Microencapsulation by Complex Coacervation Notes

Microencapsulation by Complex Coacervation at Room Temperature

Introduction

  • The invention relates to a microencapsulation process using complex coacervation at room temperature. This new method encapsulates hydrophobic liquids or particles without exposing them to temperatures exceeding 30°C for more than one minute.
  • This differentiates it from existing processes.
  • It is suited for volatile, thermolabile, or thermosensitive products that degrade above 40°C for several minutes.
  • The process is particularly useful for encapsulating essential oils and other products sensitive to temperatures above 40°C.

Coacervation Mechanism

  • Coacervation involves the separation of a colloid-rich layer in hydrophilic sols, resembling demixing.
  • This phenomenon is complex and challenging to analyze using phase theory due to difficulties in determining the number of constituents and differentiating phases.
  • The separation of a sol into two layers may not always indicate a change in the number of phases.
  • The term "coacervat" refers to the colloid-rich layer, while "equilibrium liquid" or "supernatant" denotes the colloid-poor layer.
  • "Demixing" is often replaced by "coacervation."

Flocculation vs. Coacervation

  • Conditions for flocculation and coacervation in hydrophilic sols are similar.
  • Coacervation is considered a step after flocculation.
  • The difference between flocculation and coacervation is a matter of degree.
  • Coacervation involves initial flocculation, an intermediate stage between solution (isolated macromolecules) and phase separation (macromolecular aggregation).
  • Polymer solutions are typically clear, becoming turbid during flocculation and separating into two phases during coacervation.

Process Control

  • By varying temperature, adding alcohol or electrolytes, or gradually inducing coagulation, pronounced liquid precipitation can be achieved instead of flocculation.
  • A floc should not be seen as merely aggregated micelles but as numerous adhering coacervated droplets, invisible under a microscope.
  • If conditions favor coalescence (low coacervat viscosity), droplets become visible microscopically.
  • Under more favorable conditions, separation into two distinct layers (coacervated layer and equilibrium liquid layer) can occur rapidly.

Solvation and Coacervation

  • Coacervation of hydrophilic colloids is generally caused by their desolvation.
  • In a coacervated system, the water in the colloid-rich layer (coacervat) must be bound to the colloids; otherwise, it would move to the colloid-poor layer.
  • Non-colloidal matter is bound to colloids, forming a significant part of the coacervat and acting as the remaining solvating envelope of the primitive sol micelles.
  • Solvation stabilizes non-charged particles by surrounding the micelle with water, replacing the micelle surface with a solvating layer.
  • Solvating layers lack concrete boundaries, with solvation involving liquid binding to micelles, decreasing in strength outwards until merging with the free liquid of the dispersing medium.

Coacervat Characteristics

  • A defined boundary is difficult to establish, suggesting a diffuse water envelope.
  • Factors determining coacervation make the solvating envelope less diffuse, defining the boundary between the envelope and dispersing medium more precisely, increasing surface free energy.
  • In a sol, particles are free and dispersed, while in a coacervat, they form a condensed system in contact only with solvent molecules involved in its constitution.
  • Coacervats consist of independent, touching but unbound particles.

Complex Coacervation

  • Complex coacervation, a term coined by Bungenberg de Jong, describes the spontaneous liquid/liquid phase separation when oppositely charged polyelectrolytes mix in an aqueous medium.
  • This results in two layers: one rich in polymers and the other poor, due to electrostatic bonds between the two oppositely charged hydrophilic polymers.
  • The anionic polymer is a polyanion, while the cationic polymer is a polycation.

Factors Affecting Complex Coacervation

  • Not all mixtures of such polyelectrolytes form a complex coacervat.
  • The phenomenon is limited to polyelectrolytes with suitable charge density and chain length.
  • Figure 2 illustrates the electrostatic interaction between a polycation and a polyanion.
  • A distinction must be made between complex coacervats and