Study on the monomer reactivity ratio and performance of EPEG-AA (ethylene-glycol monovinyl polyethylene glycol–acrylic acid) copolymerization system

Liu, Guanjie; Qin, Xin; Wei, Xuehong; Wang, Ziwei; Ren, Jianguo

doi:10.1080/10601325.2020.1753537

Cited by 12 publications

(16 citation statements)

References 34 publications

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“…Thus it is of utmost importance to determine the reactivity ratios of HEMA (r HEMA ) and Boc-Phe-EMA (r Boc-Phe-EMA ) to understand the macromolecular configuration of the copolymers. To determine monomer reactivity ratios at low conversions, several well-established methods like Mayo-Lewis, [39,40] Finemann-Ross, [41,42] Kelen-Tüdös, [43,44] and extended Kelen-Tüdös (extended K-T) methods [34] were reported in the literature. But the extended K-T method contemplates the drift in the comonomer and copolymer compositions along with monomer conversion which validates the manipulation for high conversion data.…”

Section: Determination Of Reactivity Ratiosmentioning

confidence: 99%

Phenylalanine‐Tethered pH‐Responsive Poly(2‐Hydroxyethyl Methacrylate)

Choudhury

Das

Samadder

et al. 2021

Chemistry An Asian Journal

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A series of pH-responsive random copolymers comprised of 2-hydroxyethyl methacrylate (HEMA) and tertbutyl carbamate (Boc)-protected phenylalanine methacryloyloxyethyl ester (Boc-Phe-EMA) were synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization in N,N'-dimethylformamide (DMF) at 70°C. The synthesized copolymers were comprehensively characterized using a combination of techniques, including 1 H NMR, FT-IR spectroscopy and size exclusion chromatography (SEC). Reactivity of each monomers towards controlled radical polymerization was evaluated by determining the reactivity ratios by virtue of extended Kelen-Tüdös method at high conversions revealed the higher reactivity of non-modified HEMA (r HEMA = 1.03) in contrast to Boc-Phe-EMA (r Boc-Phe-EMA = 0.48). Furthermore, the expulsion of the Boc-groups resulted copolymers with ionizable pendant primary ammonium and hydroxyl groups. To understand the glass transition behaviours of homo-and co-polymers, differential scanning calorimetric (DSC) measurements were carried out. The effect of HEMA content on the pH-sensitivity of the copolymers in aqueous medium was investigated through turbidity measurements. Finally, the counteranion exchange from trifluoroacetate to chloride provided copolymers with enhanced water solubility and unaltered phase transition pH.

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Section: Determination Of Reactivity Ratiosmentioning

confidence: 99%

Phenylalanine‐Tethered pH‐Responsive Poly(2‐Hydroxyethyl Methacrylate)

Choudhury

Das

Samadder

et al. 2021

Chemistry An Asian Journal

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“…This arrangement leads to a shift in the electron cloud distribution of the double bond, ultimately enhancing the reactivity of the monomers. Liu et al 16 conducted a calculation of EPEG‐AA copolymerization using both linear and nonlinear least squares methods. They demonstrated that the macromonomer activity of EPEG is closer to that of AA, resulting in higher copolymerization efficiency.…”

Section: Introductionmentioning

confidence: 99%

Research on the performances of VPEG macromonomer grafted different functional groups to prepare polycarboxylate superplasticizers

Dong,

Liu,

et al. 2024

J of Applied Polymer Sci

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The advent of novel polyether macromonomer has garnered significant attention within the industrial domain. In this study, a range of polycarboxylate superplasticizers (PCEs) was produced via free radical polymerization, employing a new polyether monomer, 4‐hydroxybutyl vinyl polyethylene glycol ether (VPEG). This monomer served as the predominant component and was grafted with various functional monomers on its main chain. The molecular configuration of the resultant PCEs was discerned through Fourier infrared spectroscopy and gel permeation chromatography, while the surface tension underwent assessment via a surface tension meter. Both the initial and subsequent fluidity of cement paste and mortar were leveraged to ascertain the dispersion and retention efficacy of the synthetic PCEs. The ramifications of diverse functional group grafts of the new polyether monomer on the cement hydration procedure and strength attributes were elucidated via setting time, hydration heat assays of cement paste, SEM analysis, and compressive strength evaluations of mortar. Observations reveal that the carboxylic acid group significantly reduces surface tension, whereas the sulfonic acid group's effect remains minimal. The incorporation of both the amide and sulfonic acid groups marginally impacts the preliminary dispersion efficacy of PCEs but notably affects dispersion retention. Furthermore, these functional groups facilitate cement hydration, expedite the primary setting time of the cement paste, and bolster the initial compressive strength of the mortar. Specifically, the grafted of sodium methacrylsulfonate (SMAS) yields the most noticeable results. Finally, the working mechanism of PCEs with varying molecular structures has been explained in light both theoretical and experimental results. This research offers valuable insights for subsequent investigations into the fabrication of polycarboxylate superplasticizers using the VPEG macromonomer.

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“…Open literature about the reactivity ratios of these types of macromonomers is very scarce. In fact, the results are limited to a couple of sources available. ,, So far, three of these macromonomers have been studied together with acrylic acid. These are polyethylene glycol monovinyl ether (EPEG), polyethylene glycol 3-methyl-3-butenyl ether (IPEG), and polyethylene glycol 2-methyl-2-propenyl ether (HPEG).…”

Section: Introductionmentioning

confidence: 99%

Acidic Aqueous-Phase Copolymerization of AA and HPEG Macromonomer: Influence of Monomer Concentration on Reactivity Ratios

Palma-Lemus,

Hamzehlou,

Froidevaux

et al. 2023

Ind. Eng. Chem. Res.

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Poly(acrylic acid-co-polyethylene glycol 2-methyl-2-propenyl ether) copolymers are comb-like water-soluble copolymers produced by the copolymerization of acrylic acid (AA) and polyethylene glycol 2-methyl-2-propenyl ether (HPEG). The main application of these copolymers is as superplasticizers for cementitious materials, also known as polycarboxylate ethers (PCE’s). The kinetics of the water-soluble monomers is substantially more complex than that of non-water-soluble monomers as their kinetics depend on various parameters such as monomer concentration, pH, and ionic strength. In this work, aqueous in situ 1H NMR copolymerizations of AA and HPEG at different initial overall monomer weight fractions and comonomer molar ratios under acidic media were carried out. The gathered kinetic data were used for the estimation of the reactivity ratios of AA-HPEG. A nonlinear least-squares (NLLSQ) method based on the Mayo–Lewis composition equation was used to estimate the reactivity ratios by fitting the cumulative copolymer composition or free monomer molar fraction as a function of overall monomer conversion. The estimation indicates that the reactivity ratio of acrylic acid is higher than that of the HPEG monomer, which is estimated as close to zero. In addition, the reactivity ratio of AA depends on the overall monomer weight fraction; the higher the initial overall monomer concentration, the higher the reactivity ratio is. An empirical expression is derived that describes the dependency of the reactivity ratio of AA on the overall monomer mass fraction (r AA = 1.76 (±0.062) + 0.0275 (±4.37 × 10–3) w M (%); r HPEG = 2.3 × 10–14 (±6.02 × 10–3)).

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Study on the monomer reactivity ratio and performance of EPEG-AA (ethylene-glycol monovinyl polyethylene glycol–acrylic acid) copolymerization system

Cited by 12 publications

References 34 publications

Phenylalanine‐Tethered pH‐Responsive Poly(2‐Hydroxyethyl Methacrylate)

Phenylalanine‐Tethered pH‐Responsive Poly(2‐Hydroxyethyl Methacrylate)

Research on the performances of VPEG macromonomer grafted different functional groups to prepare polycarboxylate superplasticizers

Acidic Aqueous-Phase Copolymerization of AA and HPEG Macromonomer: Influence of Monomer Concentration on Reactivity Ratios

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