Synthesis of highly pure poly(aryleneethnylene)s using palladium supported on calcium carbonate as an eco‐friendly heterogeneous catalyst

Thavornsin, Nopparat; Chamrasboon, Pitchaporn; Kiatmongkolkul, Pongsathorn; Sakthanasait, Ryo; Sukwattanasinitt, Mongkol; Wacharasindhu, Sumrit

doi:10.1002/pola.29419

Cited by 8 publications

(4 citation statements)

References 67 publications

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“…Different from OPV, the phenyl rings are linked by ethynylenes (triple bond) instead of vinylenes (double bond), which makes the oligo( p -phenylene ethynylene) (OPE) molecule adopt a conformation with all phenyl rings in the same plane and along a straight line. In addition, OPE and its derivatives display excellent stability in air with fascinating optoelectronic properties. − Herein, as a further step toward expanding the scope of living CDSA to diverse π-conjugated polymers and obtaining deeper insight into living CDSA of π-conjugated polymers, we report the synthesis of a series of BCPs containing π-conjugated crystalline core-forming OPE segments of different chain lengths and a corona-forming poly( N -isopropylacrylamide) (PNIPAM 47 ) or poly(2-vinylpyridine) (P2VP 56 ) block (OPE 5 - b -PNIPAM 47 , OPE 7 - b -PNIPAM 47 , OPE 9 - b -PNIPAM 47 , and OPE 9 - b -P2VP 56 ; subscripts represent the number of repeat units, Scheme ). We first examined the influence of the structure of the core-forming OPE segment on the self-assembly of OPE-based BCPs in ethanol.…”

Section: Introductionmentioning

confidence: 99%

Uniform Continuous and Segmented Nanofibers Containing a π-Conjugated Oligo(p-phenylene ethynylene) Core via “Living” Crystallization-Driven Self-Assembly: Importance of Oligo(p-phenylene ethynylene) Chain Length

et al. 2020

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π-Conjugated nanofibers of controlled length and composition show promising potential applications from biomedicine to optoelectronics. However, efficient preparation of uniform nanofibers from π-conjugated polymers with precise control over length and composition poses an outstanding challenge. Herein, we report the synthesis of a suite of block copolymers (BCPs) containing πconjugated crystalline oligo(p-phenylene ethynylene) (OPE) segments of different chain lengths and a poly(N-isopropylacrylamide) (PNIPAM) or a poly(2-vinylpyridine) (P2VP) block (OPE 5 -b-PNIPAM 47 , OPE 7 -b-PNIPAM 47 , OPE 9 -b-PNIPAM 47 , and OPE 9 -b-P2VP 56 ; subscripts indicate the number of repeat units). The length of OPE segment significantly affected the self-assembly OPE-based BCPs. OPE 5 -b-PNIPAM 47 chains were molecularly dissolved in ethanol. Although OPE 7 -b-PNIPAM 47 formed fiber-like micelles of uniform width initially, these micelles were not frozen at room temperature (23 °C), leading to the transformation from regular fiber-like micelles to irregular spherical aggregates upon aging for 7 days. Polydisperse fiber-like micelles of uniform width with kinetically frozen morphology at 23 °C were formed for OPE 9 -b-PNIPAM 47 in ethanol by a direct heating−cooling cycle. The results were supported by the observations in dynamic light scattering, UV−vis, and fluorescence measurements, which indicated the resistance of OPE-based micelles toward micelle dissolution increased with the rising of OPE chain length. By the self-seeding approach of living crystallization-driven self-assembly (CDSA), uniform continuous micelles of controlled length (∼40 nm−1.2 μm) consisting of an OPE core and PNIPAM or P2VP shell can be obtained although micelles of OPE 9 -b-PNIPAM 47 and OPE 9 -b-P2VP 56 exhibited different resistance toward micelle dissolution. Significantly, a series of uniform segmented OPE-based fiber-like comicelles and their hybrid nanostructures with excellent length and composition tunability can be achieved by the seeded growth approach of living CDSA. Overall, we provided a facile access to the fabrication of OPE-based nanofibers with precise control over their length and composition along with instructive information about the influence of structure of π-conjugated block on the CDSA of BCPs containing a crystalline π-conjugated segment.

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Section: Introductionmentioning

confidence: 99%

Uniform Continuous and Segmented Nanofibers Containing a π-Conjugated Oligo(p-phenylene ethynylene) Core via “Living” Crystallization-Driven Self-Assembly: Importance of Oligo(p-phenylene ethynylene) Chain Length

et al. 2020

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“…All commercially available chemicals and reagents were bought from Energy Chemical and used directly without further purification. 1,4-Diethynylbenzene and tetrakis(4-bromophenyl)silane were prepared as described in the previous literature. , …”

Section: Methodsmentioning

confidence: 99%

“…1,4-Diethynylbenzene and tetrakis(4-bromophenyl)silane were prepared as described in the previous literature. 23,24 Synthesis of Alkynyl Imine-Containing POPs (AIPOPs). AIPOP-1.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Engineering Functionality in Organic Porous Networks by Multicomponent Polymerization

et al. 2021

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Developing a simple and efficient methodology to engineer functionality of porous materials is highly desirable due to the significant relationship between functionality and applications. Herein, we report alkynyl imine-containing porous organic polymers (AIPOPs) by a one-pot multicomponent polymerization reaction of tetrabromoarene, isonitrile, and diyne. The introduction of alkynyl imine groups in the porous networks imparts the materials functionality and leads to significantly enhanced iodine adsorption capacity in comparison to an alkynyl-linked comparative porous polymer with higher porosity, evidenced by the iodine capture in vapor. By altering the amount of isonitrile, the content of alkynyl imine groups in the networks is varied and their iodine capture performances are tuned with the maximum adsorption capacity of iodine vapor of 4.10 g g–1, which is comparable to or higher than many iodine adsorbents. The mechanism investigation demonstrates that the adsorption is due to chemisorption, that is, electron transfer from electron-rich units (imine, phenyl rings, and triple bonds) in the adsorbents to I2 with the formation of polyiodides and physisorption. These materials can also remove I2 in n-hexane solutions and the process fits well with the Freundlich model. These results indicate their promising potentials as efficient adsorbents for iodine capture in vapor and solutions. This work represents the first example of amorphous functional porous polymers synthesized by multicomponent reactions and thus may pave a new way for developing porous polymers with intriguing functionality and applications based on the present and more multicomponent reactions.

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“…Sonogashira cross-coupling is a widely useful synthetic tool allowing the introduction of an acetylenic moiety in a variety of molecular structures. − Since the seminal work by Sonogashira and Hagihara, the protocol has been largely studied and improved by exploiting the use of inorganic or organic bases under homogeneous or heterogeneous conditions and in the presence of a wide range of reaction media. − …”

Section: Introductionmentioning

confidence: 99%

Biomass Waste-Derived Pd–PiNe Catalyst for the Continuous-Flow Copper-Free Sonogashira Reaction in a CPME–Water Azeotropic Mixture

Ferlin

Valentini

Sciosci

et al. 2021

ACS Sustainable Chem. Eng.

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Herein, we report on the development of a waste minimization/valorization methodology applied to the representative benchmark Sonogashira cross-coupling reaction performed in a continuous-flow reactor, featuring a continuous-flow downstream membrane organic/aqueous separator to recover medium and products with minimal waste. The protocol is based on the use of a biomass waste-derived heterogeneous Pd-based catalyst, which is obtained from the valorization of urban-waste pine needles (PiNe). In a circular economy approach, the PiNe biomass has been proven to be capable of producing an effective active carbon support for Pd nanoparticle immobilization. In addition, the catalyst has been utilized in an azeotropic mixture formed by industrial wastederived cyclopentyl methyl ether (CPME) and water. Thanks to this combination and with the adoption of flow conditions, high yields of final target products could be accessed with high stability and durability of the catalyst. Final isolation of the products has been realized by setting an in-line liquid−liquid separator in flow, which has also allowed CPME recovery with a significant reduction of the waste generated. The protocol has been applied to the representative preparation of eniluracil, a GSK API.

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Synthesis of highly pure poly(aryleneethnylene)s using palladium supported on calcium carbonate as an eco‐friendly heterogeneous catalyst

Cited by 8 publications

References 67 publications

Uniform Continuous and Segmented Nanofibers Containing a π-Conjugated Oligo(p-phenylene ethynylene) Core via “Living” Crystallization-Driven Self-Assembly: Importance of Oligo(p-phenylene ethynylene) Chain Length

Uniform Continuous and Segmented Nanofibers Containing a π-Conjugated Oligo(p-phenylene ethynylene) Core via “Living” Crystallization-Driven Self-Assembly: Importance of Oligo(p-phenylene ethynylene) Chain Length

Engineering Functionality in Organic Porous Networks by Multicomponent Polymerization

Biomass Waste-Derived Pd–PiNe Catalyst for the Continuous-Flow Copper-Free Sonogashira Reaction in a CPME–Water Azeotropic Mixture

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