Copolymerization of amine-containing monomers and dodecyl (meth)acrylate in toluene: controlling compositional heterogeneity

Казанцев, О. А.; Каморин, Д. М.; Sivokhin, А. P.; Samodurova, S. I.; Orekhov, Dmitry V.; Korotkova, Tatiana V.

doi:10.1007/s10965-013-0353-8

Cited by 15 publications

(7 citation statements)

References 18 publications

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“…27−29 In addition, copolymerizations between monomers that form prepolymerization aggregates also have been reported to demonstrate deviations from the Mayo−Lewis theory. 30,31 In all these cases, the unconventional behavior is attributed to emergent conditions that differentially influence the collision frequencies of various comonomer pairs. Such complexities may be expected to exert even more of an influence on the sequences of step-growth copolymers than on those of the chain-growth copolymers described above, but little work has been done, either experimentally or computationally, to investigate how emergent collective behaviors among the growing chains might influence the sequences of these step-growth copolymers.…”

Section: Introductionmentioning

confidence: 99%

Modeling the Influence of Emergent and Self-Limiting Phase Separations among Nascent Oligomers on Polymer Sequences Formed during Irreversible Step-Growth Copolymerizations

Zhang

DuBay

2019

Macromolecules

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The sequential ordering of different monomers within synthetic copolymers is remarkably difficult to control. Our understanding of the determinants of and variations within copolymer sequences, even in simple step-growth reactions, remains limited. In this work, we perform simulations on a generic model of irreversible step-growth copolymerization between two types of monomers, A and B, in solution. Our results demonstrate that relatively weak attractions among nascent oligomers can exert considerable influence over the sequential arrangement of monomers in the final set of copolymers, even when identical reaction barriers exist between all monomer pairs. The observed effects cannot be fully accounted for within conventional polymerization theories due to a breakdown in Flory’s principle of equal reactivity that occurred in some cases. Nonetheless, these anomalous results can be readily explained by the Flory–Huggins theory, as a phase separation between A-rich and B-rich segments can emerge from and also be limited by the copolymerization process itself. This observation suggests that new routes for the one-pot synthesis of sequence-biased copolymers may be available through the coupling of step-growth copolymerizations and emergent phase separations.

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Section: Introductionmentioning

confidence: 99%

Modeling the Influence of Emergent and Self-Limiting Phase Separations among Nascent Oligomers on Polymer Sequences Formed during Irreversible Step-Growth Copolymerizations

Zhang

DuBay

2019

Macromolecules

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“…Recently the formation of monomer assemblies with interposition of vinyl groups favorable for the polymerization was shown to be the reason of anomalous acceleration of the homopolymerization of higher alkyl acrylates and N‐alkylacrylamides in toluene. For the radical copolymerization of dodecyl acrylate or dodecyl methacrylate with DMAPMA in toluene, the total initial monomer concentration (at the constant monomer ratio) significantly affects the composition of copolymers obtained at low conversions . The authors suggested that this concentration effect was also related to the influence of monomers association.…”

Section: Introductionmentioning

confidence: 99%

Influences of monomer self‐association on the radical solution homopolymerization of N‐[3‐(dimethylamino)propyl](meth)acrylamide

Каморин

Rumyantsev

Казанцев

et al. 2016

J of Applied Polymer Sci

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The specific dependencies of the initial reduced polymerization rate on the initial monomer concentration were introduced for the radical homopolymerization of N‐[3‐(dimethylamino)propyl]acrylamide (DMAPA) and N‐[3‐(dimethylamino)propyl]methacrylamide (DMAPMA) in toluene, DMF, and water at 60 °С. The degree of the monomer self‐association and the ratio of the amides constituting various types of associates were evaluated using FT‐IR spectroscopy and computer simulation for the solutions of DMAPA and DMAPMA in toluene with different monomer concentrations. The hypothesis linking the type of predominant pre‐reaction monomer assemblies and the revealed concentration effects was proposed for the homopolymerization of aminoamide monomers and explaining unconventional experimental data. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44412.

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“…For the synthesis and analysis of polymer samples, we used the methods that were previously developed for homopolymers and copolymers of higher alkyl methacrylates and alkyl acrylates [20,21] as well as their copolymers with amine-containing methacrylic esters and amides [22], N-alkyl (meth)acrylamides [23], AOEGM [24], and VBE [15]. For the purposes of the comparative assessment of dispersion properties, we also tested, under similar conditions, a number of commercial additives, specifically: polymethacrylate viscosity index improvers Viscoplex 0-220 and Viscoplex 7-610, polymethacrylate dispersant/VII Viscoplex 12-310 (all manufactured by Evonik RohMaX Additives GmbH), succinimide dispersant S-40 (NPP Qualitet, Russia), and thickener Syntolux V-15 (SOVKHIMTEKH, Russia; this represents a VBE homopolymer).…”

Section: Methodsmentioning

confidence: 99%

Polymers of Higher Alkyl (Meth)acrylates: The Effects of Structure on Dispersion Properties in Petroleum Oil I-20A

et al. 2021

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The paper describes a comparative study on the effects of the composition of polymers of higher alkyl (meth)acrylates on their dispersion degree in petroleum oil I-20A. The dispersion degree parameter is evaluated in accordance with a modified spectrophotometric method proposed in the study. It was found that increasing the polymer amphiphilicity by introducing nitrogen-based units in an amount of 5-15% dramatically enhances the dispersion properties, and that amide groups have a stronger effect than amine ones. Increasing the polyalkyl methacrylate amphiphilicity by introducing (in an amount of 5-40%) alkoxy oligo(ethylene glycol) methacrylate (AOEGM) units containing 3-7 ethoxy groups does not enhance the polymer's dispersion ability. The only exception was a single case of a fairly high dispersion ability achieved for a copolymer containing 30% of AOEGM units with long hydrophilic chains consisting of ten ethoxy groups.

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Copolymerization of amine-containing monomers and dodecyl (meth)acrylate in toluene: controlling compositional heterogeneity

Cited by 15 publications

References 18 publications

Modeling the Influence of Emergent and Self-Limiting Phase Separations among Nascent Oligomers on Polymer Sequences Formed during Irreversible Step-Growth Copolymerizations

Modeling the Influence of Emergent and Self-Limiting Phase Separations among Nascent Oligomers on Polymer Sequences Formed during Irreversible Step-Growth Copolymerizations

Influences of monomer self‐association on the radical solution homopolymerization of N‐[3‐(dimethylamino)propyl](meth)acrylamide

Polymers of Higher Alkyl (Meth)acrylates: The Effects of Structure on Dispersion Properties in Petroleum Oil I-20A

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