Thermoresponsive UCST‐Type Behavior of Interpolymer Complexes of Poly(ethylene glycol) and Poly(poly(ethylene glycol) methacrylate) Brushes with Poly(acrylic acid) in Isopropanol

Szabó, Ákos; Bencskó, György; Szarka, Györgyi; Iván, Béla

doi:10.1002/macp.201600466

Cited by 9 publications

(10 citation statements)

References 38 publications

(59 reference statements)

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“…It is known that PEG can form strong hydrogen bonding with −COOH groups. 43,44 The pegylated polypeptoids or polypeptides were reported to demonstrate LCST behavior because of the reversible hydrogen bonding between the polymer and the water molecule. 8,34,45 To balance the amphiphilicity and molecular interactions, we simultaneously introduce the carboxylic acid and EG groups on the side chains by a facile strategy (Scheme 2).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Tunable LCST/UCST-Type Polypeptoids and Their Structure–Property Relationship

Xing

Sun

2020

Biomacromolecules

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Bioinspired thermoresponsive polymeric materials with tunable phase-transition behaviors are highly desirable for biomedical applications. Here, we reported a facile approach for the synthesis of both lower critical solution temperature (LCST) and upper critical solution temperature (UCST) types of thermoresponsive polypeptoids with tunable phase-transition temperature in the range of 29––55 °C. The introduction of alkyl groups and ethylene glycol (EG) units results in a controlled phase-transition behavior under fairly mild conditions. A very sharp transition (ΔT ≤ 1.5 °C) is observed by simply adjusting pH and the alkyl chain length. In particular, the carboxyl-containing polypeptoids display designable UCST behavior, which can be finely tuned in both water and methanol. All these features make the obtained polymers beneficial for practical applications. More interestingly, we demonstrate that the hydrophilic EG group behaves as an excellent regulator to tune the UCST behavior, while the hydrophobic alkyl residues show remarkable capability to regulate the LCST behavior of the system. We hope that such systematic structure–property studies will enable the design of smart polymer materials to meet the specific needs of future applications.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Tunable LCST/UCST-Type Polypeptoids and Their Structure–Property Relationship

Xing

Sun

2020

Biomacromolecules

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“…PPEGMA (Figure S1) was synthesized using a procedure from the literature . In an example reaction, an EBIB solution was prepared by combining EBIB (0.2 mL, 1.3 mmol) with toluene (0.8 mL).…”

Section: Methodsmentioning

confidence: 99%

“…PPEGMA (Figure S1) was synthesized using a procedure from the literature. 51 In an example reaction, an EBIB solution was prepared by combining EBIB (0.2 mL, 1.3 mmol) with toluene (0.8 mL). Then, 0.08 mL of the solution was added to a reaction vessel containing toluene (2 mL), PEGMA (1 mL, 3.5 mmol), and copper chloride (CuCl) (10.4 mg, 0.1 mmol).…”

Section: ■ Introductionmentioning

confidence: 99%

Design of Mixed Electron- and Ion-Conducting Radical Polymer-Based Blends

et al. 2021

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Mixed electron- and ion-conducting polymers have received considerable interest over the last few years due to their applicability in a variety of organic electronic devices. To achieve this mixed conduction, researchers tend to rely on copolymerizing or blending two polymers, where one conducts ions and the other conducts electrons. Despite their potential as solid-state charge conductors, radical polymers have received less attention than their conjugated counterparts. This work addresses this unmet opportunity by developing a blended radical polymer poly(4-glycidyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl) (PTEO), poly(poly(ethylene oxide) methyl ether methacrylate) (PPEGMA), and lithium hexafluorophosphate system. PPEGMA, similar to previous publications, had one of the highest polymer-based room-temperature ionic conductivity of 10–4 S cm–1. In addition to conducting charges, PTEO had an ionic conductivity of 10–6 S cm–1. A blend of the two polymers at equal weight ratios had a room-temperature ionic conductivity of 10–4 S cm–1 and an electronic conductivity of 10–2 S cm–1 similar to pristine PPEGMA and PTEO thin films, respectively. This similarity resulted from the formation of distinct pathways of ion (i.e., through PPEGMA domains) and electron (i.e., through PTEO domains) conduction due to microscale phase separation between the two polymers with the lithium ions mainly incorporating in the PPEGMA domains. With the addition of lithium salt, the electronic conductivity of the blend increased by 1.7 times. However, at [Li+]/[O] ratios higher than 0.08, the electronic conductivity suffered due to poor film quality. Ultimately, this effort establishes a template for determining mixed conduction in radical polymer-based blends and for developing the next generation of simultaneous conduction devices.

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“…Gibson and coworkers have explored copolymer blending to modulate phase behavior, demonstrating that a single cooperative transition could be achieved upon blending thermoresponsive homopolymers with varying molecular weights formed from the same monomer 32,33. In addition, Iván and coworkers have demonstrated that blending different thermoresponsive homopolymers resulted in the reversible formation of interpolymer complexes, for which the CST could be tuned in either aqueous or organic media upon varying the molar mixing ratio, pH, and/or polymer molecular weight 34,35. Furthermore, Burel and coworkers discovered that the cloud point temperature of thermoresponsive micellar solutions could be modulated via blending two amphiphilic block copolymers comprised of a lipid core and two different thermoresponsive corona‐forming blocks 36.…”

Section: Figurementioning

confidence: 99%

“…[32,33] In addition, Iván and coworkers have demonstrated that blending different thermoresponsive homopolymers resulted in the reversible formation of interpolymer complexes, for which the CST could be tuned in either aqueous or organic media upon varying the molar mixing ratio, pH, and/or polymer molecular weight. [34,35] Furthermore, Burel and coworkers discovered that the cloud point temperature of thermoresponsive micellar solutions could be modulated via blending two amphiphilic block copolymers comprised of a lipid core and two different thermoresponsive corona-forming blocks. [36] Despite the advantages of using copolymer blending to prepare thermoresponsive nanostructures over alternative methods, there exists a limited number of reports focused upon blending thermoresponsive amphiphilic block copolymers in self-assembled systems.…”

Section: Doi: 101002/marc201900599mentioning

confidence: 99%

The Importance of Cooperativity in Polymer Blending: Toward Controlling the Thermoresponsive Behavior of Blended Block Copolymer Micelles

Keogh

Blackman

Foster

et al. 2020

Macromol. Rapid Commun.

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Understanding, predicting, and controlling the self‐assembly behavior of stimuli‐responsive block copolymers remains a pertinent challenge. As such, the copolymer blending protocol provides an accessible methodology for obtaining a range of intermediate polymeric nanostructures simply by blending two or more block copolymers in the desired molar ratio to target specific stimuli‐responsiveness. Herein, thermoresponsive diblock copolymers are blended in various combinations to investigate whether the resultant cloud point temperature can be modulated by simple manipulation of the molar ratio. Thermoresponsive amphiphilic diblock copolymers composed of statistical poly(n‐butyl acrylate‐co‐N,N‐dimethylacrylamide) core‐forming blocks and four different thermoresponsive corona‐forming blocks, namely poly(diethylene glycol monomethyl ether methacrylate) (p(DEGMA)), poly(N‐isopropylacrylamide), poly(N,N‐diethylacrylamide), and poly(oligo(ethylene glycol) monomethyl ether methacrylate) (p(OEGMA)) are selected for evaluation. Using variable temperature turbidimetry, the thermoresponsive behavior of blended diblock copolymer self‐assemblies is assessed and compared to the thermoresponsive behavior of the constituent pure diblock copolymer micelles to determine whether comicellization is achieved and more significantly, whether the two blended corona‐forming thermoresponsive blocks exhibit cooperative behavior. Interestingly, blended diblock copolymer micelles composed of p(DEGMA)/p(OEGMA) mixed coronae display cooperative behavior, highlighting the potential of copolymer blending for the preparation of stimuli‐responsive nanomaterials in applications such as oil recovery, drug delivery, biosensing, and catalysis.

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Thermoresponsive UCST‐Type Behavior of Interpolymer Complexes of Poly(ethylene glycol) and Poly(poly(ethylene glycol) methacrylate) Brushes with Poly(acrylic acid) in Isopropanol

Cited by 9 publications

References 38 publications

Tunable LCST/UCST-Type Polypeptoids and Their Structure–Property Relationship

Tunable LCST/UCST-Type Polypeptoids and Their Structure–Property Relationship

Design of Mixed Electron- and Ion-Conducting Radical Polymer-Based Blends

The Importance of Cooperativity in Polymer Blending: Toward Controlling the Thermoresponsive Behavior of Blended Block Copolymer Micelles

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