Effect of Molecular Weight on Competitive Self-Assembly of Poly(3-dodecylthiophene)-<i>block</i>-poly(methyl methacrylate) Copolymers

Park, Jicheol; Lee, Kyu Seong; Choi, Chungryong; Kwak, Jongheon; Moon, Hong Chul; Kim, Jin Kon

doi:10.1021/acs.macromol.6b00513

Cited by 15 publications

(15 citation statements)

References 44 publications

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“…Interestingly, P3DDT fibrils are clearly observed in phase contrast AFM images at both thicknesses. The formation of P3DDT fibrils at the film surface is attributed to the fact that the molecular weight of P3DDT block is large for the formation of folding of P3DDT chains. ,, When the hydrophobic P3DDT chains with a large molecular weight maintain the end-on orientation without chain folding up to the air/polymer surface, the coverage of P3DDT chains at the air surface would be small, which results in a large enthalpic penalty. Thus, fibril structures with edge-on orienation capable of covering a large area are preferred near the top of the film surface.…”

Section: Resultsmentioning

confidence: 99%

End-on Chain Orientation of Poly(3-alkylthiophene)s on a Substrate by Microphase Separation of Lamellar Forming Amphiphilic Diblock Copolymer

Lee¹,

Kim²,

Lee³

et al. 2019

Macromolecules

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We obtained the end-on orientation of poly(3-dodecylthiophene) (P3DDT) chains where the main chains are vertically oriented on a substrate by synthesizing poly(3-dodecylthiophene)-block-poly(3-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)methyl thiophene) copolymer (P3DDT-b-P3TEGT) with two different weight fractions of P3DDT block (w P3DDT = 0.48 and 0.65). Both block copolymers showed well-ordered lamellar microdomains in bulk, verified by small-angle X-ray scattering (SAXS). Because of the high incompatibility of the two blocks, P3DDT-b-P3TEGT thin films prepared by spin-coating on a substrate followed by thermally annealing showed parallel oriented lamellar microdomains to the substrate. Hydrophilic P3TEGT microdomains were located at the substrate/polymer interface, while hydrophobic P3DDT microdomains were located at the polymer/air interface. Thus, both P3DDT and P3TEGT backbone chains were oriented perpendicularly to the lamellar layer (namely, film thickness direction), and the end-on orientations of P3DDT and P3TEGT chains were obtained. The hole mobility was measured by fabricating a space-charge-limited current (SCLC) device. P3DDT-b-P3TEGT showed much enhanced mobility compared with the device made of neat P3DDT film with edge-on orientation, indicating that end-on orientation is very effective for improving the hole mobility along the vertical direction.

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Section: Resultsmentioning

confidence: 99%

End-on Chain Orientation of Poly(3-alkylthiophene)s on a Substrate by Microphase Separation of Lamellar Forming Amphiphilic Diblock Copolymer

Lee¹,

Kim²,

Lee³

et al. 2019

Macromolecules

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“…In the case of PDPP- b -PCL, the PDPP block is percolated within the aliphatic PCL block, resulting in high mobility and flexibility. While these examples successfully combine the electrical property of the CP block and the mechanical property of the amorphous polymer block, the synthesis is not trivial as they need two different polymerization methods, which additionally require end-capping, coupling, or post-modification steps for the formation of BCPs. − Moreover, the control of the BCP morphology to form percolated CP structures is often hindered by the strong immiscibility between chemically different blocks, leading to a poor electrical performance. − Meanwhile, regioregular- b -regiosymmetric P3HT copolymers consisting of two semicrystalline blocks are recently reported. , While they exhibit distinct morphological features and tunable electrical properties, their mechanical properties are unknown.…”

Section: Introductionmentioning

confidence: 99%

Regioregular-block-Regiorandom Poly(3-hexylthiophene) Copolymers for Mechanically Robust and High-Performance Thin-Film Transistors

Park¹,

Soo²,

Kim³

et al. 2019

Macromolecules

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In this work, we develop mechanically robust and high-performance organic thin-film transistors (OTFTs) based on poly(3-hexylthiophene) (P3HT) regioblock copolymers (block-P3HTs). These block-P3HTs consist of regioregular (rre) and regiorandom (rra) P3HTs, where the highly crystalline rre block allows efficient charge transport while the amorphous rra block provides mechanical robustness and interdomain connection. To examine the effects of the molecular architecture on the OTFT performance and stretchability, we prepare a series of block-P3HTs having different number-average molecular weight (M n) values of rra blocks (from 0 to 32 kg mol–1) and a fixed M n of rre blocks (11 kg mol–1). Thin films of all of the block-P3HTs exhibit a high charge-carrier mobility due to the formation of well-developed edge-on crystallites from the rre blocks confined within the rra domains, leading to a hole mobility of 1.5 × 10–1 cm2 V–1 s–1, which is superior to that of the rre P3HT homopolymer. In addition, the mechanical toughness of block-P3HT thin films is remarkably enhanced by the rra block. While the rre P3HT homopolymer thin film shows a brittle behavior with an elongation at break of only 0.3%, the elongation at break of the block-P3HT thin films increases by a factor of 100, yielding 30.2% with increasing M n of the rra block, without sacrificing the electrical properties. In particular, a noticeable enhancement of both elongation at break and toughness is observed between M n values of the rra block of 8 and 20 kg mol–1, indicating that the critical molecular weight of rra P3HT plays an important role in determining the mechanical response of the block-P3HT thin films. This study provides guidelines and strategies to improve the mechanical properties of organic electroactive materials without the disruption of optoelectrical properties, which is critical to fabricate high-performance soft electronics.

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“…Recently, Coulembier and coworkers synthesized a new type of P3HT‐ block ‐poly(phthalaldehyde) (P3HT‐ b ‐PPA) based on the CuAAC reaction, in which the PPA segment was formed by anionic cyclo‐polymerization ( M n = 8.90–27.1 kDa, Ð M = 1.26–1.34) . Very recently, Kim and coworkers utilized the CuAAC reaction between α‐alkyne‐chain‐end‐functional P3HT and ω‐azido‐chain‐end‐functional PMMA for the synthesis of poly(3‐dodecylthiophene)‐ block ‐PMMA (P3DDT‐ b ‐PMMA) ( M n = 8.40–27.4 kDa) …”

Section: Synthesis Of P3at‐based Block Copolymers By Combination Of Lmentioning

confidence: 99%

Precise Synthesis of Block and Miktoarm Star‐Branched Polymers Containing Polythiophene Segments with Low Dispersity by Combination of Living Anionic Polymerization and Catalyst‐Transfer Polycondensation Systems

Higashihara

2016

Macro Chemistry & Physics

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In this Talent article, the synthesis of well‐defined block and miktoarm star‐branched polymers is described by the combination of living anionic polymerization (LAP) and Kumada catalyst‐transfer polymerization (KCTP), mostly focusing on poly(3‐alkylthiophene) (P3AT)‐based block copolymers and miktoarm star‐branched polymers. The two synthetic methodologies are introduced as follows: (a) a chain‐extension method using chain‐end‐functional polymers via site transformation reaction, and (b) a linking reaction method between two polymer building blocks. The most promising method (b) can further be divided into four different approaches, (b‐1) direct addition reaction of living anionic polymers with chain‐end‐functional P3HT; (b‐2) “Click” reaction between two chain‐end‐functional polymers; (b‐3) direct coupling reaction of living anionic polymers with chain‐end‐functional P3HT; and (b‐4) ionic bond formation of chain‐end‐functional polymers. Based on the recent progresses in synthetic methodologies, versatile block copolymers and miktoarm star‐branched polymers have been successfully produced, well controlling the molecular weights (MW) and dispersities (ÐM).

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Effect of Molecular Weight on Competitive Self-Assembly of Poly(3-dodecylthiophene)-block-poly(methyl methacrylate) Copolymers

Cited by 15 publications

References 44 publications

End-on Chain Orientation of Poly(3-alkylthiophene)s on a Substrate by Microphase Separation of Lamellar Forming Amphiphilic Diblock Copolymer

End-on Chain Orientation of Poly(3-alkylthiophene)s on a Substrate by Microphase Separation of Lamellar Forming Amphiphilic Diblock Copolymer

Regioregular-block-Regiorandom Poly(3-hexylthiophene) Copolymers for Mechanically Robust and High-Performance Thin-Film Transistors

Precise Synthesis of Block and Miktoarm Star‐Branched Polymers Containing Polythiophene Segments with Low Dispersity by Combination of Living Anionic Polymerization and Catalyst‐Transfer Polycondensation Systems

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