Facile synthesis of block copolymers from a cinnamate derivative by combination of AGET ATRP and click chemistry

Cheng, Chuanjie; Bai, Xiongxiong; Zhang, Xu; Chen, Ming; Huang, Qiwen; Zhong-yu, HU; Tu, Yuanming

doi:10.1007/s13233-014-2180-0

Cited by 7 publications

(6 citation statements)

References 36 publications

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“…In practice, however, functional polymers prepared by ATRP are prone to side reactions including radical–radical coupling ,, of bromine termini and Glaser coupling of alkyne termini, ,,− which compromise the macromonomer functionality and their subsequent utility for the synthesis of well-defined, hierarchically structured materials by CuAAC end-linking reactions.…”

Section: Introductionmentioning

confidence: 99%

Preventing Alkyne–Alkyne (i.e., Glaser) Coupling Associated with the ATRP Synthesis of Alkyne-Functional Polymers/Macromonomers and for Alkynes under Click (i.e., CuAAC) Reaction Conditions

et al. 2017

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Alkyne-functional polymers synthesized by ATRP exhibit bimodal molecular weight distributions indicating the occurrence of some undesirable side reaction. By modeling the molecular weight distributions obtained under various reaction conditions, we show that the side reaction is alkyne-alkyne (i.e., Glaser) coupling. Glaser coupling accounts for as much as 20% of the polymer produced, significantly compromising the polymer functionality and undermining the success of subsequent click reactions in which they are used. Glaser coupling does not occur during ATRP but during postpolymerization workup upon first exposure to air. Two strategies are reported that effectively eliminate these coupling reactions without the need for a protecting group for the alkyne-functional initiator: (1) maintaining low temperature post-ATRP upon exposure to air followed by immediate removal of copper catalyst; (2) adding excess reducing agents post-ATRP which prevent the oxidation of Cu(I) catalyst required by the Glaser coupling mechanism. Post-ATRP Glaser coupling was also influenced by the ATRP synthesis ligand used. The order of ligand activity for catalyzing Glaser coupling was: linear bidentate > tridentate > tetradentate. We find that Glaser coupling is not problematic in ARGET-ATRP of alkyne-terminated polymers because a reducing agent is present during polymerization, however the molecular weight distribution is broadened compared to ATRP due to the presence of oxygen. Glaser coupling can also occur for alkynes held under CuAAC reaction conditions but again can be eliminated by adding appropriate reducing agents.

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Section: Introductionmentioning

confidence: 99%

Preventing Alkyne–Alkyne (i.e., Glaser) Coupling Associated with the ATRP Synthesis of Alkyne-Functional Polymers/Macromonomers and for Alkynes under Click (i.e., CuAAC) Reaction Conditions

et al. 2017

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“…The answer is positive. Actually, concurrent ATRP/CuAAC has been used as a very efficient tool to synthesize block copolymers [ 64 ], brush polymers [ 65 , 66 , 67 ], polymers with functional side groups [ 68 , 69 ], networks [ 70 ], etc.…”

Section: Concurrent Reactions Used Together With Atrpmentioning

confidence: 99%

Macromolecular Engineering by Applying Concurrent Reactions with ATRP

2020

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Modern polymeric material design often involves precise tailoring of molecular/supramolecular structures which is also called macromolecular engineering. The available tools for molecular structure tailoring are controlled/living polymerization methods, click chemistry, supramolecular polymerization, self-assembly, among others. When polymeric materials with complex molecular architectures are targeted, it usually takes several steps of reactions to obtain the aimed product. Concurrent polymerization methods, i.e., two or more reaction mechanisms, steps, or procedures take place simultaneously instead of sequentially, can significantly reduce the complexity of the reaction procedure or provide special molecular architectures that would be otherwise very difficult to synthesize. Atom transfer radical polymerization, ATRP, has been widely applied in concurrent polymerization reactions and resulted in improved efficiency in macromolecular engineering. This perspective summarizes reported studies employing concurrent polymerization methods with ATRP as one of the reaction components and highlights future research directions in this area.

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“…Atom transfer radical polymerization (ATRP) [26], a well-known controlled radical polymerization (CRP) technique, not only shares a number of attractive features with "click chemistry", such as a high tolerance toward a wide range of functional groups and protic solvents, but also uses the same copper catalyst system [27]. The combination of these two techniques in one-pot synthesis provides a versatile approach for the preparation of block copolymers [28][29][30], functional macromolecules [31][32][33][34] and interpenetrating network hydrogels [13], among others. However, the combination of two chemistries has rarely been utilized to prepare the functional polymeric NPs in one-pot synthesis [35].…”

Section: Introductionmentioning

confidence: 99%

“…The combination of these two techniques in one-pot synthesis provides a versatile approach for the preparation of block copolymers [28][29][30], functional macromolecules [31][32][33][34] and interpenetrating network hydrogels [13], among others. However, the combination of two chemistries has rarely been utilized to prepare the functional polymeric NPs in one-pot synthesis [35].…”

Section: Introductionmentioning

confidence: 99%

PEGylated Fluorescent Nanoparticles from One-Pot Atom Transfer Radical Polymerization and “Click Chemistry”

Zhang

et al. 2015

Polymers

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Abstract:The preparation of PEGylated fluorescent nanoparticles (NPs) based on atom transfer radical polymerization (ATRP) and "click chemistry" in one-pot synthesis is presented.First, poly(p-chloromethyl styrene-alt-N-propargylmaleimide) (P(CMS-alt-NPM)) copolymer was prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization. Subsequently, the azido-containing fluorene-based polymer, poly[(9,9-dihexylfluorene)-alt-(9,9-bis-(6-azidohexyl)fluorene)] (PFC6N 3 ), was synthesized via Suzuki coupling polymerization, followed by azidation. Finally, the PEGylated fluorescent NPs were prepared via simultaneous intermolecular "click" cross-linking between P(CMS-alt-NPM) and PFC6N 3 and the ATRP of poly(ethylene glycol) methyl ether methacrylate (PEGMMA) using P(CMS-alt-NPM) as the macroinitiator. The low cytotoxicity of the PEGylated fluorescent NPs was revealed by incubation with KB cells, a cell line derived from carcinoma of the nasopharynx, in an in vitro experiment. The biocompatible PEGylated fluorescent NPs were further used as a labeling agent for KB cells.

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Facile synthesis of block copolymers from a cinnamate derivative by combination of AGET ATRP and click chemistry

Cited by 7 publications

References 36 publications

Preventing Alkyne–Alkyne (i.e., Glaser) Coupling Associated with the ATRP Synthesis of Alkyne-Functional Polymers/Macromonomers and for Alkynes under Click (i.e., CuAAC) Reaction Conditions

Preventing Alkyne–Alkyne (i.e., Glaser) Coupling Associated with the ATRP Synthesis of Alkyne-Functional Polymers/Macromonomers and for Alkynes under Click (i.e., CuAAC) Reaction Conditions

Macromolecular Engineering by Applying Concurrent Reactions with ATRP

PEGylated Fluorescent Nanoparticles from One-Pot Atom Transfer Radical Polymerization and “Click Chemistry”

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