Morphology-controlled growth of perylene derivative induced by double-hydrophilic block copolymers

Abstract

Controlled growth of technically relevant perylene derivative 3, 4, 9, 10-perylenetetracarboxylic acid potassium salt (PTCAPS), with tuneable morpologies, has been successfully realized by a recrystallization method using a double-hydrophilic block copolymer poly (ethylene glycol)-block poly (ethyleneimine) (PEG-b-PEI) as the structure directing agent. The {001} faces of PTCAPS are most polar and adsorb the oppositively charged polymer additive PEG-b-PEI well by electrostatic attraction. By simply adjusting the PEG-b-PEI concentration, systematic morphogenesis of PTCAPS from plates to microparticles composed of various plates splaying outwards could be realized. Furthermore, the variation of pH value of the recrystallization solution could induce the change of the interaction strength between PEG-b-PEI additive and PTCAPS and thus modify the morphology of PTCAPS from microparticles composed of various plates to ultralong microbelts.

Crystallization Control of N,N′-Dioctyl Perylene Diimide by Amphiphilic Block Copolymers Containing poly(3-Hexylthiophene) and Polyethylene Glycol

“…The addition of polyacrylate, polyethylene glycol (PEG) and other polymers can also improve the molecular orientation of TP and enhance its long-range ordering (He et al, 2013;He et al, 2020). Huang et al used the amphiphilic block copolymer PEG-block-poly(ethyleneimine) (PEG-b-PEI) as the additive of a perylene derivative (Huang et al, 2016). By adjusting the concentration of the block copolymer and the pH of the solution, a series of perylene derivative with different crystal morphologies can be obtained.…”

Bottom-Up Synthesis of Polymeric Micro- and Nanoparticles with Regular Anisotropic Shapes

“…For example, the few cases available in the literature of these techniques applied to particles of organic molecules are related to the crystallization of dyes or other complex structures rather than direct synthesis of polymers. 23,24 A much more popular modification of this method is the directed precipitation of dissolved polymers via evaporation 25,26 or, more recently, by means of a directed flow gradient. 27,28 Commonly, this modification of the method leads to the formation of polymeric fibers with different aspect ratios.…”

“…There are several major techniques for the synthesis of shape-anisotropic particles. − Probably the most common method among them is the emulsion polymerization technique coupled with phase separation. − The method is based on emulsification of a monomer or monomers mixture and their subsequent polymerization. On the basis of well-designed phase transitions, one could obtain various morphological modifications ranging from indented spheres to raspberry-like particles or even crescent-shaped particles. , …”

“…Alteration of crystal growth in supersaturated solutions could be used for the growth of cubic, pyramidal, spherical, ellipsoidal, rod-like, and platelet-like particles. − This method, however, is predominantly used for inorganic particles and can barely contribute to the shaping of polymeric ones. For example, the few cases available in the literature of these techniques applied to particles of organic molecules are related to the crystallization of dyes or other complex structures rather than direct synthesis of polymers. , A much more popular modification of this method is the directed precipitation of dissolved polymers via evaporation , or, more recently, by means of a directed flow gradient. , Commonly, this modification of the method leads to the formation of polymeric fibers with different aspect ratios.…”