Morphology control and inducing a curvature on the domain interface by increasing the steric bulk of polymethacrylate in POSS-containing diblock copolymers

Kato, Fuminobu; Sugimoto, Shin-ichiro; Hayakawa, Teruaki

doi:10.1002/pola.28610

Cited by 6 publications

(6 citation statements)

References 34 publications

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“…In addition, the self-complementary hydrogen bonding of adenine groups of PVBA decreases the flexibility of PVBA chain. , Consequently, even at a smaller volume fraction of PVBA, the interface between the PVBA and PS microdomains prefers to be flat rather than a curvature toward PVBA microdomains to accommodate the increased cross-sectional area and the stiffness of PVBA chains. This is consistent with the phase behavior of POSS-containing block copolymers such as poly(methyl methacrylate)- block -poly(polyhedral oligomeric silsesquioxane methacrylate) copolymer (PMMA- b -PMAPOSS), where the lamellar structure was observed even at a volume fraction of flexible PMMA block ( f PMMA ) with 0.78. , …”

Section: Resultssupporting

confidence: 84%

“…This is consistent with the phase behavior of POSS-containing block copolymers such as poly(methyl methacrylate)-block-poly-(polyhedral oligomeric silsesquioxane methacrylate) copolymer (PMMA-b-PMAPOSS), where the lamellar structure was observed even at a volume fraction of flexible PMMA block (f PMMA ) with 0.78. 36,37 When f PS was further increased (0.80), PVBA 6.5k -b-PS 22.5k showed hexagonally packed PVBA cylindrical microdomains, as demonstrated by SAXS profile (Figure 5) whose peaks of The subscript next to each block represents the number-average molecular weight of each block. b Calculated by 1 H NMR.…”

Section: Resultsmentioning

confidence: 91%

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Phase Behavior of Adenine-Containing Block Copolymer

et al. 2018

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Nucleobase-containing polymers have received great attention for their complementary multiple hydrogen bonding between nucleobases. However, their polymerization is difficult due to poor solubility in a solvent. In this study, we successfully synthesized adenine-containing block copolymers, poly(9-(4-vinylbenzyl)adenine)-block-polystyrene (PVBA-b-PS), using reversible addition–fragmentation chain transfer (RAFT) polymerization in polar solvents of dimethyl sulfoxide and N , N-dimethylformamide and characterized them by size exclusion chromatography and nuclear magnetic resonance spectroscopy. We measured the temperature dependence of the Flory–Huggins interaction parameter (χ) between PVBA and PS as χ = 0.3847 + 55.763/T. The χ was very large (∼0.5 at 200 °C). The phase behavior of PVBA-b-PS with various volume fractions of PS block (f PS) was investigated via small-angle X-ray scattering and transmission electron microscopy. With increasing f PS from 0.1 to 0.8, body-centered-cubic spheres of PS, hexagonally packed (HEX) cylinders of PS, lamellae, and HEX cylinders of PVBA were observed. Interestingly, PVBA-b-PS with f PS = 0.75 showed asymmetric lamellar microdomains. We also prepared a thin film of PVBA-b-PS on a substrate as a template for spatial arrangement of gold nanoparticles (AuNPs). When the surface of AuNPs was modified with thymine-containing polymer chains, AuNPs were selectively sequestered into PVBA microdomains through the complementary hydrogen bonding between thymine and adenine units.

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Section: Resultssupporting

confidence: 84%

Section: Resultsmentioning

confidence: 91%

Phase Behavior of Adenine-Containing Block Copolymer

et al. 2018

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“…The so‐called reversible deactivation radical polymerization (RDRP) and living anionic polymerization are the powerful synthetic tools that have been successfully employed to achieve well‐defined POSS based hybrid (co)polymers of different composition and topologies . As an example, Hirai et al successfully polymerized POSS‐MA up to a degree of polymerization (DP) = 29 with a dispersity Ð –1.04 by living anionic polymerization that was successfully chain extended with styrene (S) and methyl methacrylate (MMA), subsequently affording well‐defined block copolymers, which could self‐assemble into hierarchical nanostructures .…”

Section: Introductionmentioning

confidence: 99%

Nitroxide‐mediated radical polymerization of methacryloisobutyl POSS and its block copolymers with poly(n‐acryloylmorpholine)

Ullah

Shah

Hassan

et al. 2020

Journal of Polymer Science

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Nitroxide-mediated radical polymerization (NMP) of the bulky methacryloisobutyl-polyhedral oligomeric silsesquioxane (POSS-MA) is successfully achieved after optimizing reaction conditions such as selection of controlling comonomer, comonomer feed molar ratio, and temperature (10 mol % styrene (S) comonomer at 110 C using the commercially available BlocBuilder as the NMP initiator). The P(POSS-MA-co-S) with a molecular weight of~8000 g/ mol and dispersity Ð-1.2 is afforded under the optimized reaction conditions. The chain-end fidelity is verified by chain extension experiments with N-acryloyl morpholine (ACM) via NMP that produces well-defined amphiphilic hybrid P(POSS-MA-co-S)-b-P(ACM) x block copolymers, where the subscript "x" represents the degree of polymerization of (ACM) block (182 < x < 695). The size exclusion chromatography (SEC) of the as-synthesized samples reveals the presence of some dead P(POSS-MA-co-S) chains that could be removed by a simple purification step. Kinetic investigations reveal a first-order kinetics for the polymerization of ACM using P(POSS-MA-co-S) as the macroinitiator under NMP conditions. The kinetic and SEC data confirms the controlled nature of the NMP of ACM. Being amphiphilic, the formed P(POSS-MA-co-S)-b-P(ACM) x block copolymers self-assembled in aqueous solution as revealed by the fluorescence spectroscopy experiments with pyrene as the probe for determination of the critical micelle concentration and dynamic light scattering studies.

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“…The thermodynamics of all organic electrolytes with salt has been extensively studied in experimental [2][3][4][5][6][7][8][9][10][11][12] and theoretical systems. [13][14][15] Though there have been studies conducted on the electrochemical properties, [16][17][18][19][20] mechanical properties, 21,22 and ordered phases of hybrid inorganic-organic copolymers, [23][24][25][26][27][28][29][30][31][32][33][34] the thermodynamic behavior of inorganicorganic copolymers containing salt has yet to be systematically studied.…”

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confidence: 99%

Structure and Thermodynamics of Hybrid Organic–Inorganic Diblock Copolymers with Salt

et al. 2019

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We examine the phase behavior of a hybrid organic-inorganic diblock copolymer/salt mixtures. The experimental system comprises 1 poly(ethylene oxide)-block-polyhedral oligomeric silsesquioxane (PEO-POSS) mixed with a lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) salt. While the diblock copolymers without salt exhibit classical order-to-disorder transition behavior with increasing temperature, the PEO-POSS/salt mixtures exhibit disorder-to-order transitions with increasing temperature. Analysis of small angle x-ray scattering data from the disordered state using Leibler's Random Phase Approximation enables the determination of an effective Flory-Huggins interaction parameter, χ eff , for the electrolytes. Unlike conventional systems, χ eff increases with increasing temperature. A simple expression is proposed to describe the dependence of χ eff on temperature and salt concentration. This enables calculation of the segregation strength, χ eff N, for both ordered and disordered electrolytes. The composition of the electrolytes is quantified by f EO/LiTFSI , the volume fraction of the salt-containing poly(ethylene oxide)-rich phase. The morphology of electrolytes is presented on a χ eff N versus f EO/LiTFSI phase diagram. Over the values of f EO/LiTFSI studied (0.61-0.91) only two ordered phases were found: lamellae and coexisting lamellae/hexagonally packed cylinders. INTRODUCTION. Solid polymer electrolytes are more electrochemically and thermally stable in comparison to conventional liquid electrolytes for lithium batteries 1. Linear block copolymers, wherein two chemically distinct polymer chains are chemically bonded together, can provide separate ion-conduction channels as well as mechanically rigid, non-conducting channels. The classic

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Morphology control and inducing a curvature on the domain interface by increasing the steric bulk of polymethacrylate in POSS-containing diblock copolymers

Cited by 6 publications

References 34 publications

Phase Behavior of Adenine-Containing Block Copolymer

Phase Behavior of Adenine-Containing Block Copolymer

Nitroxide‐mediated radical polymerization of methacryloisobutyl POSS and its block copolymers with poly(n‐acryloylmorpholine)

Structure and Thermodynamics of Hybrid Organic–Inorganic Diblock Copolymers with Salt

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