Blue light-induced iniferter RAFT polymerization in aqueous-alcoholic media as a universal tool for the homopolymerization of various monomer families: kinetic investigations on different scales

Hub, Lara; Koll, Joachim; Radjabian, Maryam; Abetz, Volker

doi:10.1039/d3py00241a

Cited by 10 publications

(7 citation statements)

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“…To synthesize the P4VP– b –PS copolymers via the semibatch process, 4VP and DDMAT (20% w / w ) were diluted in the water–ethanol mixture (50:50 w / w ) with a ratio of [DDMAT] 0 /[4VP] 0 = 1:500. The homopolymerization was performed at a light intensity of 49 mW·cm –2 at 70 °C for 6 h, and thus 4 h longer than for PDMA and at elevated temperature, due to the significantly lower propagation rate of 4VP compared to DMA . After 6 h, a 4VP conversion of 61% was obtained (see Figure S13).…”

Section: Resultsmentioning

confidence: 99%

“…Homopolymerizations of DMA and 4VP were conducted as previously reported . The polymerizations were carried out on a 250 mL scale and were terminated upon reaching approximately 50% conversion.…”

Section: Resultsmentioning

confidence: 99%

“…Homopolymerizations of DMA and 4VP were conducted as previously reported. 69 The polymerizations were carried out on a 250 mL scale and were terminated upon reaching approximately 50% conversion. Both PDMA and P4VP macroCTAs were synthesized to achieve a comparable degree of polymerization (N ≈ 200, see Table 1).…”

Section: Resultsmentioning

confidence: 99%

“…Recently, we have shown that a homemade blue LED reactor can be effectively used for the excitation of the 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid (DDMAT) RAFT agent for the visible-lightinduced iniferter homopolymerizations of monomers of different families. 69 Good control of the polymerizations and high robustness in terms of scalability were proved. Compared to the previously investigated homogeneous polymerization systems, conducting the light-induced RAFT polymerization in heterogeneous polymerization systems is more complex.…”

Section: Introductionmentioning

confidence: 93%

“…In addition, for a highly efficient initiation, an LED with a suitable wavelength can be chosen according to the absorption range of the RAFT agent. Recently, we have shown that a homemade blue LED reactor can be effectively used for the excitation of the 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid (DDMAT) RAFT agent for the visible-light-induced iniferter homopolymerizations of monomers of different families . Good control of the polymerizations and high robustness in terms of scalability were proved.…”

Section: Introductionmentioning

confidence: 99%

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Amphiphilic Block Copolymers via Blue-Light-Induced Iniferter RAFT Ab Initio Emulsion Polymerization in Water–Alcoholic Media

Hub,

Koll,

Held

et al. 2024

Macromolecules

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Amphiphilic block copolymers comprise a fascinating class of smart materials due to their unique ability to selforganize, making them attractive candidates for a wide range of applications in materials engineering and medical sciences. The synthesis of these copolymers commonly involves harmful solvents, especially in classical living anionic polymerization. With the development of reversible addition−fragmentation chain transfer (RAFT) and polymerization−induced self-assembly (PISA), an environmentally more friendly and versatile method has been established for the synthesis of such amphiphilic block copolymers. Through the utilization of visible light to initiate polymerization through the so-called photoiniferter process, we emphasize the adaptability of this photopolymerization in different scales although the incident light illuminates only the surface area of the reaction vessels. We describe an easily adjustable, blue-lightinitiated RAFT PISA approach to synthesize a series of amphiphilic poly(N,N-dimethylacrylamide)−block−polystyrene (PDMA−b− PS) and poly(4-vinylpyridine)−block−polystyrene (P4VP−b−PS) diblock copolymers with low molecular weight dispersities. The polymerizations were conducted as both two-step and semibatch processes. Furthermore, the effect of scalability on the polymerization kinetics was investigated, proving the light-induced RAFT polymerization as a scalable polymerization method in a batch process with a reaction volume of up to 500 mL. The bulk morphology of both resulting diblock copolymers having different weight fractions of the minor and major blocks was analyzed. While a cylindrical PDMA microdomain in a PS matrix can be observed at 20−25% by weight of PDMA, the equivalent composition reveals a spherical morphology of P4VP domains in a PS matrix. In essence, the scalable, rather eco-friendly photoinduced synthesis of tailored, nanostructured block copolymers without harmful solvents significantly increases their suitability for applications.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 93%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Amphiphilic Block Copolymers via Blue-Light-Induced Iniferter RAFT Ab Initio Emulsion Polymerization in Water–Alcoholic Media

Hub,

Koll,

Held

et al. 2024

Macromolecules

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Toward Predicting the Formation of Integral‐Asymmetric, Isoporous Diblock Copolymer Membranes

Blagojevic,

Das,

Xie

et al. 2024

Advanced Materials

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The self‐assembly and nonsolvent‐induced phase separation (SNIPS) process of block copolymers and solvents enables the fabrication of integral‐asymmetric, isoporous membranes. An isoporous top layer is formed by evaporation‐induced self‐assembly (EISA) and imparts selectivity for ultrafiltration of functional macromolecules or water purification. This selective layer is supported by a macroporous bottom structure that is formed by nonsolvent‐induced phase separation (NIPS) providing mechanical stability. Thereby the permeability/selectivity tradeoff is optimized. The SNIPS fabrication involves various physical phenomena—e.g., evaporation, self‐assembly, macrophase separation, vitrification – and multiple structural, thermodynamic, kinetic, and process parameters. Optimizing membrane properties and rationally designing fabrication processes is a challenge which particle simulation can significantly contribute to. Using large‐scale particle simulations, it is observed that 1) a small incompatibility between matrix‐forming block of the copolymer and nonsolvent, 2) a glassy arrest that occurs at a smaller polymer concentration, or 3) a higher dynamical contrast between polymer and solvent results in a finer, spongy substructure, whereas the opposite parameter choice gives rise to larger macropores with an elongated shape. These observations are confirmed by comparison to experiments on polystyrene (PS)‐block‐poly(4‐vinylpyridine) (P4VP) diblock copolymer membranes, varying the chemical nature of the coagulant or the temperature of coagulation bath.

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Near‐Infrared Light‐Induced Reversible Deactivation Radical Polymerization: Expanding Frontiers in Photopolymerization

Wu,

Boyer

2023

Advanced Science

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Photoinduced reversible deactivation radical polymerization (photo‐RDRP) or photoinduced controlled/living radical polymerization has emerged as a versatile and powerful technique for preparing functional and advanced polymer materials under mild conditions by harnessing light energy. While UV and visible light (λ = 400–700 nm) are extensively employed in photo‐RDRP, the utilization of near‐infrared (NIR) wavelengths (λ = 700–2500 nm) beyond the visible region remains relatively unexplored. NIR light possesses unique properties, including enhanced light penetration, reduced light scattering, and low biomolecule absorption, thereby providing opportunities for applying photo‐RDRP in the fields of manufacturing and medicine. This comprehensive review categorizes all known NIR light‐induced RDRP (NIR‐RDRP) systems into four mechanism‐based types: mediation by upconversion nanoparticles, mediation by photocatalysts, photothermal conversion, and two‐photon absorption. The distinct photoinitiation pathways associated with each mechanism are discussed. Furthermore, this review highlights the diverse applications of NIR‐RDRP reported to date, including 3D printing, polymer brush fabrication, drug delivery, nanoparticle synthesis, and hydrogel formation. By presenting these applications, the review underscores the exceptional capabilities of NIR‐RDRP and offers guidance for developing high‐performance and versatile photopolymerization systems. Exploiting the unique properties of NIR light unlocks new opportunities for synthesizing functional and advanced polymer materials.

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Blue light-induced iniferter RAFT polymerization in aqueous-alcoholic media as a universal tool for the homopolymerization of various monomer families: kinetic investigations on different scales

Abstract: Photo-iniferter RAFT polymerization offers an opportunity to synthesize polymers without the requirements of external initiators. Blue light-induced iniferter RAFT polymerization was performed in a water-ethanol mixture (50:50 w/w) as an...

Cited by 10 publications

References 54 publications

Amphiphilic Block Copolymers via Blue-Light-Induced Iniferter RAFT Ab Initio Emulsion Polymerization in Water–Alcoholic Media

Amphiphilic Block Copolymers via Blue-Light-Induced Iniferter RAFT Ab Initio Emulsion Polymerization in Water–Alcoholic Media

Toward Predicting the Formation of Integral‐Asymmetric, Isoporous Diblock Copolymer Membranes

Near‐Infrared Light‐Induced Reversible Deactivation Radical Polymerization: Expanding Frontiers in Photopolymerization

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