomers equalize under the experimental conditions examined. Thus, the batch and semi‐batch terpolymerization data collected are represented equally well by a reduced acrylate/t‐BuAAm copolymerization model and the full terpolymerization implementation.

show abstract

Radical polymerization kinetics of water-soluble monomers

Cited by 20 publications

References 134 publications

One-Step Synthesis of Self-Stratification Core-Shell Latex for Antimicrobial Coating

One-Step Synthesis of Self-Stratification Core-Shell Latex for Antimicrobial Coating

Kinetic Hydrate Inhibitors: The Effect of Pre- or Postpolymerization Solvent Addition on Performance and a Powerful New Glycol Ether Solvent Synergist

A systematic study of tert‐butylacrylamide‐methyl acrylate‐acrylic acid radical solution terpolymerization

Contact Info

Product

Resources

About