Baroplastics with Robust Mechanical Properties and Reserved Processability through Hydrogen-Bonded Interactions

Lv, Zhi; Qiao, Jia-Ning; Song, Yajing; Ji, Xu; Tang, Jianhua; Yan, Ding‐Xiang; Lei, Jun; Li, Zhong‐Ming

doi:10.1021/acsami.8b20676

Cited by 23 publications

(12 citation statements)

References 49 publications

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“…The strength and modulus of the reinforced composites were as high as 5.6 and 10 MPa, respectively, which increased ca. 73 and 400% compared to the unreinforced baroplastics . Although the enhancement is remarkable, its Young’s modulus is still at a relatively low level.…”

Section: Introductionsupporting

confidence: 72%

Baroplastics with Ultrahigh Strength and Modulus via Hydrogen-Bonding Interactions with Agar

Qiao

Yang

et al. 2020

ACS Appl. Polym. Mater.

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For the traditional processing of polymers, a high temperature, generally above 200 °C, is needed to melt the polymers. The high temperature not only causes a large amount of energy consumption but also thermal degradation of the polymers. In this work, we have prepared a representative baroplastic poly(nbutyl acrylate)@polystyrene (PBA@PS) core−shell polymer, which can be processed at a much lower temperature multiple times to overcome the abovementioned problems. To address their poor mechanical property issue, such as weak strength and low modulus, we introduced stronger hydrogen bonds of agar into PBA@PS matrix. The results show that the PBA@PS/agar composites possess significantly improved strength and ultrahigh modulus, much higher than that of previously reported core−shell baroplastics. The tensile strength and Young's modulus are as high as 8.4 and 350.6 MPa, respectively, which are enhanced by 265 and 4702% compared with the pure PBA@PS baroplastic. The reinforcement results from the hydrogen bonds of agar. In addition, the baroplastics can be repeatedly processed at 100 °C at the same condition with a small loss of mechanical properties. This work provides a way to strengthen the baroplastics and thus increases their application potential.

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Section: Introductionsupporting

confidence: 72%

Baroplastics with Ultrahigh Strength and Modulus via Hydrogen-Bonding Interactions with Agar

Qiao

Yang

et al. 2020

ACS Appl. Polym. Mater.

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“…However, constructing a reversible covalent network in rubbers is difficult because most the required functional groups are not congenial for commercial rubbers. In contrast, networks based on noncovalent bonds such as ionic bonds, , hydrogen bonds, − and so forth, are readily incorporated into the rubber matrix. Unfortunately, the issue that pristine reinforcing fillers retained in recycled rubbers still remains unresolved.…”

Section: Introductionmentioning

confidence: 99%

Strengthened, Recyclable, Weldable, and Conducting-Controllable Biobased Rubber Film with a Continuous Water-Soluble Framework Network

Chen

Nie

et al. 2019

ACS Sustainable Chem. Eng.

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At present, recycling of rubbers is the main method to achieve their sustainable development. However, it is a challenge to recycle rubbers without retaining pristine reinforcing-fillers. Herein, we report fully biobased rubber films prepared by mixing epoxidized natural rubber (ENR) latex and carboxymethyl chitosan (CMCS) solution. CMCS was regenerated and selectively located in the interstitial space between the ENR latex particles during the film-forming process, forming a CMCS framework network in the films. The special CMCS network with hydrogen bonding interactions with ENR endowed rubber films with improved mechanical properties. At the same time, the self-sticky characteristic of ENR with the assistance of chain diffusion and reversible hydrogen bonding interactions made the cut films to be welded. Because the water-soluble CMCS is a continuous phase, the ENR could be perfectly recycled by soaking films in water to remove the CMCS. Furthermore, the CMCS framework running through the whole films provided a wonderful 3D network for conducting. The ENR/CMCS films could turn into conductive films when the moisture content was higher than 1 wt %. The conductivity of the ENR/CMCS films could be tailored conveniently by controlling the moisture content or changing the concentration of the electrolyte in the absorbed water. Thus, we provide a convenient approach to prepare strengthened, recyclable, weldable, and conductive biobased rubber films that can find applications in humidity sensors.

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“…Polymer networks that contain dynamic reversible bonds exhibit unusual properties such as extraordinary toughness, self‐healing capabilities, and time dependent reversible elasticity . These networks typically use reversible interactions such as metal–ligand coordination bonds, hydrogen bonds, ionic bonds, and hydrophobic interactions . Catechol motifs are of particular interest owing to their ability to form many types of reversible bonds .…”

Section: Methodsmentioning

confidence: 99%

Dynamic Contributions to the Bulk Mechanical Properties of Self‐Assembled Polymer Networks with Reconfigurable Bonds

Tang

Wang

Eristoff

et al. 2019

Macromol. Rapid Commun.

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Catechol motifs are of particular interest owing to their ability to form many types of reversible bonds. [15][16][17][18][19] Polymer networks with catechol-cation coordination bonds have relaxation times that are governed by the affinity of the cation with the catechol group. [20][21][22] Grindy et al. [23] measured the viscoelastic modulus for networks with kinetically distinct metal coordinate crosslinks and demonstrated that reversible coordination junctions dominate the viscoelasticity of bulk materials. Catechol motifs with two hydroxy groups can also form hydrogen bonds among themselves. [24] Comparatively, there have been few reports on the role of hydrogen bonds between catechols in crosslinked networks. [25] Furthermore, the role of catechol concentration on bulk mechanics of polymer networks has yet to be elucidated in networks composed of model polymers. Here, we describe the role of hydrogen-bonded catechols on the bulk mechanical properties of the resulting networks.We recently synthesized catecholbearing ABA triblock copolymers that can self-assemble into mechanically robust networks wherein physical crosslinks are stabilized by inter-chain hydrogen bonding. [26] The copoly mer is synthesized through three steps and is processed into a network as shown in Scheme 1. Poly(ethylene glycol)-bromide (PEG-Br) macroinitiators are first prepared and then extended with an active esterified methacrylic acid (N-hydroxysuccinimide ester; NHSMA) by atom transfer radical polymerization. A blocks are then conjugated with dopamine to produce poly(NHSMA) 60 -b-PEG 227 -b-poly(NHSMA) 60 -Cat (ABA-Cat) polymers with a targeted conjugation ratio (r cat ) defined as the fraction of NHSMA monomers functionalized with a pendant catechol. Solutions of ABA-Cat polymer in N,Ndimethylformamide (DMF) self-assemble into networks through solvent exchange with water. We posit the network contains physical crosslinks composed of catechol-rich A blocks bridged together by PEG-based B blocks for following reasons. First, A and B blocks are immiscible in water and will be phase separated. Our previous study on structure showed solvent exchange disrupts crystalized PEG block by differential scanning calorimetry [26] and hydrogen-bonded Soft materials that contain dynamic and reversible bonds exhibit unique properties including unusual extensibility, reversible elasticity, and self-healing capabilities, for example. Catechol motifs are of particular interest owing to their ability to form many kinds of reversible bonds; however, there are few reports on the role of hydrogen bonds between catechols. Here, physically crosslinked self-assembled networks composed of catechol-functionalized ABA triblock co-polymers are synthesized and characterized to elucidate the role of intermolecular bonding between catechol motifs on bulk mechanical properties. The Young's moduli of equilibrated networks range from 16 to 43 MPa. Furthermore, the concentration of intermolecular interaction is controlled indirectly by synthesizing polymers with prescri...

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Baroplastics with Robust Mechanical Properties and Reserved Processability through Hydrogen-Bonded Interactions

Cited by 23 publications

References 49 publications

Baroplastics with Ultrahigh Strength and Modulus via Hydrogen-Bonding Interactions with Agar

Baroplastics with Ultrahigh Strength and Modulus via Hydrogen-Bonding Interactions with Agar

Strengthened, Recyclable, Weldable, and Conducting-Controllable Biobased Rubber Film with a Continuous Water-Soluble Framework Network

Dynamic Contributions to the Bulk Mechanical Properties of Self‐Assembled Polymer Networks with Reconfigurable Bonds

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