Poly(3-hexylthiophene) Grains Synthesized by Solvent-Free Oxidative Coupling Polymerization and Their Use as Light-Responsive Liquid Marble Stabilizer

Inoue, Hiroki; Hirai, Tomoyasu; Hanochi, Haruka; Oyama, Keigo; Mayama, Hiroyuki; Nakamura, Yoshinobu; Fujii, Syuji

doi:10.1021/acs.macromol.8b02426

Cited by 25 publications

(16 citation statements)

References 69 publications

(110 reference statements)

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“…After addition of the monomers to the FeCl 3 powder, an exothermic reaction occurred and temperatures increased to 350, 213, and 190 °C from 25 °C for PPy, PMPy, and PEPy systems, indicating progress of the polymerization. The yields after the purification were gravimetrically determined to be 74% (PPy), 56% (PMPy), and 63% (PEPy), which were similar to those reported previously for P3HT 30 and PEDOT 31 synthesized by solvent-free polymerization (67 and 52%). As comparison, the yields of PPy, PMPy, and PEPy synthesized by aqueous chemical oxidative polymerization were gravimetrically determined to be 89%, 47%, and 2%.…”

Section: Resultssupporting

confidence: 86%

“… 28 Huang et al synthesized polyaniline (PANI) by solvent-free mechanochemical oxidative polymerization of anilinium salts using ammonium persulfate. 29 Recently, we succeeded in syntheses of poly(3-hexylthiophene) (P3HT) 30 and poly(3,4-ethylenedioxythiophene) (PEDOT) 31 by solvent-free chemical oxidative polymerization in a one-step and one-pot manner and characterized the size and morphology of the products. PPy and its derivatives are promising and the most studied conjugated polymers; however and surprisingly, there has been no study on solvent-free chemical oxidative polymerization of Py and its derivatives by mechanical mixing to the best of our knowledge.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis of Polypyrrole and Its Derivatives as a Liquid Marble Stabilizer via a Solvent-Free Chemical Oxidative Polymerization Protocol

et al. 2022

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Solvent-free chemical oxidative polymerizations of pyrrole and its derivatives, namely N -methylpyrrole and N -ethylpyrrole, were conducted by mechanical mixing of monomer and solid FeCl 3 oxidant under nitrogen atmosphere. Polymerizations occurred at the surface of the oxidant, and optical and scanning electron microscopy studies confirmed production of atypical grains with diameters of a few tens of micrometers. Fourier transform infrared spectroscopy studies indicated the presence of hydroxy and carbonyl groups which were introduced during the polymerization due to overoxidation. The polymer grains were doped with chloride ions, and the chloride ion dopant could be removed by dedoping using an aqueous solution of sodium hydroxide, which was confirmed by elemental microanalysis and X-ray photoelectron spectroscopy studies. Water contact angle measurements confirmed that the larger the alkyl group on the nitrogen of pyrrole ring the higher the hydrophobicity and that the contact angles increased after dedoping in all cases. The grains before and after dedoping exhibited photothermal properties: the near-infrared laser irradiation induced a rapid temperature increase to greater than 430 °C. Furthermore, dedoped poly( N -ethylpyrrole) grains adsorbed to the air–water interface and could work as an effective liquid marble stabilizer. The resulting liquid marble could move on a planar water surface due to near-infrared laser-induced Marangoni flow and could disintegrate by exposure to acid vapor via redoping of the poly( N -ethylpyrrole) grains.

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Section: Resultssupporting

confidence: 86%

Section: Introductionmentioning

confidence: 99%

Synthesis of Polypyrrole and Its Derivatives as a Liquid Marble Stabilizer via a Solvent-Free Chemical Oxidative Polymerization Protocol

et al. 2022

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“…However, post‐functionalization exhibits poor conversion with many unreacted reaction sites. Aqueous polymerization of water‐soluble monomers is an alternate approach realized through Heck, [ 38,39 ] Sonogashira, [ 40,41 ] Suzuki, [ 42,43 ] and FeCl 3 ‐mediated oxidative [ 44,45 ] polymerizations. These reactions are successful when the active species tolerates the presence of water.…”

Section: Methodsmentioning

confidence: 99%

Aqueous Palladium‐Catalyzed Direct Arylation Polymerization of 2‐Bromothiophene Derivatives

Lin

Sun

Yang

et al. 2020

Macromol. Rapid Commun.

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Conjugated polyelectrolytes have been utilized in applications including chemical/biosensing, [30][31][32] cell imaging, [33][34][35] and disease diagnosis/therapy. [36,37] Their synthesis comprises the preparation of organic-soluble conjugated polymers followed by post-functionalization. A typical post-functionalization reaction is the nucleophilic substitution of an alkyl-bromide with amines to afford ammonium salts, which render the resultant conjugated polyelectrolytes aqueous soluble. However, post-functionalization exhibits poor conversion with many unreacted reaction sites. Aqueous polymerization of water-soluble monomers is an alternate approach realized through Heck, [38,39] Sonogashira, [40,41] Suzuki, [42,43] and FeCl 3 -mediated oxidative [44,45] polymerizations. These reactions are successful when the active species tolerates the presence of water.Reports of aqueous palladium-catalyzed DArP are scarce. [9,46,47] DArP also requires a carbonate base and carboxylic acid additive. Compared to water, carbonate bases display higher Lewis basicities, while carboxylic acids are more acidic. Palladium species preserve the reactivity in the presence of carbonates and carboxylic acids, making them tolerant to water. This study examines the aqueous palladium-catalyzed DArP of 2-bromothiophene derivatives, T1 and T2. The initially selected ligand, triphenylphosphine-3,3′,3″-trisulfonic acid trisodium salt (m-TPPTs), was functional in the DArP; however, its separation from the resultant polymers by dialysis was challenging due to its strong aggregation in water and N,N-dimethylacetamide (DMAc). This was supported by dynamic light scattering (DLS), X-ray crystallography, and gel permeation chromatography (GPC). Thus, pyrimidine-Pd(OAc) 2 was employed in the DArP of T1 to afford PT1 with no ligand (pyrimidine) contamination. Density functional theory (DFT) binding energy calculations revealed that the coordinating ability to palladium was of the order carboxylate > pivalic acid (PivOH) > water, rationalizing the feasibility of executing DArP in water. Finally, the polyelectrolyte molecular-weight overestimation by GPC in water was attributed to the polyelectrolyte effect. Experimental results indicated that the conjugated polyelectrolytes aggregate in DMAc to form a folding structure with the polar groups pointing outwards and conjugated moieties directed inwards, corresponding to a reduced hydrodynamic volume. The polyelectrolyte molecular weight and dispersity (Đ) values determined by GPC in DMAc were, therefore, questionable.

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“…Furthermore, we confirmed that these conjugated polymer grains could adsorb to air‐water surface to stabilize LMs. Thanks to the coating with these conjugated polymer grains as an LM stabilizer, near‐infrared (NIR) light‐to‐heat photothermal properties could be introduced to the LM, and NIR laser irradiation could induce motion of the LM on a planar air‐water surface based on the light‐induced Marangoni propulsion 30,36,37 . Here, local irradiation of the LM with the NIR laser could generate a thermal gradient, and therefore surface tension gradient, around the LM, which could work as a driving force.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of dioctyl sulfosuccinate‐doped polypyrrole grains by aqueous chemical oxidative polymerization and their use as light‐responsive liquid marble stabilizer

Osumi

Seike

Oyama

et al. 2021

J of Applied Polymer Sci

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Polypyrrole grains are synthesized by aqueous chemical oxidative polymerization using ferric chloride as an oxidant in the presence of bis(2‐ethylhexyl) sulfosuccinate sodium salt as both a dopant and a hydrophobizing agent. The resulting grain products are characterized in terms of their size, morphology, surface and bulk chemical compositions, hydrophilicity‐hydrophobicity balance, (photo) thermal property, and electrical conductivity. Scanning electron microscopy studies indicate that the grains are aggregates of atypical primary grains with submicrometer size. Elemental microanalysis and thermogravimetric analysis confirm that the polypyrrole is preferably doped with dioctyl sulfosuccinate compared with chloride ion, and dioctyl sulfosuccinate/chloride ion dopant ratio increases with an increase of bis(2‐ethylhexyl) sulfosuccinate sodium salt concentration in the polymerization systems. The grains show near‐infrared light‐to‐heat photothermal property, which is confirmed by thermography. The data obtained through X‐ray photoelectron spectroscopy indicate the presence of dioctyl sulfosuccinate dopants on the surface of the grains, and therefore the dried polypyrrole grains show hydrophobic character. The dried grains can work as a light‐responsive liquid marble (LM) stabilizer. Motions of the LM can be driven by near‐infrared laser irradiation‐induced Marangoni flow on planar air‐water surface. The release of internal liquid can be achieved by controlled disruption of the LM via external stimulus application.

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Poly(3-hexylthiophene) Grains Synthesized by Solvent-Free Oxidative Coupling Polymerization and Their Use as Light-Responsive Liquid Marble Stabilizer

Cited by 25 publications

References 69 publications

Synthesis of Polypyrrole and Its Derivatives as a Liquid Marble Stabilizer via a Solvent-Free Chemical Oxidative Polymerization Protocol

Synthesis of Polypyrrole and Its Derivatives as a Liquid Marble Stabilizer via a Solvent-Free Chemical Oxidative Polymerization Protocol

Aqueous Palladium‐Catalyzed Direct Arylation Polymerization of 2‐Bromothiophene Derivatives

Synthesis of dioctyl sulfosuccinate‐doped polypyrrole grains by aqueous chemical oxidative polymerization and their use as light‐responsive liquid marble stabilizer

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