Synthesis of a doubly thermo-responsive schizophrenic diblock copolymer based on poly[N-(4-vinylbenzyl)-N,N-diethylamine] and its temperature-sensitive flip-flop micellization

Li, Shentong; Huo, Fei; Li, Quanlong; Gao, Chengqiang; Su, Yang; Zhang, Wangqing

doi:10.1039/c4py00077c

Cited by 16 publications

(14 citation statements)

References 81 publications

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“…Supramolecular polymers based on UPy groups have been widely investigated and materials with important characteristics such as stimuli-responsive [23], self-healing [10,11,[49][50][51][52] and temperature responsive [53,54] properties have found applications within printing [55][56][57][58], cosmetics [59,60], adhesives [61] and coatings [62]. As an example of how supramolecular associations can play an important role, for inkjet printing applications a UPy-modified polyether mixed with stabilizers, antioxidants and colourants was used in work by Jaeger et al [55].…”

Section: Introductionmentioning

confidence: 99%

Linear shear and nonlinear extensional rheology of unentangled supramolecular side-chain polymers

Cui

Boudara

Huang

et al. 2018

Journal of Rheology

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Supramolecular polymers are important within a wide range of applications including printing, adhesives, coatings, cosmetics, surgery and nano-fabrication. The possibility to tune polymer properties through the control of supramolecular associations makes these materials both versatile and powerful. Here, we present a systematic investigation of the linear shear rheology for a series of unentangled ethylhexyl acrylate based polymers for which the concentration of randomly distributed supramolecular side-groups are systematically varied. We perform a detailed investigation of the appplicability of Time Temperature Superposition (TTS) for our polymers; small amplitude oscillatory shear rheology is combined with stress relaxation experiments to identify the dynamic range over which TTS is a reasonable approximation. Moreover, we find that the "stickyRouse" model normally used to interpret the rheological response of supramolecular polymers fits our experimental data well in the terminal regime, but is less successful in the rubbery plateau regime. We propose some modifications to the "sticky-Rouse" model, which includes more realistic assumptions with regards to (i) the random placement of the stickers along the backbone, (ii) the contributions from dangling chain ends and (iii) the chain motion upon dissociation of a sticker and re-association with a new co-ordination which involves a finite sized "hop" of the chain. Our model provides an improved description of the plateau region. Finally, we measure the extensional rheological response of one of our supramolecular polymers. For the probed extensional flow rates, which are small compared to the characteristic rates of sticker dynamics, we expect a Rouse-type description to work well. We test this by modeling the observed strain hardening using the upper convected Maxwell model and demonstrate that this simple model can describe the data well, confirming the prediction and supporting our determination of sticker dynamics based on linear shear rheology. * k.j.l.mattsson@leeds.ac.uk 2

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Section: Introductionmentioning

confidence: 99%

Linear shear and nonlinear extensional rheology of unentangled supramolecular side-chain polymers

Cui

Boudara

Huang

et al. 2018

Journal of Rheology

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“…At the end of this section, it should be pointed out that the PVEA is a new thermo-responsive polymer and its LCST was dependent on the polymer molecular weight and polymer concentration. [ 47,48 ] However, in the case of this study due to zwitterionic behavior, the synthesized PSEMA- b -PVEA diblock copolymer did not showed thermo-sensitivity. [ 46 ]…”

Section: Resultsmentioning

confidence: 64%

Novel ‘schizophrenic’ diblock copolymer synthesized via RAFT polymerization: poly(2-succinyloxyethyl methacrylate)-b-poly[(N-4-vinylbenzyl),N,N-diethylamine]

Ghamkhari

Massoumi

Jaymand

2016

Designed Monomers and Polymers

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This article describes the synthesis and characterization of a novel ‘schizophrenic’ diblock copolymer [poly(2-succinyloxyethyl methacrylate)-b-poly[(N-4-vinylbenzyl),N,N-diethylamine)]; PSEMA-b-PVEA] via reversible addition of fragmentation chain transfer (RAFT) polymerization technique. The chemical structures of all samples as representatives were characterized by means of Fourier transform infrared (FTIR), and 1H nuclear magnetic resonance (NMR) spectroscopies. The molecular weights of PHEMA and PVEA segments were calculated to be 9770 and 12,630 gmol−1, respectively, from 1H NMR spectroscopy. The self-assembly behavior of the synthesized PSEMA-b-PVEA diblock copolymer was investigated by means of 1H NMR spectroscopy, dynamic light scattering (DLS) measurements, and transmission electron microscopy (TEM) observation. The average sizes of the PSEMA-b-PVEA micelles at pHs 3.0, 6.0, and 10.0 were obtained to be 294, 237, and 201 nm, respectively, from DLS analysis. The zeta potential measurements at various pHs demonstrated that the synthesized PSEMA-b-PVEA diblock copolymer has zwitterionic properties, and the range of isoelectric point’s (IEP’s) was determined as 5.8–7.3. It is expected that the synthesized PSEMA-b-PVEA diblock copolymer considered as a prospective candidate in nanomedicine applications such as drug delivery, mainly due to its excellent ‘schizophrenic’ micellization behavior.

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“…In another study by Zhou et al., poly[1′‐(2‐methacryloxyethyl)‐3′,3′‐dimethyl‐6‐nitrospiro‐(2 H ‐1‐benzopyran‐2,2′‐indoline)‐ b ‐acrylic acid] not only showed light‐ and pH‐dual‐stimuli responsiveness, but also showed schizophrenic behavior 105. Other reports on schizophrenic micelles include CO 2 and temperature‐responsive switching from vesicles to micelles,106 salt‐responsive reversible micellization,107 double‐thermo‐ responsive flip‐flop micellization,108 and so forth.…”

Section: Schizophrenic Micellesmentioning

confidence: 99%

Multi‐Stimuli‐Responsive Polymeric Materials

Guragain

Bastakoti

Malgras

et al. 2015

Chemistry A European J

201

114

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Stimuli-responsive materials are of immense importance because of their ability to undergo alteration of their properties in response to their environment. The properties of such materials can be tuned by subtle adjustments in temperature, pH, light, and so forth. Among such smart materials, multi-stimuli-responsive polymeric materials are of pronounced significance as they offer a wide range of applications and their properties can be tuned through several mechanisms. Here, we aim to highlight some recent studies showcasing the multi-stimuli-responsive character of these polymers, which are still relatively little known compared to their single-stimuli-responsive counterpart.

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Synthesis of a doubly thermo-responsive schizophrenic diblock copolymer based on poly[N-(4-vinylbenzyl)-N,N-diethylamine] and its temperature-sensitive flip-flop micellization

Abstract: A doubly thermo-responsive schizophrenic diblock copolymer, poly(tert-butyl methacrylate)-block-poly[N-(4-vinylbenzyl)-N,N-diethylamine], was synthesized and its flip-flop micellization was demonstrated.

Cited by 16 publications

References 81 publications

Linear shear and nonlinear extensional rheology of unentangled supramolecular side-chain polymers

Linear shear and nonlinear extensional rheology of unentangled supramolecular side-chain polymers

Novel ‘schizophrenic’ diblock copolymer synthesized via RAFT polymerization: poly(2-succinyloxyethyl methacrylate)-b-poly[(N-4-vinylbenzyl),N,N-diethylamine]

Multi‐Stimuli‐Responsive Polymeric Materials

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