Elsevier

Chemical Engineering Journal

Volume 448, 15 November 2022, 137749
Chemical Engineering Journal

Bio-based recyclable Form-Stable phase change material based on thermally reversible Diels–Alder reaction for sustainable thermal energy storage

https://doi.org/10.1016/j.cej.2022.137749Get rights and content

Highlights

  • Bio-based solid–solid phase change polymer material was successfully prepared.

  • The reversible D-A reaction endowed the phase change material with ability to recycle.

  • The chemical structure and phase change latent heat of phase change material were all unchanged after reprocess.

  • The potential application of the phase change material was explored in the field of intelligent thermal management.

Abstract

Polymer-based form-stable phase change materials (FPCMs) have attracted much attention due to their excellent shape stability and facileness, low-energy-consumption preparation. However, bio-based recyclable phase change energy storage materials (PCMs), crucial for reducing pollution and sustainable energy storage, have not yet been prepared. Herein, we prepared a novel bio-based recyclable PCM (DGEM-18/FA/MA/xBW), in which a novel epoxy resin (DGEM) was synthesized by using bio-based magnolol and epichlorohydrin, bio-based 2-Furanmethanamine (FA) and C36-alkylenediamines bismaleimide (MA) were used to construct a reversible crosslinked network based on epoxy-amine ring opening and Diels-Alder (D-A) reactions as the supporting frame. And 1-Octadecanethiol (ODT) and bio-based beeswax (BW) with phase change property were introduced into this supporting frame by grafting on the C=C of Magnolol via “thiol-ene” click reaction and physical blending, respectively. The D-A and rD-A reactions proceed at the temperature below 80 ℃ and above 120 °C, respectively, which provides recyclability of the crosslinked network. The ODT and beeswax provide phase change latent heat up to 119.1 J/g for the sample DGEM-18/FA/MA/1.1BW. Furthermore, taking DGEM-18/FA/MA/0.4BW as an example, its shape memory performance has been explored, as well as its potential applications in recyclable thermal management coatings. To the best of our knowledge, this is the first report on the preparation of bio-based recyclable FPCMs.

Introduction

Phase change energy storage materials (PCMs) have attracted extensive attention due to their storing and releasing heat energy at almost constant temperature by phase change, and applied widely in the fields of energy collection devices, infrared stealth, thermal switches, hyperthermia, thermochromic displays and smart wearable devices [1]. So far, form-stable phase change materials (FPCMs) with shape stability are the most important part of PCMs. FPCMs are mainly composed of two parts: one is the support structure to maintain the shape stability, including 3D porous materials [2], [3], [4], shell materials of micro-/nanocapsules [5], [6] and polymers [7], [8], [9], [10], [11], [12], [13], [14], [15], [16], [17], [18], [19], [20], [21], [22], [23], [24], [25], [26], [27], [28], [29], [30]; and the other is the phase change structure to provide latent heat, such as polyethylene glycol [3], [8], [9], [10], [12], [13], [15], [16], [17], [18], [19], [20], [21], [22], [23], [24], [27], [28], [31] and paraffin [7], [30], [32], [33], [34], [35]. These two parts are combined by chemical bonding [7], [9], [11], [12], [13], [14], [15], [16], [17], [18], [19], [20], [21], [22], [23], [24], [25], [27], [28], [29], [30] or physical interaction [2], [3], [4], [7], [10], [11], [30], [32], [33], [34], [35], [36].

As a support material, polymer is the first choice for the recyclable ones due to the characteristics of degradable chain segments, easy molding, low cost, and easy large-scale preparation [1]. Jingxin Lei et al. synthesized some kinds of polyethylene glycol-based polyurethane phase change materials, and introduced reversible D-A chemical bond, disulfide bond and ionic bond, respectively, into the polyurethane structure to achieve the recovery of the PCMs [22], [28], [37]. Haibo Wang et al. used furan-modified polydopamine particles, which can be used as a photothermal conversion filler for solar energy storage, to cure polyethylene glycol baseline-type polyurethane with maleimide groups. The recyclable property of PCM was realized by D-A reversible reaction [16]. In addition, they also designed a flame retardant and recyclable PCM produced by phosphorus-containing trifunctional maleimide curing agent to cure the furan blocking polyethylene glycol polyurethane [13]. Recently, our team has prepared polysiloxane PCM, which has a phase transition latent heat as high as 125 J/g, by “thiol-ene” click chemical reaction using ODT as the phase change component. Recyclable performance was achieved by the reversible reaction of polysiloxane hydrolysis to silanol. At the same time, it can be used in the field of 3D printing due to its advantages of fast light-click reaction and high resolution [1].

Currently, the research of recyclable PCM is mainly focused on non-renewable petroleum-based materials. Bio-based material as a renewable alternative to petroleum-based material, has caught extensive attention from researchers. The current researches on bio-based material are mainly focused on the performance improvement, and the research on its functionalization is fewer, because the performance of the bio-based material mainly based on soybean oil and cardanol, etc. is poor, compared with petroleum-based material [38], [39], [40], [41], [42], [43], [44], [45], [46], [47], [48]. It is equally important to endow bio-based materials with specific functions, as these tend to be more specific and more valuable for application. Songqi Ma et al. prepared a phosphorus-containing multifunctional aldehyde-based compound by the substitution reaction of vanilline and phosphorus oxychloride, and then cured and molded by reacting with a primary amine to form a Schiff base. At last, the obtained product had flame retardant property [49]. Ica Manas-Zloczower et al. prepared a fully bio-based adhesive formulation derived from bio-based raw materials [50]. Wei Zhao et al. prepared a novel lignin/polyurethane composite, which can be used as a temperature-sensitive smart label [51]. Yazhou Tian of our team explored resveratrol-based thermosetting resins with flame retardant, low dielectric and fluorescent functions [41], [42]. Bingtao Tang and Maryam R. Yazdani used bio-based sodium alginate and cellulose nanofibrils as support materials, and the polyethylene glycol was encapsulated in a bio-hydrogels through hydrogen bond [52], [10]. However, their application is largely limited due to the weak mechanical properties of hydrogel materials, and the exploration of recyclable performance did not be reported. In general, bio-based recyclable PCM has not been reported. In fact, the design and preparation of such material is significant for the sustainable storage of thermal energy.

In this work, we designed and fabricated a new bio-based recyclable phase change energy storage material. Firstly, bio-based magnolol difunctional epoxy resin (DGEM) was synthesized by one pot method; secondly, the crystalline ODT was used as the energy storage material and grafted onto the allyl of magnolol epoxy resin by “thiol-ene” click reaction (DGEM-18); subsequently, a linear epoxy resin prepolymer (DGEM-18/FA) with furan side groups was obtained by the “epoxy-amine” ring-opening reaction of bio-based 2-Furanmethanamine (FA) and DGEM-18; finally, it was cured and molded (DGEM-18/FA/MA) by the D-A reaction between DGEM-18/FA and bio-based C36-alkylenediamines bismaleimide (MA). In addition to being used independently as an PCM, this cross-linked polymer material can also be used as a Supporting Material for other PCMs. We chose bio-based beeswax as the second phase energy storage material, which greatly improved phase change latent heat of this material. Most importantly, the thermally reversible D-A reaction enables the material to be recyclable and remodelable.

Section snippets

Materials

Magnolol (98%, Aladdin Reagent Co., LTD from Shanghai of China), Tetramethyl ammonium bromide (TMAB) (99%, Beijing Chemical Works from China), Epichlorohydrin (ECH) (95%, FUCHEN from Tianjin of China), Sodium hydroxide (NaOH) (96%, Beijing Chemical Works from China), Toluene (99%, FUCHEN from Tianjin of China), 1-Octadecanethiol (97%, MACKLIN Biochemistry Technology Co. Ltd from Shanghai of China), 2-Hydroxy-2-Methylpropiophenone (1173) (97%, MACKLIN Biochemistry Technology Co. Ltd from

Synthesis and characterization of DGEM, DGEM-18, DGEM-18/FA and DGEM-18/FA/MA

The DGEM, DGEM-18, DGEM-18/FA, DGEM-18/FA/MA were synthesized via the chemical routes shown in Scheme 1 and Fig. 1a-c. As shown in Fig. 1a, d, during the preparation of DGEM from Magnolol, the O–H peak at around 3300 cm−1 almost disappeared. It should be noted that absorption peaks around 913 cm−1 appeared in the FTIR spectra of Magnolol and DGEM, because the characteristic peak of epoxy group is similar to that of out-of-plane deformation vibration of allyl CH2 [29]. For DGEM, the absorption

Conclusions

In summary, a bio-based, recyclable SSPCM, which uses thermosetting epoxy resin as a support material, ODT and beeswax as a phase change material, has been designed and prepared. The reversible furan/maleimide D-A reaction contained in the epoxy resin system makes its recyclability. It has been shown that the DGEM-18/FA/MA/xBW has a phase change latent heat of 119.1 J/g, and does not have a significant leakage in multiple recovery experiments. Among them, DGEM-18/FA/MA/xBW (x ≤ 4) has good

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

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