Facilely Recyclable Cu(II) Macrocomplex with Thermoregulated Poly(ionic liquid) Macroligand: Serving as a Highly Efficient Atom Transfer Radical Polymerization Catalyst

Zhang, Bingjie; Yao, Lan; Liu, Xiaodong; Zhang, Lifen; Cheng, Zhenping; Zhu, Xiulin

doi:10.1021/acssuschemeng.6b01961

Cited by 19 publications

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“…Upon increasing T , the mixture becomes homogeneous and the polymerization occurs. Cooling the final solution results in the separation of the polymer from the catalyst/ionic liquid layer . Moreover, in water‐induced phase separable catalysis (WPSC) as little as 10 vol% water was added to induce phase separation between the hydrophilic polymer and the solvents mixture containing the copper complex …”

Section: Removal Of Atrp Catalystsmentioning

confidence: 99%

Atom Transfer Radical Polymerization: Billion Times More Active Catalysts and New Initiation Systems

Ribelli

Lorandi

Fantin

et al. 2018

Macromol. Rapid Commun.

235

184

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polymerizing styrene in the presence of 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) radicals. [10] Later, Wayland et al. used a cobalt(II) porphyrin complex to reversibly trap radical species during the polymerization of acrylate monomers, which showed living features: i) linear increase of polymer MW with monomer conversion, and ii) narrow MWD. [11] These techniques set the basis for the development of nitroxide-mediated polymerization (NMP) [12,13] and organometallic mediated radical polymerization (OMRP). [14][15][16] Within the past three decades, controlled radical polymerization (CRP) has been established as a new field in polymer chemistry, in which exceptional control was achieved over polymer architectures, thus enabling the preparation of commercially relevant polymer-based materials for advanced applications. Following IUPAC recommendations, CRP should be termed as reversible deactivation radical polymerization (RDRP). [17] Besides the aforementioned NMP and OMRP, the most affirmed RDRPs are atom transfer radical polymerization (ATRP) [18][19][20] and reversible additionfragmentation chain transfer (RAFT) polymerization. [21] RDRP ensures comparable degree of control as living ionic polymerization, while retaining the versatility and the scope of conventional radical polymerization. The fraction of terminated chains in RDRP is small, typically below a few mol%. Polymers and copolymers prepared by RDRP methods can have defined topologies (stars, brushes, networks, combs), compositions (block, gradient, graft, alternate) and chain-end functionalities. [22] This review will focus on ATRP, with particular attention to the design and application of progressively more active and selective copper-based catalysts, and the development of novel, more benign initiation systems. The correlation between the structure of Cu complexes and their catalytic activity will be discussed in detail, also taking into account the effect of solvent and, when present, surfactants and other additives. Mechanisms of Reversible Deactivation Radical Polymerization ProcessesThe core of all RDRP systems is the increase of chain lifetime by reversibly deactivating the propagating radical species, thus forming dormant species that can be subsequently reactivated. As opposed to conventional RP in which the 25 Years of ATRP Approaching 25 years since its invention, atom transfer radical polymerization (ATRP) is established as a powerful technique to prepare precisely defined polymeric materials. This perspective focuses on the relation between structure and activity of ATRP catalysts, and the consequent choice of the initiating system, which are paramount aspects to well-controlled polymerizations. The ATRP mechanism is discussed, including the effect of kinetic and thermodynamic parameters and side reactions affecting the catalyst. The coordination chemistry and activity of copper complexes used in ATRP are reviewed in chronological order, while emphasizing the structure-activity correlation. ATRP-initiating systems are described, from ...

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Section: Removal Of Atrp Catalystsmentioning

confidence: 99%

Atom Transfer Radical Polymerization: Billion Times More Active Catalysts and New Initiation Systems

Ribelli

Lorandi

Fantin

et al. 2018

Macromol. Rapid Commun.

235

184

View full text Add to dashboard Cite

show abstract

“…Besides BPO/DMA, ammonium persulfate (APS)/ N , N , N , N ‐tetramethylethylenediamine (TEMED) couples are also redox initiators . Moreover, atom transfer radical polymerization (ATRP) catalyzed by a transition metal/ligand complex is well‐known as one of successful reversible deactivation radical polymerizations . ATRP involves redox reactions between the organic halide initiator and metal halides as a catalyst, such as the initiator system of carbon tetrachloride (CCl 4 )/ferrous chloride (FeCl 2 ).…”

Section: Introductionmentioning

confidence: 99%

Effect of different initiators on temperature‐sensitive monolithic columns and application in online enrichment of β‐sitosterol

Guo

Wang

Lan

et al. 2019

J of Applied Polymer Sci

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Three temperature‐sensitive monolithic columns were prepared by atom transfer radical polymerization and oxidation–reduction method using the initiator systems of CCl4/FeCl2, BPO/DMA, and APS/TEMED, respectively. The three monoliths were characterized by scanning electron microscopy, nitrogen adsorption, and thermogravimetric analysis. The obtained monolithic columns were used as on‐line solid phase extraction sorbent coupled with high‐performance liquid chromatography for the enrichment of β‐sitosterol. By comparing some influencing factors on the adsorption, the optimum temperature‐sensitive monolithic column which was initiated by CCl4/FeCl2 was selected for enrichment of β‐sitosterol from plant oil. The maximum adsorption capacity of the monolith for β‐sitosterol was 10.0031 mg/g. The limit of detection and limit of quantitation were 0.039 and 0.13 mg/mL, respectively. The recovery was in the range of 90.21–98.26%. The results showed that the monolith had better selectivity for β‐sitosterol and could be used for enrichment of β‐sitosterol in food samples. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47683.

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“…The temperature-sensitive phase containing the catalyst complex can be separated from the nonpolar organic phase containing production easily. Recently, we have extended the concept of TPSC to an ATRP process [ 26 , 27 , 28 , 29 , 30 ]. Herein, the ATRP catalyst complexes dissolve in one phase (usually in a polar solvent) while monomer and other substrates with excellent solubility in another phase (usually a nonpolar solvent).…”

Section: Introductionmentioning

confidence: 99%

“…[ 40 ]. Poly(ionic liquid)s (PILs) refer to a kind of ionic polymers connected through a polymeric backbone to form a macromolecular architecture [ 30 ]. Therefore, it is a kind of a unique material which has the special qualities both of polymers and ionic liquids.…”

Section: Introductionmentioning

confidence: 99%

“…In addition, methyl methacrylate (MMA) is an important monomer in industry, which plays a vital role in manufacturing of organic glass, coatings, adhesives, and medical polymers [ 51 ], therefore MMA was used as a model monomer for this novel polymerization system. In addition, we chose a thermoregulated IL monomer, MPEG350-MI-MA, which was first synthesized in our group to polymerize the aim PIL [ 30 ]. The synthetic pathway is shown in Scheme 1 .…”

Section: Introductionmentioning

confidence: 99%

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Poly(Ionic Liquid): A New Phase in a Thermoregulated Phase Separated Catalysis and Catalyst Recycling System of Transition Metal-Mediated ATRP

et al. 2018

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Poly(ionic liquid)s (PILs) have become the frontier domains in separation science because of the special properties of ionic liquids as well as their corresponding polymers. Considering their function in separation, we designed and synthesized a thermoregulated PIL. That is, this kind of PIL could separate with an organic phase which dissolves the monomers at ambient temperature. When heated to the reaction temperature, they become a homogeneous phase, and they separate again when the temperature falls to the ambient temperature after polymerization. Based on this, a thermoregulated phase separated catalysis (TPSC) system for Cu-based atom transfer radical polymerization (ATRP) was constructed. The copper catalyst (CuBr 2 ) used here is easily separated and recycled in situ just by changing the temperature in this system. Moreover, even when the catalyst had been recycled five times, the controllability over resultant polymers is still satisfying. Finally, only 1~2 ppm metal catalyst was left in the polymer solution phase, which indicates the really high recycling efficiency.

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Facilely Recyclable Cu(II) Macrocomplex with Thermoregulated Poly(ionic liquid) Macroligand: Serving as a Highly Efficient Atom Transfer Radical Polymerization Catalyst

Cited by 19 publications

References 50 publications

Atom Transfer Radical Polymerization: Billion Times More Active Catalysts and New Initiation Systems

Atom Transfer Radical Polymerization: Billion Times More Active Catalysts and New Initiation Systems

Effect of different initiators on temperature‐sensitive monolithic columns and application in online enrichment of β‐sitosterol

Poly(Ionic Liquid): A New Phase in a Thermoregulated Phase Separated Catalysis and Catalyst Recycling System of Transition Metal-Mediated ATRP

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