The copolymerization of carbon monoxide with olefins

Sen, Ayusman

doi:10.1007/3-540-15786-7_8

Cited by 116 publications

(21 citation statements)

References 54 publications

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“…A Pd–diimine complex 1 in combination with the exchanging bipy ligand at an equimolar amount is employed herein as the catalyst system for the coordinative polymerization. For polyketone synthesis by catalytic alkene-CO alternating copolymerization, Pd-based catalysts with bidentate phosphines or bidentate nitrogen ligands are most commonly used. − While the bidentate phosphine-ligated catalysts are more efficient for copolymerization of ethylene or aliphatic α-olefin with carbon monoxide, − the bidentate nitrogen-ligated catalysts are favored for the copolymerization of vinylarene (such as styrene and TBS) with CO. − To date, various bidentate nitrogen ligands have been successfully applied to Pd-catalyzed TBS/CO copolymerization, including 1,10-phenanthroline, bipy, oxazoline, α-diimine, and pyrazole-based bidentate ligands. − …”

Section: Resultsmentioning

confidence: 99%

“…Polyketones synthesized by coordinative alternating copolymerization of olefins with carbon monoxide are valuable, attractive engineering plastics because of their unusual properties, such as high melting point or glass-transition temperature, tunable mechanical properties, biodegradability, the low monomer costs, and the presence of carbonyl functionalities ready for further functionalization. − A large class of linear-structured polyketones has been synthesized, − with some commercialized ones. However, the synthesis of polyketones with complex topologies such as hyperbranched polyketones or star polyketones (SPKs) has been extremely rare, while they are expected to be valuable with desired properties anticipated.…”

Section: Introductionmentioning

confidence: 99%

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One-Pot Synthesis of Hyperbranched and Star Polyketones by Palladium-Catalyzed Terpolymerization of 4-tert-Butylstyrene, Divinylbenzene, and Carbon Monoxide

Zhang

Han

et al. 2019

Macromolecules

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We demonstrate in this article the first synthesis of a class of hyperbranched and star polyketones by Pd-catalyzed terpolymerization of 4-tertbutylstyrene (TBS), divinylbenzene (DVB), and carbon monoxide (CO), where TBS/DVB undergoes alternating copolymerization with CO. Hyperbranched polyketones are first synthesized by direct one-pot terpolymerization, where difunctional DVB monomer serves as the branching agent. A simple variation of the feed ratio of TBS and DVB facilitates the efficient tuning of the branching density in the hyperbranched polymers. The success of the terpolymerization enables the subsequent one-pot synthesis of star polyketones by both "core-first" and "arm-first" strategies. In the "core-first" strategy, multinuclear Pdcontaining hyperbranched cross-linked polyketone cores are first formed by TBS/DVB/CO terpolymerization and serve as multifunctional initiating cores for subsequent multidirectional arm growth upon TBS addition. In the "arm-first" strategy, "living" TBS/CO alternating copolymerization is first carried out to grow linear polyketone arms, followed by the addition of DVB for star formation by cross-linking the linear arms. Tuning the polymerization parameters in both strategies allows the efficient design of star polyketones of varying arm lengths and average arm numbers.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

One-Pot Synthesis of Hyperbranched and Star Polyketones by Palladium-Catalyzed Terpolymerization of 4-tert-Butylstyrene, Divinylbenzene, and Carbon Monoxide

Zhang

Han

et al. 2019

Macromolecules

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“…OH-grafted and alkyl-grafted polyketones were also incorporated into the formulations to tune the mechanical properties of the products. Polyketones were used due to their versatility and straightforward chemical modification with amine-substituted compounds by the Paal-Knorr reaction which is safe and eco-friendly to work with. ,,− Through this approach, we obtained polymer composites that show efficient SHE and SME induced by electricity as well as shape reprogrammability, reprocessability, and tunable properties.…”

Section: Introductionmentioning

confidence: 99%

Electroactive Self-Healing Shape Memory Polymer Composites Based on Diels–Alder Chemistry

Orozco

Kaveh

Santosa

et al. 2021

ACS Appl. Polym. Mater.

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Both shape memory and self-healing polymers have received significant attention from the materials science community. The former, for their application as actuators, selfdeployable structures, and medical devices; and the latter, for extending the lifetime of polymeric products. Both effects can be stimulated by heat, which makes resistive heating a practical approach to trigger these effects. Here we show a conductive polyketone polymer and carbon nanotube composite with crosslinks based on the thermo-reversible furan/maleimide Diels−Alder chemistry. This approach resulted in products with efficient electroactive shape memory effect, shape reprogrammability, and self-healing. They exhibit electroactive shape memory behavior with recovery ratios of about 0.9; requiring less than a minute for shape recovery; electroactive self-healing behavior able to repair microcracks and almost fully recover their mechanical properties; requiring a voltage in the order of tens of volts for both shape memory and self-healing effects. To the best of our knowledge, this is the first report of electroactive self-healing shape memory polymer composites that use covalent reversible Diels−Alder linkages, which yield robust solvent-resistant polymer networks without jeopardizing their reprocessability. These responsive polymers may be ideal for soft robotics and actuators. They are also a step toward sustainable materials by allowing an increased lifetime of use and reprocessability.

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“…Besides, the ketone auxochrome group on the main chain also provides polyketone with excellent photo decomposition property [2]. Currently, research on polyketone are mostly focused on the copolymerization of CO with ethane, styrene and their derivatives [3][4][5][6][7]. In the middle of 1980s, Shell successfully developed Palladium-double phosphorus ligand complexes as catalyst in the copolymerization of CO with ethylene in the presence of a strong acid, which is a breakthrough improvement in this field.…”

Section: Introductionmentioning

confidence: 99%

Copolymerization of polyketones catalyzed by polyacrylonitrile resin-supported palladium acetate

Guo

Wang

2008

Front. Chem. Eng. China

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The crosslinked polyacrylonitrile (PAN) was synthesized by suspension polymerization using acrylonitrile (ANT) and divinylbenzene (DVB). Effects of a variety of conditions on the polymerization of PAN particle size and stiffness were investigated. Polyketone was prepared by the copolymerization of carbon monoxide (CO) and styrene (ST) catalyzed by PAN resin-supported palladium acetate. The resin-supported catalyst and the copolymerization product were characterized by infrared spectroscopy (IR) and Scanning Electron Microscopy (SEM). Effects of the components of a catalytic system and reaction time on the catalytic activity were studied. The reusability of the resin-supported catalyst was also investigated. Results indicated that the resin-supported catalyst has excellent catalytic property. The yield of polyketone was 6.2348 g when using 1 g of resin and 22.4 mg of palladium acetate.

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The copolymerization of carbon monoxide with olefins

Cited by 116 publications

References 54 publications

One-Pot Synthesis of Hyperbranched and Star Polyketones by Palladium-Catalyzed Terpolymerization of 4-tert-Butylstyrene, Divinylbenzene, and Carbon Monoxide

One-Pot Synthesis of Hyperbranched and Star Polyketones by Palladium-Catalyzed Terpolymerization of 4-tert-Butylstyrene, Divinylbenzene, and Carbon Monoxide

Electroactive Self-Healing Shape Memory Polymer Composites Based on Diels–Alder Chemistry

Copolymerization of polyketones catalyzed by polyacrylonitrile resin-supported palladium acetate

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