Simple synthesis of end functionalized regioregular poly(3‐hexyl thiophene) by catalytic‐initiated Kumada catalyst transfer polymerization

Khawas, Koomkoom; Daripa, Soumili; Kumari, Pallavi; Bera, Manas Kumar; Malik, Sudip; Kuila, Biplab Kumar

doi:10.1002/pola.29349

Cited by 12 publications

(24 citation statements)

References 52 publications

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“…Scheme displays the total schematic diagram for the synthesis of rod–coil conjugated block copolymer P3HT‐ b ‐PSSA. To prepare Ni(II) catalytic initiator ( 2 ), 1‐bromo‐4‐(bromomethyl) benzene in toluene was added dropwise to in situ prepared Ni(0)(dppp) 2 ( 1 ) solution (Supporting Information for synthesis of Ni(0)(dppp) 2 ) under argon . The reaction mixture was stirred for 6 h and the transformation from 1 to 2 was indicated by a color change from orange to red wine with the precipitation of excess of dppp (white precipitate).…”

Section: Resultsmentioning

confidence: 99%

“…The synthesis of catalytic initiator and bromobenzyl end‐functionalized P3HT is described in the previous report . In brief, 1‐bromo‐4‐(bromomethyl)benzene, 104 mg (0.412 mmol) and 10 mL toluene were charged in a Schlenk flask containing Ni(dppp) 2 under Argon atmosphere (supporting information) . The reaction mixture was then stirred for 6 h and used as the catalytic initiator.…”

Section: Methodsmentioning

confidence: 99%

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Highly Water‐Soluble Rod–Coil Conjugated Block Copolymer for Efficient Humidity Sensor

Khawas

Daripa

Kumari

et al. 2019

Macro Chemistry & Physics

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In this report, the preparation of highly water‐soluble rod–coil conjugated block copolymer poly(3‐hexylthiophene)‐b‐polystyrenesulfonic acid (P3HT‐b‐PSSA) is demonstrated using a facile method with its moisture sensing properties. The block copolymer synthesis method comprises Kumada catalyst transfer polymerization and atom transfer radical polymerization from a bifunctional initiator followed by sulfonation of polystyrene using moderate reaction conditions. The polymerization results in the synthesis of well‐defined block copolymers with controllable block length. The successful synthesis of the block copolymer is studied by NMR and FTIR spectroscopy while optical and structural properties of the block copolymer are investigated using UV–vis, photoluminescence spectroscopy, XRD, and FESEM. In water, the block copolymer shows aggregated structure with crystalline core formed by rod‐like P3HT chain with absorption maxima at 558 nm, whereas in solid state the absorption maxima is blue shifted to 548 nm. The proton conductivity of the block copolymer P3HT‐b‐PSSA with ≈91% of PSSA (by weight) is measured from impedance study, and the values for bulk and grain conductivities are 5.25 × 10−4 and 4.66 × 10−6 S cm−1, respectively, at room temperature. The as‐synthesized block copolymer shows a very high water uptake with maximum ≈80% in comparison with its initial weight. The I–V measurement of the device made from block copolymer shows nonlinear, rectifying characteristic and the current increases with increase of relative humidity (RH%). The block copolymer device shows well‐correlated systemic and reversible resistance change with RH both in doped and undoped state. It is believed that the interesting and highly reversible moisture‐sensitive electronic properties of this block copolymer will be useful for the fabrication of moisture‐sensitive polymer‐based flexible electronic devices.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Highly Water‐Soluble Rod–Coil Conjugated Block Copolymer for Efficient Humidity Sensor

Khawas

Daripa

Kumari

et al. 2019

Macro Chemistry & Physics

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“…However, it sometimes suffers from the instability of the functional initiators derived from the low ability of the coexistence of functional moieties and Ni species. b) Termination method: [ 10,35–42 ] a method involving the reaction between Ni‐Br chain‐end‐functionalized P3HT and a Grignard‐type terminator having a functional group. This method is simple because Ni‐based functional initiators are unnecessary.…”

Section: Methodsmentioning

confidence: 99%

Direct Synthesis of Chain‐end‐functionalized Poly(3‐hexylthiophene) without Protecting Groups Using a Zincate Complex

Inagaki

Yamamoto

Higashihara

2020

Macromol. Rapid Commun.

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and such a breakthrough allows the synthesis of more complicated block copolymers and branched polymers, such as star and graft copolymers, containing P3HT segments with low Ð M values. [13][14][15][16][17][18][19][20][21][22][23][24] Chain-end-functionalized P3HTs, which can also be easily synthesized by such a living polymerization, have received much attention, because the chain-end moiety itself frequently affects device performances in organic electronics. [25][26][27] In addition, chain-end-functionalized P3HTs are used to prepare quantum dots through the coordination between the functional groups and heavy metals. [28] Such quantum dots improve their dispersibility while maintaining a higher conductivity than using normal nonconjugated dispersants. In addition, the chain ends can be used as reactive sites, when synthesizing block and branched copolymers via a crossover reaction, linking reaction, etc. A summary of the synthesis and utilization of chain-end-functionalized P3HTs has been well reviewed elsewhere. [29] Currently, there are three major methods for chain-end functionalization based on the KCTP: a) Initiation method: [30][31][32][33][34] a method using an initiator having a functional group. Since the initiation reaction in a living polymerization is utilized, the quantitative chain-end functionality (Fn) is guaranteed unless the initiation efficiency is incomplete or chain transfer reactions occur. However, it sometimes suffers from the instability of the functional initiators derived from the low ability of the coexistence of functional moieties and Ni species. b) Termination method: [10,[35][36][37][38][39][40][41][42] a method involving the reaction between Ni-Br chain-end-functionalized P3HT and a Grignard-type terminator having a functional group. This method is simple because Ni-based functional initiators are unnecessary. However, excess amounts of the terminators are required to achieve a high functionality. c) Postfunctionalization method: [43][44][45] a method involving site transformation reactions of α-chain-endor ω-chain-end-functionalized polymers. This method is more generalized because various functional groups can be introduced through the precursory chain ends. However, it requires tedious multistep reactions. Each method has advantages and disadvantages, however, method b has been still widely used because of its straightforward strategy. Even when selecting method b, the Grignard reagents having a high basicity must be used in the KCTP method.

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“…In 2019, Koomkoom Khawas and co-workers reported the catalytic-initiated Kumada catalyst transfer polymerization (KCTP) protocol for the synthesis of aromatic endfunctionalized, defect-free poly(3-hexylthiophene), P3HTs, with controlled molecular weight. 216 Oxidative addition of aromatic bromide to in situ formed Ni(0) complex of diphenylphosphino propane (dppp) 2 , generated Ni(II) catalytic initiators 66, which were used to synthesize a series of end-functionalized P3HTs having different aromatic end groups (Scheme 21). For the synthesis of Ar-terminated P3HTs (Ar-P3HT), four aromatic bromides namely (4-bromophenoxy)(tert-butyl)dimethylsilane 65a, 4-bromobenzyl bromide 65b, 4-bromotoluene 65c and 4bromoanisole 65d were employed.…”

Section: Diblock Copolymers Amentioning

confidence: 99%

Recent developments in the synthesis of regioregular thiophene-based conjugated polymers for electronic and optoelectronic applications using nickel and palladium-based catalytic systems

et al. 2020

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Simple synthesis of end functionalized regioregular poly(3‐hexyl thiophene) by catalytic‐initiated Kumada catalyst transfer polymerization

Abstract: Additional supporting information may be found in the online version of this article.

Cited by 12 publications

References 52 publications

Highly Water‐Soluble Rod–Coil Conjugated Block Copolymer for Efficient Humidity Sensor

Highly Water‐Soluble Rod–Coil Conjugated Block Copolymer for Efficient Humidity Sensor

Direct Synthesis of Chain‐end‐functionalized Poly(3‐hexylthiophene) without Protecting Groups Using a Zincate Complex

Recent developments in the synthesis of regioregular thiophene-based conjugated polymers for electronic and optoelectronic applications using nickel and palladium-based catalytic systems

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