Effects of solvents and temperature on spherulites of self-assembled phloroglucinol tristearate

doi:10.1007/s11705-019-1911-3

Front. Chem. Sci. Eng.

2020, Vol. 14

Issue (3) : 389-396 https://doi.org/10.1007/s11705-019-1911-3

RESEARCH ARTICLE

Effects of solvents and temperature on spherulites of self-assembled phloroglucinol tristearate

Yawen Yao¹, Sabine Rosenfeldt², Kai Zhang¹(

)

¹. Wood Technology and Wood Chemistry, Georg-August-University of Goettingen, 37077 Göttingen, Germany
². Department of Chemistry and Bavarian Polymer Institute, University of Bayreuth, 95447 Bayreuth, Germany

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Abstract

Herein, phloroglucinol tristearate (PhgTS) was used to study the crystallization process due to its unique symmetric structure containing a benzene ring and three aliphatic chains. Spherulites of crystallized PhgTS from four solvents under diverse conditions were analyzed in detail and their formation process was studied. Maltese cross is shown by PhgTS spherulites obtained from aprotic solvents via polarized optical microscopy. In comparison, no Maltese cross can be observed from branch-like crystals formed from protic solvents. Independent on the microscaled morphology, lamellae were found to be the basic blocks constructing both PhgTS spherulites and branch-like crystals, which were formed predominantly by stacked PhgTS molecules. Although differential characters of the solvents did not affect the formation of lamellas, the solvents played a crucial role in the formation of self-assembled microscaled morphologies. In particular, the morphologies of spherulites were strongly affected by the concentration of PhgTS solutions, surrounding temperature and evaporation rate of solvents. Generally, a higher concentration of PhgTS led to more homogeneous spherulites, a lower evaporation rate resulted in more compact spherulites, and a higher surrounding temperature generated preferentially more ring-banded spherulites of PhgTS.

Keywords phloroglucinol tristearate aprotic and protic solvent self-assembly spherulites

Corresponding Author(s): Kai Zhang

Online First Date: 21 February 2020 Issue Date: 28 April 2020

Cite this article:

Yawen Yao,Sabine Rosenfeldt,Kai Zhang. Effects of solvents and temperature on spherulites of self-assembled phloroglucinol tristearate[J]. Front. Chem. Sci. Eng., 2020, 14(3): 389-396.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-019-1911-3
https://academic.hep.com.cn/fcse/EN/Y2020/V14/I3/389

Fig.1 Scheme 1 Schematic illustration for the synthesis and crystallization process.

Fig.2 (a) ¹³C NMR spectrum (180?0 ppm) of PhgTS recorded in chloroform-d under ambient conditions; (b) TGA of phloroglucinol and PhgTS between 100°C and 600°C (T₁ and T₂ are the first and second onset temperature in the TGA curve of phloroglucinol, respectively. T₃ is the onset temperature in the TGA curve of PhgTS).

Fig.3 Morphologies of PhgTS crystals from solutions of PhgTS in various solvents with diverse concentrations at 20°C. (a1?c1) Polarized optical microscope images of PhgTS crystals from THF solutions with the concentration of 1, 5 and 10 mg/mL, respectively; (d1?f1) Polarized optical microscope images of PhgTS crystals from its solutions in DCM, toluene and 1-butanol with the concentration of 10 mg/mL, respectively; (a2?f2 and a3?f3) SEM images of PhgTS crystals of higher magnifications corresponding to images (a1?f1).

Fig.4 (a) Heating and (b) cooling DSC curves as well as (c) 1D SAXS-patterns of PhgTS crystals various solvents. The theoretical intensity of a lamella crystal lattice with a lattice constant of 40 Å (green intensity) and a typical scaling law for big 3-dimensional objects (purple line) are also given.

Fig.5 Schematic illustration for the formation process of PhgTS spherulites.

Fig.6 PhgTS spherulites formed from PhgTS solutions in (a, b) THF and (c, d) toluene with the concentration of 10 mg/mL at diverse temperatures; (a1 and b1) Polarized optical microscope images of PhgTS spherulites from THF at 20°C with the evaporation time of 156±20 s and at 28°C with the evaporation time of 143±25 s, respectively; (c1 and d1) Polarized optical microscope images of PhgTS spherulites from toluene at 20°C with the evaporation time of 306±50 s and at 28°C with the evaporation time of 291±45 s, respectively; (a2?d2) SEM images of corresponding PhgTS spherulites in (a1?d1).

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