ATRP of MIDA Boronate-Containing Monomers as a Tool for Synthesizing Linear Phenolic and Functionalized Polymers

Li, Xin; He, Congze; Matyjaszewski, Krzysztof; Pan, Xiangcheng

doi:10.1021/acsmacrolett.1c00592

Cited by 14 publications

(11 citation statements)

References 35 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Nature shows impressive precision in the biosynthesis of biopolymers with a precise molecular weight, molecular weight distribution ( Đ ), and architecture. To mimic natural power, the precise control of molecular weight, Đ , and architecture of manmade polymers is the holy grail in polymer chemistry. − The successful achievements in this field with well-controlled polymers allow polymers to be regarded as organic (macro)molecules rather than ill-defined mixtures, which enables the precise synthesis of polymers and is of significant importance in polymer science. − …”

mentioning

confidence: 99%

Living Covalent-Anionic-Radical Polymerization via a Barbier Strategy

Sheng

Chen

et al. 2022

ACS Macro Lett.

View full text Add to dashboard Cite

The developments of the living alkene polymerization method have achieved great progress and enabled the precise synthesis of important polyalkenes with controlled molecular weight, molecular weight distribution, and architecture through an anionic, cationic or radical strategy. However, it is still challenging to develop a living alkene polymerization method through an all-in-one strategy where anionic and radical characteristics are merged into one polymerization species. Here, a versatile living polymerization method is reported by introducing a well-established all-in-one covalent-anionic-radical Barbier strategy into a living polymerization. Through this living covalent-anionic-radical Barbier polymerization (Barbier CARP), narrow distributed polystyrenes, with Đ as low as 1.05, are successfully prepared under mild conditions with a full monomer conversion by using wide varieties of organohalides, for example, alkyl, benzyl, allyl, and phenyl halides, as initiators with Mg in one pot. This living covalent-anionic-radical polymerization via a Barbier strategy expands the methodology library of polymer chemistry and enables living polymerization with an unconventional polymerization mode.

show abstract

mentioning

confidence: 99%

Living Covalent-Anionic-Radical Polymerization via a Barbier Strategy

Sheng

Chen

et al. 2022

ACS Macro Lett.

View full text Add to dashboard Cite

show abstract

“…These polymers can be utilized as a versatile platform for postpolymerization modification, including Suzuki–Miyaura coupling and boronate ester transformations (Figure b). Moreover, these monomers could also be applied in the atom transfer radical polymerization (ATRP) system with superior results . The ATRP method eliminated the color of the RAFT polymerization products and the side reactions caused by the presence of terminal thiocarbonyl groups.…”

Section: Synthesis Of Polymers Containing N→b Dative Bondmentioning

confidence: 99%

N-Coordinated Organoboron in Polymer Synthesis and Material Science

Dong

et al. 2022

ACS Polym. Au

Self Cite

View full text Add to dashboard Cite

Organoboron chemistry has been widely explored and developed in synthetic chemistry for over half a century and provides various elegant synthetic protocols in polymer synthesis. Compared with most trivalent bare organoboron compounds, Ncoordinated organoboron shows better performances, such as air and moisture stability. This review summarizes the application of various N-coordinated boranes and boronic acid/esters in polymer synthesis and materials science. We introduce the significance of N-coordinated boranes and boronate esters for controllable polymer synthesis and systematically summarize the structures and properties of polymers containing N-coordinated boronate esters. Furthermore, we highlight the effect of N→B dative bonds on improving the performance of self-healing materials. We hope that, through this review, more researchers will realize the advantages of N-coordinated organoboron and promote the development of this direction in polymer synthesis and materials science.

show abstract

“…General information of materials; synthesis and characterization of monomers and copolymers; supplemental figures and tables: gel permeation chromatograms, copies of spectra ( 1 H NMR, 19 F NMR, DSC, TGA), details of computational procedures, and atomic coordinates of compounds studied by DFT calculation (PDF)…”

Section: ■ Conclusionmentioning

confidence: 99%

“…Recently, considerable efforts have been devoted to preparing polymers with boronyl FGs. − For example, Masarwa reported ring-opening metathesis polymerization to generate gem -diboron-based polymers . A variety of groups demonstrated the syntheses of polymers with BN aromatic groups and boronate esters as side groups via free-radical (co)polymerizations (Scheme A). − Meanwhile, the incorporation of boronyl pendants on polymeric backbones could enable the generation of dynamically cross-linked networks, , nanostructures, etc., , revealing the increasing importance of B-based functionality in polymeric material engineering.…”

Section: Introductionmentioning

confidence: 99%

Facile Access to gem-Trifluoromethyl/Boron-Functionalized Polymers via Free-Radical Copolymerization and Cotelomerization

et al. 2022

View full text Add to dashboard Cite

Functional fluoropolymers are important for various applications due to the integrated characteristics of functional groups and fluorocarbon segments. Herein, we developed (1) thermally initiated and visible-light-initiated copolymerization of (trifluoromethyl)vinyl boronic esters (CF3VBs) and unconjugated alkenes (18 examples, including vinyl ethers, esters, and amides), enabling the efficient synthesis of a broad scope of fluoropolymers in 71–92% yield and variable fractions of gem-CF3/B substituents (F CF3VB = 0.26–0.84) at different molar masses (M n = 5.2–33.4 kDa) and (2) visible-light-initiated cotelomerization of CF3VB and unconjugated alkenes with p-tolyl disulfide as a telogen (M n = 3.6–13.0 kDa). Reactivity ratios for copolymerization were determined by the Meyer–Lowry method at 65 °C (for BVE: r CF3VB = 1.254, r BVE = 0.006; for VAc: r CF3VB = 0.235, r VAc = 0.042; for NVP: r CF3VB = 1.067, r NVP = 0.063). The achieved high fractions of CF3VBs in copolymers are also confirmed by density functional theory (DFT) calculation results. Through post-polymerization modifications, gem-CF3/B units could transform into various copolymers and terpolymers with geminal functionalities (e.g., gem-CF3/OH, gem-CF3/vinyl, gem-CF3/furan). The increase of geminal functionalities enables clearly amplified chemical responsiveness toward pH variation, as demonstrated by fluoropolymers with gem-CF3/OH.

show abstract

ATRP of MIDA Boronate-Containing Monomers as a Tool for Synthesizing Linear Phenolic and Functionalized Polymers

Cited by 14 publications

References 35 publications

Living Covalent-Anionic-Radical Polymerization via a Barbier Strategy

Living Covalent-Anionic-Radical Polymerization via a Barbier Strategy

N-Coordinated Organoboron in Polymer Synthesis and Material Science

Facile Access to gem-Trifluoromethyl/Boron-Functionalized Polymers via Free-Radical Copolymerization and Cotelomerization

Contact Info

Product

Resources

About