Controlled Radical Polymerization: State of the Art in 2008

Matyjaszewski, Krzysztof

doi:10.1021/bk-2009-1023.ch001

Cited by 22 publications

(16 citation statements)

References 104 publications

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“…Reversible deactivation radical polymerization (RDRP) endows polymer chains with CEFs, which can be utilized for chain extensions or to trigger depolymerization reactions, with the propensity for propagation or depropagation determined by the thermodynamics of the system. Deactivation of a polymer chain in RDRP can be through a reversible addition–fragmentation chain-transfer (RAFT) mechanism regulated by a chain-transfer agent (CTA), by reversible deactivation in a nitroxide-mediated polymerization, or by reversible halogen atom transfer between a catalyst (often copper, ruthenium, or organic photocatalysts) and the radical chain end in an atom transfer radical polymerization (ATRP). − …”

Section: Introductionmentioning

confidence: 99%

Depolymerization of P(PDMS₁₁MA) Bottlebrushes via Atom Transfer Radical Polymerization with Activator Regeneration

et al. 2021

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Depolymerization of vinyl polymers into monomers is energy-intensive due to the high thermal and chemical stability of the backbone. Depolymerizations of methacrylic polymers are typically conducted above the ceiling temperature and thermal degradation temperature to degrade polymers by bond scission. This work investigates the catalyzed depolymerization of a Clcapped poly(poly(dimethylsiloxane) methacrylate) (P-(PDMS 11 MA-Cl)) polymer mediated by an atom transfer radical polymerization catalyst: copper(II) chloride/tris(2-pyridylmethyl)amine (CuCl 2 /TPMA) at 170 °C. The depolymerization yield, rate, and selectivity were improved by increasing the ratio of [TPMA]/[CuCl 2 ]. Electron transfer from the ligand contributed to the Cu(I) activator (re)generation at high temperature (T > 130 °C), as proven by ultraviolet−visible spectroscopy. The bottlebrush could be partially depolymerized and repolymerized over a few cycles.

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Section: Introductionmentioning

confidence: 99%

Depolymerization of P(PDMS₁₁MA) Bottlebrushes via Atom Transfer Radical Polymerization with Activator Regeneration

et al. 2021

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“…These techniques include supplemental activator and reducing agent (SARA) ATRP, activators regeneration by electron transfer (ARGET) ATRP, initiators for continuous activator regeneration (ICAR), or electrochemically mediated ATRP (eATRP), where the ratio of the concentration of activator to deactivator is precisely controlled by electrochemical means . These techniques allow controlled polymerization of various vinyl and acrylic monomers under mild conditions . The control over the polymerization is of great importance for the preparation of well‐defined nanostructures as pH‐sensitive polymeric micelles on their basis, which gain increasing interest in the nanotechnology with respect to the biomedical and medical fields.…”

Section: Introductionmentioning

confidence: 99%

Design and synthesis of fluorescent shell functionalized polymer micelles for biomedical application

Ismail

Bryaskova

Georgiev

et al. 2020

Polymers for Advanced Techs

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pH-sensitive polymers can be defined as polyelectrolytes that include in their structure weak acidic or basic groups that either accept or release protons in response to a change in the environmental pH. This work summarizes the design, synthesis, and potential applications of pH-responsive fluorescent copolymers in the biomedical field.This was achieved using atom transfer radical polymerization (ATRP) of tert-butyl acrylate using a CuBr/N,N,N 0 ,N 00 N 00 -pentamethyldiethylenetriamine catalyst system in conjunction with an alkyl bromide as the initiator. Well-defined macroinitiators based on poly(tert-butyl acrylate) with narrow molecular weight distributions were obtained by the addition of an appropriate solvent system in order to create a homogeneous catalytic system. The addition of n-butyl acrylate as a second building block in order to create well-defined poly(tert-butyl acrylate)-b-poly(n-butyl acrylate) block copolymers (PtBA-b-PnBA) followed by chemical modification of the block copolymers and functionalization with an appropriate fluorescent compound are the basis for the preparation of well-defined fluorescent pH-sensitive micelles. Thus, prepared water soluble nanosized pH-sensitive micelles consisting of hydrophobic poly(n-butyl acrylate) core and hydrophilic polyacrylic acid shell decorated with an appropriate fluorescent compound determined their potential applications of these systems in the field of biomedicine as biosensors, controlled drug delivery systems, and so on. In this respect, the cell viability and internalization of the polymer micelles were studied. K E Y W O R D S bioimaging, fluorescent nanosized micelles, personalized theranostic systems, pH-sensitive block copolymers 1 | INTRODUCTION These days, a wide range of compounds being developed are polymers, because of the variety of their chemical and physical properties and the possibility to be tailored towards many applications. In the last two decades, tremendous interest has been shown in polymeric materials that could reversibly or irreversibly change their physical and chemical properties under the influence of external stimuli, eg, pH, temperature, presence of specific ions, light radiation, mechanical forces, magnetic fields, electric fields, and bioactive molecules. 1 Among them, special attention is paid to the well-defined pH block copolymers, which at physiological pH (7.1-7.3) self-assemble into micellar structures and the acidification of the media lead to controlled micelle dissociation and triggered drug release. Several modern techniques can be applied for their synthesis as atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer (RAFT), and stable free radical polymerization (SFRP). 2 These techniques are based on a reversible activation/deactivation cycle of

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“…In the realm of conventional chain-growth polymerization, reversible deactivation radical polymerization (RDRP), − living ionic polymerization, , metathesis polymerization, and supramolecular methods have been adapted and exploited to achieve this orthogonality. Specifically, the RDRP variants atom transfer radical polymerization (ATRP), reversible addition–fragmentation chain transfer (RAFT) polymerization, and nitroxide-mediated polymerization (NMP) feature unique synthetic advantages for certain monomer families. , The design of appropriate initiators and mediating agents enables the synthesis of polymers with defined end-groups amenable to efficient postmodification chemistry. − By selecting functionalities orthogonal to radical processes, an enormous breadth of end-group chemistries is accessible. , A plethora of architectures has been realized, including a vast variety of (hyper)branched polymers, , dendrimers, star polymers, , polymer brushes, comb-shaped polymers, and block copolymers, , in addition to cyclic systems, as well as rotaxanes …”

Section: Introductionmentioning

confidence: 99%

Fusing Light-Induced Step-Growth Processes with RAFT Chemistry for Segmented Copolymer Synthesis: A Synergetic Experimental and Kinetic Modeling Study

et al. 2017

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We pioneer the synthesis of well-defined high molar mass segmented copolymers, employing a unique combination of step-growth and reversible addition–fragmentation chain transfer (RAFT) polymerization. The step-growth precursor polymer is obtained via the ambient temperature UV-light-induced Diels–Alder reaction of 6′-(propane-1,3-diylbis(oxy))bis(2-methylbenzaldehyde) (AA monomer) and di(isopropionic ethyl ester fumarate) trithiocarbonate (BB monomer). Unconventional off-stoichiometric conditions (r = [AA]0:[BB]0 = 1.5–1.75) are employed to ensure a sufficiently high incorporation of BB in the step-growth product (1200 ≤ M n/g mol–1 ≤ 3950). The optimum r value is based on a detailed product distribution analysis, comparing experimental and bivariate kinetic Monte Carlo generated data, using a scheme of over 200 reactions. The analysis highlights the unexpected occurrence of AA homopolymerization and the ligation of the resulting AA segments at higher reaction times. The precursor step-growth polymer is successfully transformed into a segmented copolymer via insertion of styrene by RAFT polymerization at 60 °C (11 200 ≤ M n/g mol–1 ≤ 53 400), as confirmed both experimentally and through simulations.

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Controlled Radical Polymerization: State of the Art in 2008

Cited by 22 publications

References 104 publications

Depolymerization of P(PDMS₁₁MA) Bottlebrushes via Atom Transfer Radical Polymerization with Activator Regeneration

Depolymerization of P(PDMS₁₁MA) Bottlebrushes via Atom Transfer Radical Polymerization with Activator Regeneration

Design and synthesis of fluorescent shell functionalized polymer micelles for biomedical application

Fusing Light-Induced Step-Growth Processes with RAFT Chemistry for Segmented Copolymer Synthesis: A Synergetic Experimental and Kinetic Modeling Study

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Controlled Radical Polymerization: State of the Art in 2008

Cited by 22 publications

References 104 publications

Depolymerization of P(PDMS11MA) Bottlebrushes via Atom Transfer Radical Polymerization with Activator Regeneration

Depolymerization of P(PDMS11MA) Bottlebrushes via Atom Transfer Radical Polymerization with Activator Regeneration

Design and synthesis of fluorescent shell functionalized polymer micelles for biomedical application

Fusing Light-Induced Step-Growth Processes with RAFT Chemistry for Segmented Copolymer Synthesis: A Synergetic Experimental and Kinetic Modeling Study

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Depolymerization of P(PDMS₁₁MA) Bottlebrushes via Atom Transfer Radical Polymerization with Activator Regeneration

Depolymerization of P(PDMS₁₁MA) Bottlebrushes via Atom Transfer Radical Polymerization with Activator Regeneration