Highly Ordered Structure Formation in RAFT-Synthesized PtBOS-<i>b</i>-P4VP Diblock Copolymers

Faber, Martin; Hofman, Anton H.; Loos, Katja; Brinke, G. ten

doi:10.1002/marc.201600052

Cited by 9 publications

(14 citation statements)

References 51 publications

(87 reference statements)

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“…Even if one can promote the correct phase (i.e., the phase that corresponds to the equilibrium state at the final concentration and temperature), distortions nearly always occur during self-assembly and growth of BCP crystals, ,− for two essential reasons. First, unlike atomic and molecular crystals, structural building units in periodic BCP are themselves composed of large numbers of highly deformable collections of molecules.…”

Section: Outlook and Future Directionsmentioning

confidence: 99%

Block Copolymers beneath the Surface: Measuring and Modeling Complex Morphology at the Subdomain Scale

et al. 2021

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Block copolymer (BCP) melts are a paradigm for pluripotent molecular assembly, yielding a complex and expanding array of variable domain shapes and symmetries from a fairly simple and highly expandable class of molecular designs. This Perspective addresses recent advances in the ability to model and measure features of domain morphology that go beyond the now canonical metrics of D spacing, space group, and domain topology. Such subdomain features have long been the focus of theories seeking to explain and understand mechanisms of equilibrium structure formation in block copolymer melts, from inhomogeneous curvatures of an intermaterial dividing surface to variable domain thickness. Quantitative metrics of variable subdomain geometry, or packing frustration, are central to theoretical models of complex BCP phase formation, from bicontinuous networks to complex (e.g., Frank–Kasper) crystals, and new experimental methods bring the possibility of their quantitative tests into reach. Here we not only review generic approaches to quantify local domain morphologies that both connect directly to thermodynamic models of BCP assembly but also generalize to domains of arbitrary shape and topology. We then overview experimental methods for characterizing BCP morphology, focusing on recent advances that make accessible detailed and quantitative metrics of fine features of subdomain geometry. Beyond even the critical comparison between detailed predictive models and experimental measurements of complex BCP assembly, validation of these advances lays the foundation to “mold” morphology in BCP assemblies at ever finer subdomain scale, through controlled architectures and processing pathways.

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Section: Outlook and Future Directionsmentioning

confidence: 99%

Block Copolymers beneath the Surface: Measuring and Modeling Complex Morphology at the Subdomain Scale

et al. 2021

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“…available. Evidence suggests that trithiocarbonates, such as S -dodecyl- S ′-(α,α′-dimethyl-α″-acetic acid) trithiocarbonate (aka DDMAT or DIBTTC), in DMF at 70 °C are also very effective CTAs for the control of P4VP in addition to acrylates for BCP synthesis. , The use of 1:1 benzoyl peroxide:CTA was reported to yield narrow Đ (1.11) P2VP after 24 h at 25 °C at ∼40% conversion, providing a lower temperature preparation alternative to these materials . An area of research gaining continuous traction is visible light driven CRP, and recently Xin and co-workers described RAFT of P2VP through blue-light initiation of the DDMAT .…”

Section: Synthesis and Advancementsmentioning

confidence: 99%

Poly(vinylpyridine) Segments in Block Copolymers: Synthesis, Self-Assembly, and Versatility

2019

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This Perspective provides a current survey on the synthesis, self-assembly, and vast variety of applications possible from block copolymer (BCP) systems containing at least one segment of either poly(2-vinylpyridine), P2VP, or poly(4-vinylpyridine), P4VP. Strategies and insight toward P2VP or P4VP as the segment of choice and their influence on material properties, effective interaction parameters, and hosting a variety chemistries from small molecules to nanoparticles are provided. It is with hope that this work serves as a modern field guide to the versatility and utility of these chemistries for those new to or continuing research with these BCP systems.

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“…The complementary polystyrene (PS) and poly(4- tert -butoxystyrene) (P t BOS) blocks with an alkyne functionality are synthesized using reversible addition–fragmentation chain transfer (RAFT) polymerization according to previous literature procedures. 28,30…”

Section: Resultsmentioning

confidence: 99%

Pronounced Surface Effects on the Curie Transition Temperature in Nanoconfined P(VDF-TrFE) Crystals

et al. 2019

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Changes in the Curie transition temperature of nanoconfined poly(vinylidene fluoride–trifluoroethylene) P(VDF-TrFE) copolymers can have a severe impact on the electroactive behavior and the application range of these materials. Therefore, the origin of the change in the Curie transition temperature requires a profound understanding. In this work, block copolymer self-assembly into a spherical morphology proves to be a viable method to effectively confine P(VDF-TrFE) in three dimensions for studying the effect of nanoconfinement on the Curie transition. Using differential scanning calorimetry and wide-angle X-ray scattering, easily accessible experimental techniques, we follow the crystalline phase transitions, showing that confining P(VDF-TrFE) in a nonpolar polystyrene (PS) or poly(4-tert-butoxystyrene) (PtBOS) matrix results in an increase of the Curie transition upon cooling and heating. However, when a more polar matrix is used to nanoconfine P(VDF-TrFE), the Curie transition temperature is drastically reduced due to surface effects.

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Highly Ordered Structure Formation in RAFT-Synthesized PtBOS-b-P4VP Diblock Copolymers

Cited by 9 publications

References 51 publications

Block Copolymers beneath the Surface: Measuring and Modeling Complex Morphology at the Subdomain Scale

Block Copolymers beneath the Surface: Measuring and Modeling Complex Morphology at the Subdomain Scale

Poly(vinylpyridine) Segments in Block Copolymers: Synthesis, Self-Assembly, and Versatility

Pronounced Surface Effects on the Curie Transition Temperature in Nanoconfined P(VDF-TrFE) Crystals

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