Self-switchable polymerization catalysis with monomer mixtures: using a metal-free commercial thiourea catalyst to deliver block polyesters

Article Chemistry, Multidisciplinary

One-Pot Precision Synthesis of AB, ABA and ABC Block Copolymers via Switchable Catalysis

Zhenjie Yang et al.

Summary: Switchable catalysis has been developed and applied in the one-pot selective copolymerization from complex mixtures, leading to the synthesis of multi-block copolymers with structural diversity and functionality.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2022)

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Article Chemistry, Multidisciplinary

Switchable Polymerization Organocatalysis: From Monomer Mixtures to Block Copolymers

Jiadong Tang et al.

Summary: We have achieved the one-pot production of sequence-controlled block copolymer from mixed monomers using a switchable catalyst. The method allows for chemoselective and efficient polymerization reactions, resulting in a high conversion rate of CO2.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2022)

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Article Polymer Science

Construction of triblock copolyesters via one-step switchable terpolymerization of epoxides, phthalic anhydride and ε-caprolactone using dual urea/organic base catalysts

Limiao Lin et al.

Summary: Triblock copolyesters were successfully synthesized through a switchable terpolymerization of mixed monomers of epoxides, phthalic anhydride, and epsilon-caprolactone using cost-effective dual urea/organic base catalysts in this study. The catalytic activity and switchable selectivity were optimized by evaluating different combinations of urea/organic base pairs. The obtained copolyesters showed diverse sequence structures and the switchable mechanism of the reaction cycles was investigated through in situ analysis.

POLYMER CHEMISTRY (2022)

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Article Multidisciplinary Sciences

One-step synthesis of sequence-controlled multiblock polymers with up to 11 segments from monomer mixture

Xiaochao Xia et al.

Summary: In this study, a self-switchable polymerization method using alkali metal carboxylate catalysts is reported for the direct synthesis of multiblock polymers with multiple segments. The method allows the production of polymers with complex sequences and structures, offering potential opportunities for material design.

NATURE COMMUNICATIONS (2022)

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Review Chemistry, Multidisciplinary

Heterocycle/Heteroallene Ring-Opening Copolymerization: Selective Catalysis Delivering Alternating Copolymers

Alex J. Plajer et al.

Summary: Heteroatom-containing polymers have potential as sustainable replacements for petrochemicals, offering a wide range of properties for various applications. Catalysed ring-opening copolymerisation (ROCOP) provides a route to create precise new polymer structures, leading to a renaissance in research and commercial products.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2022)

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Article Chemistry, Multidisciplinary

Electrochemically Controlled Switchable Copolymerization of Lactide, Carbon Dioxide, and Epoxides

Yuezhou Huang et al.

Summary: This paper presents an electrochemically switchable strategy for copolymerization using heterometallic complexes, allowing control over the composition and properties of multi-block copolymers. The strategy enables the synthesis of polymers with different functionalities.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2022)

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Article Polymer Science

Self-Switchable Polymerization: A Smart Approach to Sequence-Controlled Degradable Copolymers

Chenyang Hu et al.

Summary: Degradable polymers are attractive alternatives for sustainable development. Self-switchable polymerization offers a method for the synthesis of controlled sequence copolymers with improved properties.

MACROMOLECULES (2022)

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Article Chemistry, Multidisciplinary

Multidimensional Control of Repeating Unit/Sequence/Topology for One-Step Synthesis of Block Polymers from Monomer Mixtures

Xiaochao Xia et al.

Summary: The self-switchable alternating copolymerization allows synchronous and thorough adjustment of the chemical structure difference between two blocks of the diblock copolymer, enabling precise synthesis. The reactivity ratio of the comonomers was investigated, establishing a reactivity gradient.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2022)

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Article Chemistry, Multidisciplinary

Sequence-Reversible Construction of Oxygen-Rich Block Copolymers from Epoxide Mixtures by Organoboron Catalysts

Yao-Yao Zhang et al.

Summary: This study reports a simple method to synthesize well-defined polyether-block-polycarbonate copolymers through switchable catalysis from mixtures of epoxides. This approach has a broad substrate scope and allows for the controlled construction of oxygen-rich polymers.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2022)

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Review Chemistry, Physical

Multifunctional Catalysts for Ring-Opening Copolymerizations

Claire A. L. Lidston et al.

Summary: The ring-opening copolymerization (ROCOP) of epoxides with CO2 or cyclic anhydrides using multifunctional catalysts has been explored as a versatile route for synthesizing a wide range of polycarbonate and polyester copolymers. Covalently tethering the Lewis acid catalyst and cocatalyst together has been shown to increase both catalyst activity and selectivity in epoxide ROCOP. This review examines the development of multifunctional catalysts for copolymerization of epoxides with CO2, cyclic anhydrides, carbonyl sulfide (COS), and cyclic thioanhydrides, and evaluates how the mechanisms of these catalysts lead to improved activity and selectivity in ROCOP.

ACS CATALYSIS (2022)

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Article Polymer Science

A Potential Alternative to Polystyrene: Ring-opening Terpolymerization of Different Epoxides with Phthalic Anhydride Using Metal-free Dual Catalysts

Li-Miao Lin et al.

Summary: A series of semi-aromatic polyesters named as Poly(PO-CHO-PA) were synthesized using an economical catalyst combination, showing superior thermal stability and mechanical properties. These polyesters have potential as packaging materials due to their colorless, transparent nature and low gas permeability.

CHINESE JOURNAL OF POLYMER SCIENCE (2021)

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Article Polymer Science

A Lewis Pair as Organocatalyst for One-Pot Synthesis of Block Copolymers from a Mixture of Epoxide, Anhydride, and CO2

Jinbo Zhang et al.

Summary: The ROCOP of epoxide/anhydride/CO2 is a promising process using CO2 as a renewable resource. However, the synthesis of block copolymers from mixed monomers through a one-pot polymerization remains a great challenge. This study successfully synthesized CO2-based block copolymers using an organocatalyst, presenting a potential direction for future research.

MACROMOLECULES (2021)

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Article Chemistry, Multidisciplinary

Monomer Controlled Switchable Copolymerization: A Feasible Route for the Functionalization of Poly(lactide)

Yuezhou Huang et al.

Summary: A new polymerization route based on reversible CO2 insertion and chemoselective ring opening copolymerization has been developed, allowing for the preparation of multi-block polyesters and potential wider applications.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2021)

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Article Chemistry, Multidisciplinary

ABC and ABAB Block Copolymers by Electrochemically Controlled Ring-Opening Polymerization

Zachary C. Hern et al.

Summary: An electrochemical-controlled synthesis of multiblock copolymers was achieved by altering the redox states of a specific catalyst. Various multiblock copolymers, including tetrablock and triblock copolymers, were successfully prepared with moderately narrow molecular weight distributions using this technique.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

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Review Chemistry, Multidisciplinary

Aliphatic Polycarbonates from Cyclic Carbonate Monomers and Their Application as Biomaterials

Wei Yu et al.

Summary: Aliphatic polycarbonates are gaining attention as biomaterials due to their biocompatibility and tunable degradation, with the ability to introduce functional handles through careful design of cyclic carbonate monomers. These materials have been widely explored for a variety of biomedical applications, from drug delivery to tissue regeneration and vascular graft design, showing great potential for therapeutic use in vitro and in vivo.

CHEMICAL REVIEWS (2021)

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Article Polymer Science

Triethylborane-Assisted Synthesis of Random and Block Poly(estercarbonate)s through One-Pot Terpolymerization of Epoxides, CO2, and Cyclic Anhydrides

Vamshi K. Chidara et al.

Summary: Poly(ester-carbonate) copolymers were synthesized by one-pot copolymerization of epoxides with anhydrides and CO2 activated by triethylborane (TEB). The feeding ratio of anhydrides to epoxides determined the structure of the copolymers, with random and tapered ester structures observed. Terpolymerizations and block copolymerizations were compared in terms of the obtained copolymers' structures and properties.

MACROMOLECULES (2021)

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Article Multidisciplinary Sciences

Diblock dialternating terpolymers by one-step/one-pot highly selective organocatalytic multimonomer polymerization

Jiaxi Xu et al.

Summary: The study demonstrates that the one-pot ring-opening terpolymerization using tert-butylimino-tris(dimethylamino)phosphorene as a catalyst can produce perfectly alternating diblock terpolymers with highly controllable molecular weights and narrow molecular weight distributions.

NATURE COMMUNICATIONS (2021)

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Article Polymer Science

Organocatalytic Ring-Opening Alternating Copolymerization of Epoxides and Cyclic Anhydrides by a Simple Organobase/Urea Binary Catalyst

Xingji Zhu et al.

Summary: In this research, an organic cyclic trimeric phosphazene base (CTPB) in combination with different ureas was utilized as a binary catalyst, showing high catalytic activities in the ring-opening alternating copolymerization (ROAC) of epoxides and cyclic anhydrides. The resulting polyesters exhibited diverse structures, well-defined chain-ends, and low dispersities.

MACROMOLECULAR CHEMISTRY AND PHYSICS (2021)

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Article Chemistry, Physical

Smart Access to Sequentially and Architecturally Controlled Block Polymers via a Simple Catalytic Polymerization System

Xiaochao Xia et al.

Summary: This study introduces a simple, inexpensive, and environmentally friendly polymerization method using alkali metal carboxylate catalysts to achieve sequence-controlled multiblock polyesters. The polymerization system shows high effectiveness and versatility for various monomer combinations, allowing for the preparation of complex block copolymers with potential industrial applications.

ACS CATALYSIS (2021)

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Review Chemistry, Multidisciplinary

Sequence Control from Mixtures: Switchable Polymerization Catalysis and Future Materials Applications

Arron C. Deacy et al.

Summary: The article discusses an efficient and broadly applicable method for producing copolymers using switchable polymerization catalysis, which utilizes a single catalyst switched between different catalytic cycles to prepare block sequence selective copolymers from monomer mixtures. It presents the principles of this catalysis, catalyst design criteria, selectivity and structural copolymer characterization tools, as well as the properties of resulting copolymers.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

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Article Polymer Science

Constructing ABA- and ABCBA-Type Multiblock Copolyesters with Structural Diversity by Organocatalytic Self-Switchable Copolymerization

Chen Li et al.

Summary: The self-switchable pathway for the copolymerization of epoxides, cyclic anhydrides, and cyclic esters has been shown to be effective in producing well-defined copolymers with structural diversity and functionality. Through optimization of the organocatalyst and kinetic studies, a sequence-defined triblock copolymer was successfully synthesized, demonstrating excellent chemoselectivity in terpolymerization. The newly established pathway showed broad monomer adaptability and allowed for the one-step synthesis of complex pentablock copolyesters.

MACROMOLECULES (2021)

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Article Chemistry, Multidisciplinary

Performance tailorable terpolymers synthesized from carbon dioxide, phthalic anhydride and propylene oxide using Lewis acid-base dual catalysts

Jiaxin Liang et al.

Summary: The study successfully conducted terpolymerization of carbon dioxide and phthalic anhydride with propylene oxide using metal-free and economical Lewis pairs. Different organic bases coupled with triethyl borane were able to optimize the terpolymer structure and properties. Additionally, the incorporation of phthalic anhydride effectively enhanced the thermal and mechanical properties of the resulting terpolymers.

JOURNAL OF CO2 UTILIZATION (2021)

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Article Chemistry, Multidisciplinary

Switchable Catalysis Improves the Properties of CO2-Derived Polymers: Poly(cyclohexene carbonate-b-ε-decalactone-b-cyclohexene carbonate) Adhesives, Elastomers, and Toughened Plastics

Gregory S. Sulley et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2020)

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Article Chemistry, Inorganic & Nuclear

Bimetallic Cobalt Complex-Mediated Enantioselective Terpolymerizations of Carbon Dioxide, Cyclohexene Oxide, and β-Butyrolactone

Wen-Bing Li et al.

ORGANOMETALLICS (2020)

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Review Polymer Science

Advances in urea and thiourea catalyzed ring opening polymerization: A brief overview

Isha Jain et al.

EUROPEAN POLYMER JOURNAL (2020)

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Article Chemistry, Multidisciplinary

Metal-Free Approach for a One-Pot Construction of Biodegradable Block Copolymers from Epoxides, Phthalic Anhydride, and CO2

Shuxian Ye et al.

ACS SUSTAINABLE CHEMISTRY & ENGINEERING (2020)

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Article Polymer Science

Lewis pair catalyzed highly selective polymerization for the one-step synthesis of AzCy(AB)xCyAz pentablock terpolymers

Shuaishuai Zhu et al.

POLYMER CHEMISTRY (2020)

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Article Polymer Science

One-Pot Synthesis of Diblock Polyesters by Catalytic Terpolymerization of Lactide, Epoxides, and Anhydrides

Yanchuan Zhou et al.

MACROMOLECULES (2019)

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Article Multidisciplinary Sciences

Easy access to oxygenated block polymers via switchable catalysis

Tim Stosser et al.

NATURE COMMUNICATIONS (2019)

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Review Chemistry, Physical

Catalytic Approaches to Monomers for Polymers Based on Renewables

Bernhard M. Stadler et al.

ACS CATALYSIS (2019)

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Article Polymer Science

Progress in metal-free cooperative catalysis for the ring-opening copolymerization of cyclic anhydrides and epoxides

Sreenath Pappuru et al.

EUROPEAN POLYMER JOURNAL (2019)

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Review Chemistry, Multidisciplinary

Biased Lewis Pairs: A General Catalytic Approach to Ether-Ester Block Copolymers with Unlimited Ordering of Sequences

Shan Liu et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2019)

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Article Chemistry, Multidisciplinary

Dual catalysis for the copolymerisation of epoxides and lactones Electronic supplementary information (ESI) available. See DOI: 10.1039/c9cc00493a

Naomi E. Clayman et al.

CHEMICAL COMMUNICATIONS (2019)

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Article Chemistry, Multidisciplinary

Fully alternating sustainable polyesters from epoxides and cyclic anhydrides: economical and metal-free dual catalysis

Limiao Lin et al.

GREEN CHEMISTRY (2019)

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Article Polymer Science

A facile method to prepare high molecular weight bio- renewable poly(.- butyrolactone) using a strong base/ urea binary synergistic catalytic system

Yong Shen et al.

POLYMER CHEMISTRY (2019)

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Article Chemistry, Multidisciplinary

Selective Polymerization Catalysis from Monomer Mixtures: Using a Commercial Cr-Salen Catalyst To Access ABA Block Polyesters

Tim Stoesser et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2018)

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Article Chemistry, Multidisciplinary

Lewis pairs for ring-opening alternating copolymerization of cyclic anhydrides and epoxides

He-Yuan Ji et al.

GREEN CHEMISTRY (2018)

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Article Polymer Science

Organic Ring-Opening Polymerization Catalysts: Reactivity Control by Balancing Acidity

Binhong Lin et al.

MACROMOLECULES (2018)

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Article Polymer Science

CO2 Controlled Catalysis: Switchable Homopolymerization and Copolymerization

Chenyang Hu et al.

MACROMOLECULES (2018)

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Article Chemistry, Multidisciplinary

Switch Catalysis To Deliver Multi-Block Polyesters from Mixtures of Propene Oxide, Lactide, and Phthalic Anhydride

Tim Stoesser et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2018)

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Article Chemistry, Multidisciplinary

One-Step Access to Sequence-Controlled Block Copolymers by Self-Switchable Organocatalytic Multicomponent Polymerization

He-Yuan Ji et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2018)

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Article Polymer Science

Dual Organocatalysts for Highly Active and Selective Synthesis of Linear Poly(gamma-butyrolactone)s with High Molecular Weights

Cheng-Jian Zhang et al.

MACROMOLECULES (2018)

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Article Polymer Science

Alternating copolymerization of epoxides with anhydrides initiated by organic bases

Zdenek Hostalek et al.

EUROPEAN POLYMER JOURNAL (2017)

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Article Chemistry, Multidisciplinary

Chemoselective Polymerizations from Mixtures of Epoxide, Lactone, Anhydride, and Carbon Dioxide

Charles Romain et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2016)

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Article Chemistry, Multidisciplinary

Metal-Free Alternating Copolymerization of CO2 with Epoxides: Fulfilling Green Synthesis and Activity

Dongyue Zhang et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2016)

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Article Materials Science, Characterization & Testing

Novel analytical method for determination of contents of backbone and terminal/branch vinyl acetate groups of poly(ethylene-co-vinyl acetate) using deacetylation reaction

Sung-Seen Choi et al.

POLYMER TESTING (2016)

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Review Chemistry, Multidisciplinary

Artificial switchable catalysts

Victor Blanco et al.

CHEMICAL SOCIETY REVIEWS (2015)

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Article Chemistry, Multidisciplinary

Selective Polymerization Catalysis: Controlling the Metal Chain End Group to Prepare Block Copolyesters

Yunqing Zhu et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2015)

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Article Polymer Science

Influences of a Dizinc Catalyst and Bifunctional Chain Transfer Agents on the Polymer Architecture in the Ring-Opening Polymerization of ε-Caprolactone

Yunqing Zhu et al.

MACROMOLECULES (2015)

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Article Polymer Science

Synthesis and properties of Poly(L-lactide)-Poly(ε-caprolactone) multiblock copolymers by the self-polycondensation of diblock macromonomers

Mitsutoshi Jikei et al.

POLYMER JOURNAL (2015)

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Article Chemistry, Multidisciplinary

Chemoselective Polymerization Control: From Mixed-Monomer Feedstock to Copolymers

Charles Romain et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2014)

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Article Chemistry, Organic

(Thio)urea Organocatalyst Equilibrium Acidities in DMSO

Gergely Jakab et al.

ORGANIC LETTERS (2012)

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Article Polymer Science

Ring-opening polymerization of ε-caprolactone initiated with titanium n-propoxide or titanium phenoxide

J Cayuela et al.

MACROMOLECULES (2006)

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Self-switchable polymerization catalysis with monomer mixtures: using a metal-free commercial thiourea catalyst to deliver block polyesters

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