Semi-conducting cyclic copolymers of acetylene and propyne

Miao, Zhihui; Esper, Alec; Nadif, Soufiane S.; Gonsales, Stella A.; Sumerlin, Brent S.; Veige, Adam S.

doi:10.1016/j.reactfunctpolym.2021.105088

Cited by 14 publications

(12 citation statements)

References 38 publications

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“…On the other hand, C 3 H 4 that can be manufactured from the catalytic or thermal pyrolysis of C 3 H 6 is also a fundamental material for speciality fuel and chemical intermediates. 3 To recover C 3 H 4 , solvent extraction is the current dominant technology, which is not only energy intensive but also associated with pollution. Thus, it is of urgent importance to develop new technologies for efficient C 3 H 4 /C 3 H 6 separation.…”

Section: Introductionmentioning

confidence: 99%

Insights into the thermodynamic–kinetic synergistic separation of propyne/propylene in anion pillared cage MOFs with entropy–enthalpy balanced adsorption sites

et al. 2023

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Section: Introductionmentioning

confidence: 99%

Insights into the thermodynamic–kinetic synergistic separation of propyne/propylene in anion pillared cage MOFs with entropy–enthalpy balanced adsorption sites

et al. 2023

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“…On the other hand, C 3 H 4 that can be produced by thermal or catalytic pyrolysis of C 3 H 6 is also an important feedstock used as speciality fuel and chemical intermediate. [3] To recover C 3 H 4 , solvent extraction is the current state-of-the-art technology, which is associated with pollution. Therefore, it is significant and imperative to develop new approaches to efficiently separate C 3 H 4 /C 3 H 6 .…”

Section: Introductionmentioning

confidence: 99%

Comprehensive Pore Tuning in an Ultrastable Fluorinated Anion Cross‐Linked Cage‐Like MOF for Simultaneous Benchmark Propyne Recovery and Propylene Purification

Jiang

Wang

et al. 2022

Angewandte Chemie

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Propyne/propylene (C3H4/C3H6) separation is an important but challenging industrial process to produce polymer‐grade C3H6 and recover high‐purity C3H4. Herein, we report an ultrastable TiF62− anion cross‐linked metal–organic framework (ZNU‐2) with precisely controlled pore size, shape and functionality for benchmark C3H4 storage (3.9/7.7 mmol g−1 at 0.01/1.0 bar and 298 K) and record high C3H4/C3H6 (10/90) separation potential (31.0 mol kg−1). The remarkable C3H4/C3H6 (1/99, 10/90, 50/50) separation performance was fully demonstrated by simulated and experimental breakthroughs under various conditions with excellent recyclability and high productivity (42 mol kg−1) of polymer‐grade C3H6 from a 1/99 C3H4/C3H6 mixture. A modelling study revealed that the symmetrical spatial distribution of six TiF62− on the icosahedral cage surface provides two distinct binding sites for C3H4 adsorption: one serves as a tailored single C3H4 molecule trap and the other boosts C3H4 accommodation by cooperative host–guest and guest–guest interactions.

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“…This strategy has been pioneered by Veige and co-workers utilizing a high-valent [W VI ] catalyst and a variety of terminal alkynes. [22][23][24][25][26][27][28][29] Likewise, Maeda and co-workers have also reported cyclic polyalkynes of tolanes invoking Nb, [30] Ta, [31] and W [32] alkyne adducts. More recently, we have identified [V V ] alkylidynes (Scheme 1, A) [33][34] as pre-catalysts for the cyclic polymerization of phenylacetylene (cyclic-PPA, B).…”

mentioning

confidence: 99%

Metallacyclobuta‐(2,3)‐diene: A Bidentate Ligand for Stream‐line Synthesis of First Row Transition Metal Catalysts for Cyclic Polymerization of Phenylacetylene

Russell,

Konar,

Keller

et al. 2024

Angew Chem Int Ed

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Described here is a direct entry to two the first examples of 3d transition metal catalysts that are active for the cyclic polymerization of phenylacetylene, namely, [(BDI)M{k2‐C,C‐(Me3SiC3SiMe3)}] (2‐M) (BDI = [ArNC(CH3)]2CH−, Ar = 2,6‐iPr2C6H3; M = Ti, V). Catalysts are prepared in one step by the treatment of [(BDI)MCl2] with 1,3‐dilithioallene [Li2(Me3SiC3SiMe3)]. Complexes 2‐M have been spectroscopically and structurally characterized and the polymers that are catalytically formed from phenylacetylene were verified to have a cyclic topology based on a combination of size‐exclusion chromatography (SEC) and intrinsic viscosity studies. Two‐electron oxidation of 2‐V with nitrous oxide cleanly yields a [VV] alkylidene‐alkynyl oxo complex [(BDI)V(=O){k1‐C‐(=C(SiMe3)CC(SiMe3))}] (3), which lends support for how this scaffold in 2‐M might be operating in the polymerization of the terminal alkyne. This work demonstrates how alkylidynes can be circumvented using 1,3‐dianionic allene as a segue into M–C multiple bonds.

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Semi-conducting cyclic copolymers of acetylene and propyne

Cited by 14 publications

References 38 publications

Insights into the thermodynamic–kinetic synergistic separation of propyne/propylene in anion pillared cage MOFs with entropy–enthalpy balanced adsorption sites

Insights into the thermodynamic–kinetic synergistic separation of propyne/propylene in anion pillared cage MOFs with entropy–enthalpy balanced adsorption sites

Comprehensive Pore Tuning in an Ultrastable Fluorinated Anion Cross‐Linked Cage‐Like MOF for Simultaneous Benchmark Propyne Recovery and Propylene Purification

Metallacyclobuta‐(2,3)‐diene: A Bidentate Ligand for Stream‐line Synthesis of First Row Transition Metal Catalysts for Cyclic Polymerization of Phenylacetylene

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