Angel-López Alejandro, Norambuena Ángel, Arriaza-Echanes C, Terraza Claudio A, Tundidor-Camba Alain, Coll Deysma, Ortiz Pablo A
Doctorado en Ciencias de Materiales Avanzados, Vicerrectoría de Investigación, Universidad Mayor, Santiago 8580745, Chile.
Instituto de Investigaciones y Control del Ejército de Chile (IDIC), Santiago 8370899, Chile.
Polymers (Basel). 2023 Jul 17;15(14):3069. doi: 10.3390/polym15143069.
In this research, novel, organic, solid-liquid phase-change materials (PCMs) derived from methoxy polyethylene glycol (MPEG) and aromatic acyl chlorides (ACs) were prepared through a condensation reaction. The MPEGs were used as phase-change functional chains with different molecular weights (350, 550, 750, 2000, and 5000 g/mol). The aromatic ACs, terephthaloyl chloride (TPC) and isophthaloyl chloride (IPC), were employed as bulky linker cores. Solubility tests demonstrated that this family of PCMs is soluble in protic polar solvents such as HO and MeOH, and insoluble in nonpolar solvents such as -hexane. Fourier-ransform infrared spectroscopy (FT-IR UATR) and nuclear magnetic resonance (H, C, DEPT 135°, COSY, HMQC, and HMBC NMR) were used to confirm the bonding of MPEG chains to ACs. The crystalline morphology of the synthesized materials was examined using polarized optical microscopy (POM), revealing the formation of spherulites with Maltese-cross-extinction patterns. Furthermore, it was confirmed that PCMs with higher molecular weights were crystalline at room temperature and exhibited an increased average spherulite size compared to their precursors. Thermal stability tests conducted through thermogravimetric analysis (TGA) indicated decomposition temperatures close to 400 °C for all PCMs. The phase-change properties were characterized by differential scanning calorimetry (DSC), revealing that the novel PCMs melted and crystallized between -23.7 and 60.2 °C and -39.9 and 45.9 °C, respectively. Moreover, the heat absorbed and released by the PCMs ranged from 57.9 to 198.8 J/g and 48.6 to 195.6 J/g, respectively. Additionally, the PCMs exhibited thermal stability after undergoing thermal cycles of melting-crystallization, indicating that energy absorption and release occurred at nearly constant temperatures. This study presents a new family of high-performance organic PCMs and demonstrates that the orientation of substituent groups in the phenylene ring influences supercooling, transition temperatures, and thermal energy storage capacity depending on the MPEG molecular weight.
在本研究中,通过缩合反应制备了源自甲氧基聚乙二醇(MPEG)和芳族酰氯(AC)的新型有机固-液相变材料(PCM)。MPEG用作具有不同分子量(350、550、750、2000和5000 g/mol)的相变功能链。芳族AC,对苯二甲酰氯(TPC)和间苯二甲酰氯(IPC)用作庞大的连接核。溶解度测试表明,该系列PCM可溶于质子极性溶剂如HO和MeOH,而不溶于非极性溶剂如正己烷。使用傅里叶变换红外光谱(FT-IR UATR)和核磁共振(H、C、DEPT 135°、COSY、HMQC和HMBC NMR)来确认MPEG链与AC的键合。使用偏光显微镜(POM)检查合成材料的晶体形态,揭示了具有马耳他十字消光图案的球晶的形成。此外,证实了较高分子量的PCM在室温下是结晶的,并且与其前体相比表现出增加的平均球晶尺寸。通过热重分析(TGA)进行的热稳定性测试表明,所有PCM的分解温度接近400℃。通过差示扫描量热法(DSC)表征相变性质,揭示新型PCM分别在-23.7至60.2℃和-39.9至45.9℃之间熔化和结晶。此外,PCM吸收和释放的热量分别为57.9至198.8 J/g和48.6至195.6 J/g。此外,PCM在经历熔化-结晶的热循环后表现出热稳定性,表明能量吸收和释放在几乎恒定的温度下发生。本研究提出了一种新型的高性能有机PCM,并表明亚苯基环中取代基的取向根据MPEG分子量影响过冷度、转变温度和热能存储容量。