An Industrial History of<scp>RAFT</scp>Polymerization

Moad, Graeme

doi:10.1002/9783527821358.ch24

Cited by 7 publications

(3 citation statements)

References 49 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…These methods have been widely adopted in biomedical and materials science, with numerous commercial applications. [3] Many advanced applications of controlled polymerisation require the covalent linking of the polymer with small molecules (polymer functionalisation) [4] or other macromolecules (polymer grafting). [5] Polymer grafting can be achieved by either attaching an existing polymer chain to a substrate ("grafting to") or by polymerising monomers from a reactive site present on the substrate ("grafting from").…”

Section: Introductionmentioning

confidence: 99%

RAFT Polymerisation by the Radical Decarboxylation of Carboxylic Acids**

Ayurini,

Haridas,

Mendoza

et al. 2023

Angew Chem Int Ed

View full text Add to dashboard Cite

The controlled grafting of polymers from small‐ and macro‐molecular substrates is an essential process for many advanced polymer applications. This usually requires the pre‐functionalisation of substrates with an appropriate functional group, such as a RAFT agent or ATRP initiator, which requires additional synthetic steps. In this paper, we describe the direct grafting of RAFT polymers from carboxylate containing small molecules and polymers via photochemical radical decarboxylation. This method utilises the innate functional groups present in the substrates, and achieves efficient polymer initiation in a single step with excellent control of molecular weight and dispersity.

show abstract

Section: Introductionmentioning

confidence: 99%

RAFT Polymerisation by the Radical Decarboxylation of Carboxylic Acids**

Ayurini,

Haridas,

Mendoza

et al. 2023

Angew Chem Int Ed

View full text Add to dashboard Cite

show abstract

“…30−33 Both low initiator concentrations and the rapid polymerization of monomer blocks are thus achieved. The syntheses of highmolecular-weight polymers and the polymerization of monomers with low propagation rate coefficients (k p ), which have traditionally been problematic in terms of control over MWD, 4,18 were then able to be executed with shorter reaction times than previous works in the field. 34 This has among other achievements led to the synthesis of multiblock copolymer nanoparticles demonstrating multilayer morphology, 14 enhanced mechanical properties of the resulting materials, 35 and multiblock copolymer compositions comprising high numbers of different monomer species.…”

Section: ■ Introductionmentioning

confidence: 99%

Expanding the Scope of RAFT Multiblock Copolymer Synthesis Using the Nanoreactor Concept: The Critical Importance of Initiator Hydrophobicity

et al. 2022

Self Cite

View full text Add to dashboard Cite

Precise multiblock copolymer synthesis coupled with self-assembly offers morphology control on length scales ranging from a few nanometers to micrometer scale, providing enormous opportunities for future development of advanced materials and applications. The scope of multiblock copolymer synthesis via RAFT polymerization has recently been expanded by application of the nanoreactor concept for emulsion polymerization. This enabled use of slow propagating monomers, such as styrenes and methacrylates, in multiblock synthesis. However, severe limitations attributed to the high polymer glass transition temperature (T g ) of some polymers have hitherto remained. The use of monomers that give such high-T g polymers effectively prevented penetration of aqueous-phase-generated radicals into the polymer particles wherein the RAFT functionality is located. We here demonstrate that these constraints can be relieved by judicious choice of the radical initiator. Multiblock homopolymers were synthesized by seeded RAFT emulsion polymerization using initiators that differ substantially in hydrophobicity. Ten sequential chain extensions using tert-butyl methacrylate (T g of PtBMA = 118 °C) with targeted block DP = 100 were conducted at 80 °C for each initiator. Markedly narrower molecular weight distributions were obtained when more hydrophobic initiators were used. The same polymerizations targeting low -T g polymers (PnBMA; T g = 20 °C) resulted in only minor differences in control when the different initiators were used, supporting our hypothesis on the role of radical penetration. The present results are anticipated to significantly expand the scope of RAFT polymerization in aqueous emulsion by allowing access to a wider range of low-dispersity multiblock copolymers.

show abstract

“…These methods have been widely adopted in biomedical and materials science, with numerous commercial applications. 3 Many advanced applications of controlled polymerization require the covalent linking of the polymer with small molecules (polymer functionalization) 4 or with other macromolecules (polymer grafting). 5…”

mentioning

confidence: 99%

RAFT polymerization by the radical decarboxylation of carboxylic acids

Ayurini

Hooper

2023

Preprint

View full text Add to dashboard Cite

The controlled grafting of polymers from small- and macro-molecular substrates is an essential process for many advanced polymer applications. This usually requires the pre-functionalization of substrates with an appropriate functional group, such as a RAFT agent or ATRP initiator, which requires additional synthetic steps. In this paper, we describe the direct grafting of RAFT polymers from carboxylate containing substrates via photochemical radical decarboxylation. This method utilizes the innate functional groups present in the substrates, and achieves efficient polymer initiation in a single step with excellent control of molecular weight and dispersity.

show abstract

An Industrial History ofRAFTPolymerization

Cited by 7 publications

References 49 publications

RAFT Polymerisation by the Radical Decarboxylation of Carboxylic Acids**

RAFT Polymerisation by the Radical Decarboxylation of Carboxylic Acids**

Expanding the Scope of RAFT Multiblock Copolymer Synthesis Using the Nanoreactor Concept: The Critical Importance of Initiator Hydrophobicity

RAFT polymerization by the radical decarboxylation of carboxylic acids

Contact Info

Product

Resources

About