Functionalization of carbon nanotubes by surface-initiated immortal alternating polymerization of CO<sub>2</sub>and epoxides

Wang, Yiming; Song, Xiaoyu; Shao, Songhai; Xu, Pengxiang; Ren, Wei‐Min; Lu, Xiao‐Bing

doi:10.1039/c2py20753b

Cited by 17 publications

(9 citation statements)

References 74 publications

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“…2) The copolymerization kinetic is generally controlled by the diffusion of the monomers to the catalyst because the catalyst is soluble in the substrates and the copolymerization occurs in the liquid phase. Thereof, (salen)CoX complexes are deserved to underline again because it presents "immortal" propagation in a well-controlled pathway, in which the "dead" chains can be activated by chain transfer reaction with a protic compound and rapidly re-propagate [94]. Thus, block or grafted copolymers can be synthesized through "immortal" copolymerization by introducing macromolecule chain transfer agents.…”

Section: Homogeneous Catalyst For Co 2 Copolymerizationmentioning

confidence: 99%

Using carbon dioxide and its sulfur analogues as monomers in polymer synthesis

Luo

Zhang

et al. 2016

Polymer

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The alternating copolymerization of one-carbon (C1) building blocks including carbon dioxide (CO 2 ) and its sulfur analogues of carbon disulfide (CS 2 ) and carbonyl sulfide (COS) with epoxides afford new copolymers, namely polycarbonates and polythiocarbonates, with tailored chain structures and properties. This review mainly focuses on the recent advances in C1-involved copolymerization via heterogeneous catalysis of zinc-cobalt(III) double metal cyanide complex [Zn-Co(III) DMCC] catalyst. The chemistry of zinc-hydroxyl bond of Zn-Co(III) DMCC is responsible to the copolymerization of these C1 monomers with epoxides through the formation of C-O (S) bond. The syntheses of CO 2 -based copolymers with various topologies are also reviewed in detail. The utilization of CO 2 , COS and CS 2 as monomers for polymer synthesis have significant contributions to the sustainable use of renewable resources.

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Section: Homogeneous Catalyst For Co 2 Copolymerizationmentioning

confidence: 99%

Using carbon dioxide and its sulfur analogues as monomers in polymer synthesis

Luo

Zhang

et al. 2016

Polymer

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“…Up to now, many attempts, such as terpolymerization with co-monomers [ 16 , 17 , 18 , 19 ], crosslinking [ 20 , 21 , 22 ], and fabrication with other polymers [ 23 , 24 , 25 , 26 , 27 ], inorganic fillers [ 28 , 29 , 30 , 31 , 32 ], or organic compounds [ 33 , 34 , 35 , 36 ] have been carried out to improve the thermal and mechanical properties. In addition, PPC-inorganic hybrid materials like PPC grafted multi-walled carbon nanotubes were prepared [ 37 ]. In fact, several efficient strategies have been achieved.…”

Section: Introductionmentioning

confidence: 99%

Enhanced Poly(Propylene Carbonate) with Thermoplastic Networks: A One-Pot Synthesis from Carbon Dioxide, Propylene Oxide, and a Carboxylic Dianhydride

et al. 2018

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Thermally and mechanically enhanced poly(propylene carbonate) (PPC) with networks was prepared by adding a cyclic carboxylic dianhydride, bicyclo(2,2,2)oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (BTCDA), in the CO2/propylene oxide (PO) copolymerization. The obtained copolymers were characterized by FT-IR, 1H NMR, DSC, and TGA. The gel, melt flow rate, hot-set elongation, and tensile properties were also measured. The formation of networks was confirmed by the presence of gel and the shape recovery after the hot-set elongation test. The minimum permanent deformation of the copolymer is 3.8% and that of PPC is 4539% higher than this value. The results show that BTCDA units are inserted into the backbone of PPC, and the PPC chains are connected successfully owing to cyclic multifunctional anhydride groups in BTCDA. With increasing feed molar ratio of BTCDA to PO from 1 to 4%, the yield strength of copolymers increases from 18.1 to 37.4 MPa compared to 12.9 MPa of PPC. The 5% weight-loss degradation temperatures and maximum weight-loss degradation temperatures greatly increase up to 276.4 and 294.7 °C, respectively, which are 58.6 °C and 55.1 °C higher than those of PPC. These enhanced properties originate from the formation of crosslinks by the rigid and bulky multifunctional dianhydride.

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“…Two state-of-the-art catalyst systems, (BDI)ZnOAc (BDI = β-diiminate) 1 and SalenCoTFA/PPN-TFA (TFA = trifluoroacetate, 1/1 molar ratio) 2 , were selected for this study, since their detailed mechanism studies and the controlled polymerization behavior for epoxide/CO 2 coupling reaction are well established (Figure ). ,− Several α,ω-dihydroxy end-capped polymers, i.e., PEG, PPG, PS-OH, and PNIPAM, were used with varied molecular weight and additional amount to gain access to their influence on the reaction activity and blocking efficiency, and each macro-CTA displays unimodality with quite narrow polydispersity (PDI < 1.05).…”

Section: Resultsmentioning

confidence: 99%

Synthesis of CO₂-Based Block Copolymers via Chain Transfer Polymerization Using Macroinitiators: Activity, Blocking Efficiency, and Nanostructure

et al. 2018

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Immortal copolymerization of epoxides/CO2 using macro-chain-transfer agent (macro-CTA) is a useful method to prepare CO2-based block copolymers for manufacturing high value-added materials. Despite a variety of CO2-based block copolymers that have been reported using distinct macro-CTAs, issues including catalytic activity and blocking efficiency for the immortal polymerization remain superficially understood. Here, we systematically studied the reaction activity and blocking efficiency by using various macro-CTAs (including PPG, PEG, and PS) in the presence of two classical catalyst systems ((BDI)ZnOAc and SalenCoTFA/PPN-TFA). By analysis of the gel permeation chromatograms via mathematical deconvolution, it comes to a conclusion that the size, nature, and ratio of [macro-CTA]/[Cat.] strongly influence the catalytic activity of the reaction and blocking efficiency for the resultant block copolymers. Thin film self-assembly of PS/PPC block copolymers was investigated, and the results were analyzed by SEM to ascertain the impact of blocking efficiency on nanoassembly.

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Functionalization of carbon nanotubes by surface-initiated immortal alternating polymerization of CO₂and epoxides

Cited by 17 publications

References 74 publications

Using carbon dioxide and its sulfur analogues as monomers in polymer synthesis

Using carbon dioxide and its sulfur analogues as monomers in polymer synthesis

Enhanced Poly(Propylene Carbonate) with Thermoplastic Networks: A One-Pot Synthesis from Carbon Dioxide, Propylene Oxide, and a Carboxylic Dianhydride

Synthesis of CO₂-Based Block Copolymers via Chain Transfer Polymerization Using Macroinitiators: Activity, Blocking Efficiency, and Nanostructure

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Functionalization of carbon nanotubes by surface-initiated immortal alternating polymerization of CO2and epoxides

Cited by 17 publications

References 74 publications

Using carbon dioxide and its sulfur analogues as monomers in polymer synthesis

Using carbon dioxide and its sulfur analogues as monomers in polymer synthesis

Enhanced Poly(Propylene Carbonate) with Thermoplastic Networks: A One-Pot Synthesis from Carbon Dioxide, Propylene Oxide, and a Carboxylic Dianhydride

Synthesis of CO2-Based Block Copolymers via Chain Transfer Polymerization Using Macroinitiators: Activity, Blocking Efficiency, and Nanostructure

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Functionalization of carbon nanotubes by surface-initiated immortal alternating polymerization of CO₂and epoxides

Synthesis of CO₂-Based Block Copolymers via Chain Transfer Polymerization Using Macroinitiators: Activity, Blocking Efficiency, and Nanostructure