Thermal-driven self-healing and green recyclable waterborne polyurethane films based on double reversible covalent bonds

Sai, Futao; Zhang, Haitao; Qu, Jianbo; Wang, Jianyong; Zhu, Xiuzhong; Ye, Peng; Zhang, Zhiliang

doi:10.1016/j.porgcoat.2023.107460

Cited by 19 publications

(9 citation statements)

References 48 publications

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“…For instance, the Diels–Alder reaction between furan and maleimide is thermally reversible, and takes place at low temperatures, while its reversal (retro-DA) occurs at higher temperatures. , The use of this type of thermally reversible bonds is becoming popular in polymer chemistry because at room temperature, the DA bonds are coupled, allowing polymerization, yet above the switching temperature, the material depolymerizes, facilitating material reprocessing. When this principle is used with cross-linkers, i.e., small multifunctional chemical structures with DA bonds, the mechanical properties of the final cross-linked polymer increase; nonetheless, above the switching temperature, the bonds are uncoupled and the polymer network can be uncross-linked, giving plasticity so that the material can be reshaped and subsequently recycled. − This phenomenon has been studied and proven to work even when the pieces are cut in half, damaged, and several healing cycles are performed. − Some authors synthesize polyurethanes through this furan-maleimide reaction of prepolymers (polyurethane and cross-linkers) functionalized with furan and maleimide, yet the coupling reaction turns to be slow and may not be suitable for many high-volume or industrial applications. , …”

Section: Introductionmentioning

confidence: 99%

Emerging Reprocessable and Recyclable Biobased Cross-Linked Polyurethanes Through Diels–Alder Chemistry

Restrepo-Montoya,

Larraza,

Echeverria-Altuna

et al. 2024

ACS Appl. Polym. Mater.

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Cross-linked polyurethanes (PUs) present outstanding properties and high versatility, making them ideal for use in many different applications. Nevertheless, the intersection of environmental and socioeconomic concerns regarding the recyclability of cross-linked materials presents alternative opportunities for advancing the field of cross-linked polyurethane chemistry. In this context, emerging reprocessable and recyclable biobased crosslinked PUs were synthesized within this work through Diels−Alder (DA) chemistry. Thus, a trifunctional partially biobased lowmolecular-weight polyol containing the furan−maleimide Diels− Alder adduct (DA-triol) was developed to be used as a thermoreversible cross-linker in PU synthesis. First, the thermoreversibility of the cross-linker was demonstrated at temperatures as high as 160 °C (retro-DA reaction). Afterward, the DA-triol was used together with a commercial biobased macrodiol and polymeric methylene diphenyl diisocyanate (pMDI) to synthesize different formulations of PUs that ended up with properties ranging from flexible to rigid. Then, the recyclability and reprocessability of the synthesized PUs were also evaluated by compression, injection, and extrusion. Finally, the mechanical properties of the original and recycled polyurethanes were tested, obtaining recycling efficiencies higher than 80%. Thereby, these materials offer a solution to the long-standing issue of recycling of cross-linked polyurethanes, overcoming many sustainability challenges.

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Section: Introductionmentioning

confidence: 99%

Emerging Reprocessable and Recyclable Biobased Cross-Linked Polyurethanes Through Diels–Alder Chemistry

Restrepo-Montoya,

Larraza,

Echeverria-Altuna

et al. 2024

ACS Appl. Polym. Mater.

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“…The second is an endogenous self-healing material through interactions (disulfide bonds, Diels-Alder bonds, imine bonds, ionic bonds, van der Waals forces, hydrogen bonds, etc.). [6][7][8][9][10][11][12][13] Xie et al prepared a polyurethane elastomer with ultra-robust, self-healable, and recyclable based on the combined action of hydrogen bonds, disulfide dynamic chemistry, and microphase separation. 14 Pan et al prepared a self-healing, recyclable thermoplastic polyurethane elastomer through metal-ligand bonds between cerium(III) trifluoromesylate and phloderin.…”

Section: Introductionmentioning

confidence: 99%

“…17 At present, it has been shown that the introduction of dynamic covalent bonds in polyurethane chains can give polyurethane materials excellent heat recovery capabilities, reducing resource waste and production costs. 10,[18][19][20][21] At the same time, the dynamic covalent bond in the polyurethane polymer chain can split the large molecular segments into small molecular segments under the action of high temperature and solvent. This makes the material easier to dissolve in solvents and thus has better degradability.…”

Section: Introductionmentioning

confidence: 99%

“…The second is an endogenous self‐healing material through interactions (disulfide bonds, Diels‐Alder bonds, imine bonds, ionic bonds, van der Waals forces, hydrogen bonds, etc.) 6–13 . Xie et al prepared a polyurethane elastomer with ultra‐robust, self‐healable, and recyclable based on the combined action of hydrogen bonds, disulfide dynamic chemistry, and microphase separation 14 .…”

Section: Introductionmentioning

confidence: 99%

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Healable, degradable polyurethane elastomers with excellent mechanical properties based on multiple hydrogen bonds

Gao,

Sun,

Wang

et al. 2023

J of Applied Polymer Sci

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Due to its comprehensive properties, polyurethane elastomer (PU) plays a vital role in ships, construction, transportation facilities, and other fields. However, it is challenging to design polyurethane elastomer materials with good mechanical properties, self‐healing ability, and degradable ability. Herein, a kind of polyurethane elastomer based on multiple hydrogen bond crosslinking was successfully synthesized by using polycaprolactone with substantial crystallization as a soft chain segment and introducing adipic dihydrazide (ADH) and U2‐diol (a ureido‐pyrimidinone with two hydroxyl groups at the end) to achieve ordered hydrogen bond assembly design and control. The elastomer has good tensile strength, healability, degradability, and solubility. The maximum tensile strength and toughness of the prepared polyurethane elastomer (PUAD) were 46.34 MPa and 687.66 MJ/m3, respectively. With the increase of U2‐diol content, the self‐repair efficiency was greatly enhanced. After seven repair cycles, the self‐repair efficiency can still reach 66.88%. In addition, the bacterial degradation test using Pseudomonas aeruginosa as a strain showed that PUAD film had excellent degradability. The dissolution test with N,N‐dimethylformamide (DMF) as solvent showed that the tensile strength was almost unchanged after three dissolutions.

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“…Furthermore, the limitations of molding and demolding processes hinder the attainment of complex shapes for thermoset PUs and make post-molding reshaping challenging. To solve the recycling and reprocessing issues of thermoset PUs, the incorporation of dynamic chemical bonds, such as disulfide, 26,27 thiourethane bond, [28][29][30][31] Diels-Alder adduct, [32][33][34] boronate ester bond, [35][36][37] oxime-carbamate bond 38,39 and others, into the cross-linked PU network is typically required.…”

Section: Introductionmentioning

confidence: 99%

Colorless, transparent, and shape memory polyurethane networks with high strength and recyclability

Ma,

Yue,

Huang

et al. 2023

J of Applied Polymer Sci

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The traditional thermoset polyurethanes (PUs) can be recycled through the dynamic carbamate bonds under specific conditions. However, there is limited research on the structural evolution and property changes of these PUs before and after recycling. Herein, we designed and fabricated a thermoset polyurethane network (PCU) using polyhexamethylene carbonate diol (PHMC‐diol) as soft segments, and isophorone diisocyanate (IPDI) and glycerol (GLY) as hard segments. Through careful formulation design, the PCU demonstrated colorless transparency (with up to 86% transmission), shape memory properties, and reprocessing capabilities, all achieved without introducing other dynamic covalent bonds. Furthermore, the PCU exhibited excellent mechanical properties, boasting a tensile strength of 59.2 ± 3.7 MPa and the elongation at break of 674.8 ± 37.3%. Of particular interest, the PCU samples displayed solid‐state plasticity and impressive shape memory performance, with shape fixity and recovery ratios exceeding 90%. Leveraging the combination of solid‐state plasticity and shape memory, the PCU samples demonstrated the ability to achieve arbitrary shape manipulations. Upon recycling, it was observed that the cross‐linking density of the PCU samples decreased, resulting in the formation of byproducts and subsequently leading to a reduction in tensile strength. Nonetheless, the PCU samples prepared in this study exhibit potential as thermadapt shape memory and recyclable materials.

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Thermal-driven self-healing and green recyclable waterborne polyurethane films based on double reversible covalent bonds

Cited by 19 publications

References 48 publications

Emerging Reprocessable and Recyclable Biobased Cross-Linked Polyurethanes Through Diels–Alder Chemistry

Emerging Reprocessable and Recyclable Biobased Cross-Linked Polyurethanes Through Diels–Alder Chemistry

Healable, degradable polyurethane elastomers with excellent mechanical properties based on multiple hydrogen bonds

Colorless, transparent, and shape memory polyurethane networks with high strength and recyclability

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