Regio-selective synthesis of polyepichlorohydrin diol using Zn–Co(<scp>iii</scp>) double metal cyanide complex

Wei, Ren‐Jian; Zhang, Yingying; Zhang, Xinghong; Du, Binyang; Fan, Zhiqiang

doi:10.1039/c4ra02394c

Cited by 12 publications

(9 citation statements)

References 20 publications

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“…Remarkably, the cyclic carbonate contents in the product were 5.0%-11.3% at 25-60 o C, better than those from homogeneous catalysis [141]. Moreover, the copolymer with 70.7% carbonate content presents high thermal decomposition temperature of 250 o C and relatively high T g of 31.2 o C. Although we observed that Zn-Co(III) DMCC was a regioselective catalyst for ROP of epichlorohydrin on the site of methine group [142], we had no direct evidence for supporting the regioselective CO 2 /epichlorohydrin copolymerization. Terpolymerization of two epoxides with CO 2 could also performed well by Zn-Co(III) DMCC catalyst, affording terpolymers with tunable T g s [143].…”

Section: Structural Effect Of Epoxides On Co 2 /Epoxide Copolymerizationmentioning

confidence: 70%

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: Structural Effect Of Epoxides On Co 2 /Epoxide Copolymerizationmentioning

confidence: 70%

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

Luo

Zhang

et al. 2016

Polymer

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“…DMC is a heterogeneous catalyst with the general structure of M 1 u [M 2 (CN) 6 ] v · x M 1 X w · y L· z H 2 O, where M 1 = Zn, M 2 = Co, Fe. L is an organic complexing agent, such as tert -butyl alcohol, diglyme, or other. , A proposed structure of the DMC catalyst is shown in Scheme …”

Section: Polymerization Of Alkylene Oxides: Methodsmentioning

confidence: 99%

“… a Here, the Zn–OH structure acts as the initiating group. L represents a complexing agent, used during the preparation of the catalyst, e.g., tert -butanol …”

Section: Polymerization Of Alkylene Oxides: Methodsmentioning

confidence: 99%

“…In 2012, Sun et al reported the homopolymerization of epichlorohydrin (ECH) with tri-(2-hydroxyethyl) isocyanurate as an initiator, followed by the use of PECH as chain extender for PU elastomers . Recently, the homopolymerization of racemic ECH, S -ECH, and R -ECH was reinvestigated by Zhang et al Regioregular PECH was obtained with a head-to-tail content exceeding 99%, molecular weights ranging from 900 to 2700 g/mol and PDIs of 1.42 to 1.72. Cyclic or oligomeric byproducts were completely suppressed.…”

Section: Polymerization Of Alkylene Oxides: Methodsmentioning

confidence: 99%

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Polymerization of Ethylene Oxide, Propylene Oxide, and Other Alkylene Oxides: Synthesis, Novel Polymer Architectures, and Bioconjugation

et al. 2015

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The review summarizes current trends and developments in the polymerization of alkylene oxides in the last two decades since 1995, with a particular focus on the most important epoxide monomers ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO). Classical synthetic pathways, i.e., anionic polymerization, coordination polymerization, and cationic polymerization of epoxides (oxiranes), are briefly reviewed. The main focus of the review lies on more recent and in some cases metal-free methods for epoxide polymerization, i.e., the activated monomer strategy, the use of organocatalysts, such as N-heterocyclic carbenes (NHCs) and N-heterocyclic olefins (NHOs) as well as phosphazene bases. In addition, the commercially relevant double-metal cyanide (DMC) catalyst systems are discussed. Besides the synthetic progress, new types of multifunctional linear PEG (mf-PEG) and PPO structures accessible by copolymerization of EO or PO with functional epoxide comonomers are presented as well as complex branched, hyperbranched, and dendrimer like polyethers. Amphiphilic block copolymers based on PEO and PPO (Poloxamers and Pluronics) and advances in the area of PEGylation as the most important bioconjugation strategy are also summarized. With the ever growing toolbox for epoxide polymerization, a "polyether universe" may be envisaged that in its structural diversity parallels the immense variety of structural options available for polymers based on vinyl monomers with a purely carbon-based backbone.

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“…Despite of the possibility of preparing high molar mass and often stereoregular (co)polymers of ECH, catalytic ROP of ECH suffers from some difficulties in controlling the molar mass and chain-end functionality. Also, in some instances, incomplete monomer conversion was observed. − ,, The catalytic regioselective polymerization of ECH using a Zn-Co(III) double metal cyanide complex, which favors formation predominantly of PECH diols, albeit low molar masses ( M n < 3500 g mol –1 ) and relatively high dispersity (Đ > 1.5) with semi-crystalline properties (solid–liquid transition around 100 °C), was reported recently …”

Section: Introductionmentioning

confidence: 96%

Chlorinated Solvent-Free Living Cationic Ring-Opening Polymerization of Epichlorohydrin Using BF₃•OEt₂ as Co-Initiator: Toward Perfectly Functionalized Poly(epichlorohydrin) Diols

Timofeev,

Hulnik,

Vasilenko

et al. 2023

ACS Appl. Polym. Mater.

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The cationic ring-opening polymerization of epichlorohydrin co-initiated by BF 3 •Et 2 O has been investigated here. Fast synthesis of pure poly(epichlorohydrin) diols (F n (OH) ≈ 2.0) with controlled molar mass (M n up to 4000 g mol −1 ) and low dispersity (Đ < 1.25) was performed both in toluene and in bulk. An original approach was developed here, consisting of first generating in situ the initiator through the BF 3 •Et 2 O-catalyzed reaction of ECH with water, leading to a mixture of oligomers with better solubility in the reaction medium than conventional initiators previously used. Then, through a second monomer starved-feed step, polymerization proceeds exclusively through the activated monomer mechanism, allowing perfect control of the polymer growth. The developed procedure was successfully upscaled to 100 g of polymer to validate a future industrial production of PECH, as well as its derivative glycidyl azide polymer (GAP), the most important energetic binder for solid propellants. Additionally, a separate study was performed to elucidate the reasons for coloration of the polymer observed in the course of polymerization and/or under storage.

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Regio-selective synthesis of polyepichlorohydrin diol using Zn–Co(iii) double metal cyanide complex

Abstract: This work describes the first regio-selective synthesis of poly(epichlorohydrin) diol via a simple one-pot bulk polymerization with a heterogeneous catalyst.

Cited by 12 publications

References 20 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

Polymerization of Ethylene Oxide, Propylene Oxide, and Other Alkylene Oxides: Synthesis, Novel Polymer Architectures, and Bioconjugation

Chlorinated Solvent-Free Living Cationic Ring-Opening Polymerization of Epichlorohydrin Using BF₃•OEt₂ as Co-Initiator: Toward Perfectly Functionalized Poly(epichlorohydrin) Diols

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Regio-selective synthesis of polyepichlorohydrin diol using Zn–Co(iii) double metal cyanide complex

Abstract: This work describes the first regio-selective synthesis of poly(epichlorohydrin) diol via a simple one-pot bulk polymerization with a heterogeneous catalyst.

Cited by 12 publications

References 20 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

Polymerization of Ethylene Oxide, Propylene Oxide, and Other Alkylene Oxides: Synthesis, Novel Polymer Architectures, and Bioconjugation

Chlorinated Solvent-Free Living Cationic Ring-Opening Polymerization of Epichlorohydrin Using BF3•OEt2 as Co-Initiator: Toward Perfectly Functionalized Poly(epichlorohydrin) Diols

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Chlorinated Solvent-Free Living Cationic Ring-Opening Polymerization of Epichlorohydrin Using BF₃•OEt₂ as Co-Initiator: Toward Perfectly Functionalized Poly(epichlorohydrin) Diols