Synthesis of triblock and multiblock methacrylate polymers and self‐assembly of stimuli responsive triblock polymers

Chin, Stacey M.; He, Hongkun; Konkolewicz, Dominik; Matyjaszewski, Krzysztof

doi:10.1002/pola.27271

Cited by 10 publications

(9 citation statements)

References 71 publications

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“…32 Additional issues include a decrease in chain-end fidelity with increasing the number of blocks. Recently, Cu(0)-mediated radical polymerization [33][34][35][36][37][38] and RAFT polymerization [39][40][41][42][43][44] have demonstrated great potential to produce well-defined, multiblock architectures, in particular by reaching full monomer conversion, thus avoiding tedious, intermediate purification steps.…”

Section: Introductionmentioning

confidence: 99%

Ultrafast RAFT polymerization: multiblock copolymers within minutes

et al. 2015

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The synthesis of multiblock copolymers is often considered as synthetically challenging and time consuming. In this contribution, the development of a remarkably efficient and versatile procedure to access multiblock copolymers via reversible addition-fragmentation chain transfer (RAFT) polymerization is reported. The robustness and versatility of the RAFT process is demonstrated in this report by preparing multiblock copolymers using uncommon experimental conditions. The synthesis of each block was performed in the presence of air and only required 3 minutes to reach >98% monomer conversion. This approach removes the necessity to deoxygenate the solution and permits access to complex copolymer structures in very short time periods. For example, this process allowed the preparation of a heptablock homopolymer with a well-defined architecture in just 21 minutes. We also discuss the limitations inherent to this approach. This strategy is shown to be particularly efficient when blocks with low degrees of polymerization (DP < 20) are targeted. For blocks with higher DPs (DP > 50), the procedure is typically limited to the preparation of di-or triblock copolymers.Functional block copolymers are fascinating architectures with unique properties that render them particularly attractive for applications ranging from medicine, 1,2 materials, 3 energy 4 and nanotechnology. 5,6 The access to such synthetically demanding architectures was greatly facilitated with the advent of controlled/"living" radical polymerization techniques, also known as reversible deactivation radical polymerization (RDRP), 7 such as atom transfer radical polymerization (ATRP), 8,9 nitroxide-mediated radical polymerization (NMP), 10,11 reversible addition-fragmentation chain transfer (RAFT) 12-15 and macromolecular design via interchange of xanthates (MADIX) 16-18 polymerizations. These methods enable the production of well-defined polymeric materials with predetermined molar masses, narrow molar mass distributions, chainend functionality, and they can be coupled with efficient post-polymerization modification strategies (e.g. 'click' chemistry). [19][20][21][22][23][24][25] Despite the relative ease of preparing block copolymers (i.e., di-or triblock copolymers) via RDRP methods in comparison with, for example, ionic living polymerizations, the production of multiblock copolymers still remains a challenging and time consuming task. This is mainly due to the necessity to remove any unreacted monomer before the subsequent block is synthesized, 26-31 as the non-removal of monomer would lead to the synthesis of quasi-block copolymers. 32Additional issues include a decrease in chain-end fidelity with increasing the number of blocks.Recently, Cu(0)-mediated radical polymerization 33-38 and RAFT polymerization 39-44 have demonstrated great potential to produce well-defined, multiblock architectures, in particular by reaching full monomer conversion, thus avoiding tedious, intermediate purification steps.

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Section: Introductionmentioning

confidence: 99%

Ultrafast RAFT polymerization: multiblock copolymers within minutes

et al. 2015

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“…However, as seen in Figure , the dispersity of the polymer at 11.5 h is still relatively high at M w / M n = 1.34, although the molecular weight is in acceptable agreement with the theoretical value (conversion = 60%, M n = 6.5 × 10 4 , M n,th = 5.4 × 10 4 ). This higher dispersity may be attributed to either termination reactions, or branching due to small amounts of divinyl monomer impurities in the OEOMA monomer . An additional limitation of this system was the 33% monomer by volume, making the polymerization less suitable for biological applications.…”

Section: Aqueous Photoatrp and Photoraftmentioning

confidence: 99%

“…This higher dispersity may be attributed to either termination reactions, or branching due to small amounts of divinyl monomer impurities in the OEOMA monomer. [53,89] An additional limitation of this system was the 33% monomer by volume, making the polymerization less suitable for biological applications. In a related study, Haddleton and co-workers [90] performed aqueous polymerization of oligo(ethylene oxide)methyl ether acrylate (OEOA, M n = 480), using 50% by volume water.…”

Section: Photoinduced Atrp In Aqueous Mediamentioning

confidence: 99%

Photochemistry for Well‐Defined Polymers in Aqueous Media: From Fundamentals to Polymer Nanoparticles to Bioconjugates

Burridge

Wright

Page

et al. 2018

Macromol. Rapid Commun.

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This review article highlights recent developments in the field of photochemistry and photochemical reversible deactivation radical polymerization applied to aqueous polymerizations. Photochemistry is a topic of significant interest in the fields of organic, polymer, and materials chemistry because it allows challenging reactions to be performed under mild conditions. Aqueous polymerization is of significant interest because water is an environmentally benign solvent, and the use of water enables complex polymer self-assembly and bioconjugation processes to occur. This review focuses on powerful new developments in photochemical aqueous polymerization reactions and their applications to the synthesis of well-defined polymer nano-objects and bioconjugates. It is anticipated that these aqueous photopolymerizations will enable the next generation of self-assembled structures and biohybrid materials to be developed under mild and environmentally friendly conditions.

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“…[16][17][18][19][20][21][22][23] Owing to these advantages, the groups of Hawker, Matyjaszewski, Boyer, Whittaker, Haddleton, Junkers and Perrier have reported the remarkable synthesis of sequence-controlled multiblocks. 20,[24][25][26][27][28][29][30][31][32][33][34][35][36][37][38] For instance, Whittaker and co-workers first reported the synthesis of high-order multiblocks via iterative Cu(0)-mediated radical polymerization while omitting the need for purification between the iterative block formation steps. 27 Junkers showed that photo-ATRP (atom transfer radical polymerization) could also enable the synthesis of well-defined multiblocks in the absence of dye sensitizers or photoinitiators.…”

Section: Introductionmentioning

confidence: 99%

Concurrent Control over Sequence and Dispersity in Multiblock Copolymers

Antonopoulou¹,

Whitfield²,

Truong³

et al. 2020

Preprint

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Controlling monomer sequence in synthetic macromolecules is a major challenge in polymer science and the order of building blocks has already been demonstrated to determine macromolecular folding, self-assembly and fundamental polymer properties. Dispersity is another key parameter in material design, with both low and high dispersity polymers displaying complementary properties and functions. However, synthetic approaches that can simultaneously control both sequence and dispersity remain experimentally unattainable. Here we report a simple, one pot, and rapid synthesis of sequence-controlled multiblocks with on demand control over dispersity while maintaining high livingness, excellent agreement between theoretical and experimental molecular weights and quantitative yields. Key to our approach is the regulation in chain transfer agent activity during controlled radical polymerization that enables the preparation of multiblocks with gradually ascending (Ɖ=1.16 →1.60), descending (Ɖ=1.66 →1.22), alternating low and high dispersity values (Ɖ=1.17 →1.61 →1.24 →1.70 →1.26) or any combination thereof. The enormous potential of our methodology was further demonstrated through the impressive synthesis of highly ordered pentablock, octablock and decablock copolymers yielding the first generation of multiblocks with concurrent control over both sequence and dispersity.

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Synthesis of triblock and multiblock methacrylate polymers and self‐assembly of stimuli responsive triblock polymers

Cited by 10 publications

References 71 publications

Ultrafast RAFT polymerization: multiblock copolymers within minutes

Ultrafast RAFT polymerization: multiblock copolymers within minutes

Photochemistry for Well‐Defined Polymers in Aqueous Media: From Fundamentals to Polymer Nanoparticles to Bioconjugates

Concurrent Control over Sequence and Dispersity in Multiblock Copolymers

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