Ilyina Svetlana O, Gorbunova Irina Y, Yadykova Anastasiya Y, Vlasova Anna V, Kerber Michael L, Ilyin Sergey O
A.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 29 Leninsky Prospect, 119991 Moscow, Russia.
Department of Plastics Processing Technology, D. Mendeleev University of Chemical Technology of Russia, 9 Miusskaya Square, 125047 Moscow, Russia.
Polymers (Basel). 2024 Nov 24;16(23):3264. doi: 10.3390/polym16233264.
Naphthalene is a fungicide that can also be a phase-change agent owing to its high crystallization enthalpy at about 80 °C. The relatively rapid evaporation of naphthalene as a fungicide and its shape instability after melting are problems solved in this work by its placement into a cured epoxy matrix. The work's research materials included diglycidyl ether of bisphenol A as an epoxy resin, 4,4'-diaminodiphenyl sulfone as its hardener, and naphthalene as a phase-change agent or a fungicide. Their miscibility was investigated by laser interferometry, the rheological properties of their blends before and during the curing by rotational rheometry, the thermophysical features of the curing process and the resulting phase-change materials by differential scanning calorimetry, and the blends' morphologies by transmission optical and scanning electron microscopies. Naphthalene and epoxy resin were miscible when heated above 80 °C. This fact allowed obtaining highly concentrated mixtures containing up to 60% naphthalene by high-temperature homogeneous curing with 4,4'-diaminodiphenyl sulfone. The initial solubility of naphthalene was only 19% in uncured epoxy resin but increased strongly upon heating, reducing the viscosity of the reaction mixture, delaying its gelation, and slowing cross-linking. At 20-40% mass fraction of naphthalene, it almost entirely retained its dissolved state after cross-linking as a metastable solution, causing plasticization of the cured epoxy polymer and lowering its glass transition temperature. At 60% naphthalene, about half dissolved within the cured polymer, while the other half formed coarse particles capable of crystallization and thermal energy storage. In summary, the resulting phase-change material stored 42.6 J/g of thermal energy within 62-90 °C and had a glass transition temperature of 46.4 °C at a maximum naphthalene mass fraction of 60% within the epoxy matrix.
萘是一种杀菌剂,由于其在约80°C时具有较高的结晶焓,它也可以作为一种相变剂。作为杀菌剂的萘蒸发相对较快,且熔化后形状不稳定,在这项工作中,通过将其置于固化的环氧基质中来解决这些问题。该工作的研究材料包括作为环氧树脂的双酚A二缩水甘油醚、作为固化剂的4,4'-二氨基二苯砜以及作为相变剂或杀菌剂的萘。通过激光干涉测量法研究了它们的混溶性,通过旋转流变测量法研究了固化前和固化过程中其共混物的流变特性,通过差示扫描量热法研究了固化过程和所得相变材料的热物理特性,通过透射光学显微镜和扫描电子显微镜研究了共混物的形态。当加热到80°C以上时,萘和环氧树脂是可混溶的。这一事实使得通过与4,4'-二氨基二苯砜进行高温均匀固化能够获得萘含量高达60%的高浓度混合物。萘在未固化的环氧树脂中的初始溶解度仅为19%,但加热后溶解度大幅增加,降低了反应混合物的粘度,延迟了其凝胶化,并减缓了交联。在萘的质量分数为20 - 40%时,交联后它几乎完全以亚稳溶液的形式保持溶解状态,导致固化的环氧聚合物增塑并降低其玻璃化转变温度。在萘含量为60%时,约一半溶解在固化聚合物中,而另一半形成能够结晶和储存热能的粗颗粒。总之,所得的相变材料在62 - 90°C范围内储存了42.6 J/g的热能,在环氧基质中萘的最大质量分数为60%时,其玻璃化转变温度为46.4°C。