Unity Makes Strength: Constructing Polymeric Catalyst for Selective Synthesis of CO
            <sub>2</sub>
            /Epoxide Copolymer

Zhang, Ruoyu; Kuang, Qingxian; Cao, Han; Liu, Shunjie; Chen, Xuesi; Wang, Xianhong

doi:10.31635/ccschem.022.202201952

Cited by 25 publications

(18 citation statements)

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“…The ACCs exhibited a good ability to promote chain initiation and chain transfer in the preparation of AIE-PPC by CO 2 and propylene oxide copolymerization. The aluminum porphyrin complexes have been proven to be one of the few efficient catalysts for the copolymerization of CO 2 and propylene oxide due to the high activity and polymer selectivity derived from the tunable ligand structures. − Moreover, it has excellent proton tolerance for the chain transfer agent, resulting in end-functional PPCs with narrow molecular weight distributions. To realize the regulation of AIE-PPC synthesis and chain structure, aluminum porphyrin complexes with ortho -Cl (CAT-1), meta -Cl (CAT-2), and para -Cl (CAT-3) were selected as the catalysts for copolymerization (detailed synthetic procedures are presented in Scheme S2 and Figures S9–S20), and the results are presented in Table .…”

Section: Resultsmentioning

confidence: 99%

Three-in-One: AIEgen End-Labeling of CO₂ Polymer for Visible Fiber Thermometer

Zhuo

Cheng

et al. 2023

Macromolecules

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Visual temperature sensors are of great significance for environmental management and industrial process control. Herein, we developed a visual sensing approach based on fiber fluorescent imaging by configuring aggregation-induced emission (AIE)-functionalized CO2-based poly(propylene carbonate) (PPC). A three-in-one strategy incorporating AIE (tetraphenylethylene), chain transfer (hydroxyl), and co-catalytic (pyridinium salt) properties into one system is proposed to synthesize AIEgen end-labeled PPC as a thermometer material. Based on the twisted intramolecular charge transfer effect of the AIE unit, the fiber thermometer obtained by melt spinning transforms the invisible temperature gradient information into different fluorescent colors that are visible to the naked eye. In the range of −40 to 140 °C, multiscale temperature visualization applications, such as regional temperature detection, internal one-dimensional (1D) and two-dimensional (2D) temperature mapping, etc., could be implemented at a high resolution (±1 °C, 10 μm).

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Section: Resultsmentioning

confidence: 99%

Three-in-One: AIEgen End-Labeling of CO₂ Polymer for Visible Fiber Thermometer

Zhuo

Cheng

et al. 2023

Macromolecules

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“…38 In addition, the spatial confinement of polymeric catalysts can further promote the aggregation of pendent porphyrin units. 39 More importantly, the electron-withdrawing/donating substituents on the porphyrins affect the π−π interactions, which induce different stacking patterns among the porphyrins. 40,41 Therefore, as shown in Figure 1, the PAPCs with different substituent groups were synthesized via free radical polymerization of methacrylic-based porphyrin, followed by metallization with the low-toxicity metal AlEt 2 Cl (Scheme S1).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Porphyrins were chosen as the building blocks for the construction of polymer catalysts not only because metal porphyrins were the first homogeneous catalysts found to be used in the copolymerization of carbon dioxide and epoxides but also because porphyrin is susceptible to intermolecular aggregation via π–π interactions due to its 18 π-electronic conjugated structure . In addition, the spatial confinement of polymeric catalysts can further promote the aggregation of pendent porphyrin units . More importantly, the electron-withdrawing/donating substituents on the porphyrins affect the π–π interactions, which induce different stacking patterns among the porphyrins. , Therefore, as shown in Figure , the PAPCs with different substituent groups were synthesized via free radical polymerization of methacrylic-based porphyrin, followed by metallization with the low-toxicity metal AlEt 2 Cl (Scheme S1).…”

Section: Resultsmentioning

confidence: 99%

Aggregate Catalysts: Regulating Multimetal Cooperativity for CO₂/Epoxide Copolymerization

Yang,

Liu,

Zhou

et al. 2023

Macromolecules

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Biomimetic aggregates have flourished in various fields, particularly in small-molecule catalysis, but their application in polymer synthesis remains understudied. Herein, we propose a strategy for constructing aggregate catalysts based on aggregationregulating cooperativity to enhance the copolymerization of CO 2 / propylene oxide (PO). The key design strategy involves constructing polymeric aluminum porphyrin catalysts (PAPCs) with varied stacking modes induced by substituents' electronic effects, enabling effective modulation of metal synergism. PAPCs with −Cl and −Br substitution exhibit H-aggregates of porphyrin units, leading to a strong metal synergy effect and stability at high temperatures. The H-aggregate catalysts show high activity (TOF > 10,000 h −1 ) and high selectivity (>98%). Meanwhile, the activity was maintained at a very low catalyst loading ([Al]/PO = 1/ 100,000), with the number-average molecular weight of the resulting copolymer over 480 kg/mol. Contrarily, −CH 3 -and −CH 2 CH 3 -substituted PAPCs display J-aggregates with a weak metal synergy effect (unstable at a high temperature). The Jaggregate catalysts show low activity (TOF < 2500 h −1 ) and polymer selectivity (<90%). The present strategy of designing aggregate catalysts provides a new perspective to regulate metal cooperativity, suitable not only for CO 2 /epoxide or anhydride/epoxide copolymerization but also for lactone ring-opening polymerizations.

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“…As an organic base, DMAEMA could form a Lewis pair interaction with aluminum porphyrin, which was expected to increase the catalytic activity of ROCOP. 42,43 For DMAEMA-assisted one-step synthesis with 5% DMAEMA use (mole ratio of DMAEMA/NIPAM is 5/100), the CHO conversion increased from 12.5% to 24.8% under the same reaction condition (Entry 1 vs. Entry 2 in Table S1).…”

Section: The Catalytic Efficiency Of Rocop In the One-step Processmentioning

confidence: 99%

CO₂‐based amphiphilic block copolymers: Facile one‐step synthesis and aqueous self‐assembly

Wei

Suo

et al. 2023

Journal of Polymer Science

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Construction of CO2‐based amphiphilic block copolymers (ABCs) is an efficient method for providing CO2‐based polycarbonates with self‐assembly properties in aqueous media. It is challenging to construct CO2‐based ABCs by one‐step strategies from mixed monomers because hydrophilic blocks, usually composed of polar monomers, have negative effects on the synthesis of polycarbonates. In this work, we report a one‐step method to construct CO2‐based ABCs obtained by simultaneous ring‐opening copolymerization (ROCOP) of CO2/epoxides and reversible addition‐fragmentation chain transfer (RAFT) polymerization of N‐isopropyl acrylamide (NIPAM). A trithiocarbonate/carboxy compound was used as the bifunctional chain transfer agent, and an aluminum porphyrin complex was used as the catalyst for ROCOP, which proved to be efficient in CO2 copolymerization even in the presence of NIPAM with strong polarity. This strategy allows flexible control over the molecular weight (5–16 kg/mol) and the hydrophilic‐hydrophobic balance (HLB 9–18) of the ABCs, and ensures narrow polydispersity Đ (1.1–1.3) of the polymers. The ABCs can further self‐assemble into micelles in water with controllable diameters and reversible phase transformation behavior with temperature changes from 25 to 40 °C. This simple route to CO2‐based ABCs with multiple functions has large potential in biomedical applications.

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Unity Makes Strength: Constructing Polymeric Catalyst for Selective Synthesis of CO ₂ /Epoxide Copolymer

Cited by 25 publications

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Three-in-One: AIEgen End-Labeling of CO₂ Polymer for Visible Fiber Thermometer

Three-in-One: AIEgen End-Labeling of CO₂ Polymer for Visible Fiber Thermometer

Aggregate Catalysts: Regulating Multimetal Cooperativity for CO₂/Epoxide Copolymerization

CO₂‐based amphiphilic block copolymers: Facile one‐step synthesis and aqueous self‐assembly

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Unity Makes Strength: Constructing Polymeric Catalyst for Selective Synthesis of CO 2 /Epoxide Copolymer

Cited by 25 publications

References 0 publications

Three-in-One: AIEgen End-Labeling of CO2 Polymer for Visible Fiber Thermometer

Three-in-One: AIEgen End-Labeling of CO2 Polymer for Visible Fiber Thermometer

Aggregate Catalysts: Regulating Multimetal Cooperativity for CO2/Epoxide Copolymerization

CO2‐based amphiphilic block copolymers: Facile one‐step synthesis and aqueous self‐assembly

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Product

Resources

About

Unity Makes Strength: Constructing Polymeric Catalyst for Selective Synthesis of CO ₂ /Epoxide Copolymer

Three-in-One: AIEgen End-Labeling of CO₂ Polymer for Visible Fiber Thermometer

Three-in-One: AIEgen End-Labeling of CO₂ Polymer for Visible Fiber Thermometer

Aggregate Catalysts: Regulating Multimetal Cooperativity for CO₂/Epoxide Copolymerization

CO₂‐based amphiphilic block copolymers: Facile one‐step synthesis and aqueous self‐assembly