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Progress in Chemistry 2020, Vol. 32 Issue (7): 882-894 DOI: 10.7536/PC191019 Previous Articles   Next Articles

• Review •

Fabrications, Properties, and Applications of Stimuli-Responsive Polymer Microspheres

Meng Mu1,2, Xuewen Ning1, Xinjie Luo1, Yujun Feng1,**()   

  1. 1. State Key Laboratory of Polymer Materials Engineering, Polymer Research Institute, Sichuan University, Chengdu 610065, China
    2. Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, China
  • Received: Online: Published:
  • Contact: Yujun Feng
  • About author:
    ** e-mail:
  • Supported by:
    National Natural Science Foundation of China(21273223); National Natural Science Foundation of China(U1762218)
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Polymer microspheres are considered to be the typical soft materials which are widely used in catalysis, drug delivery, biosensing, microreactors, chemical separation and coating fields because of their unique properties, such as the micro-scale, diffusion, penetration and ease of modification. In order to meet the requirement for use in hostile environments, stimuli-responsive microspheres whose properties significantly change in response to the minor variation of environmental conditions have been developed. This paper reviews the diverse fabrication strategies and morphologies of the responsive polymer microspheres which are sensitive to temperature, pH, magnetic field, ionic strength, light and CO2 stimulus, respectively. The relevant stimuli-response mechanisms, applications and the demerits of the responsive microspheres are summarized and discussed, then the potential applications and future prospects of the sensitive microspheres are also analyzed.

Contents

1 Introduction

2 Stimuli-responsive Polymer Microspheres

2.1 Fabrication of polymer microspheres

2.2 Temperature-responsive polymer microspheres

2.3 pH-responsive polymer microspheres

2.4 Magnetic field-responsive polymer microspheres

2.5 Ionic strength-responsive polymer microspheres

2.6 Light-responsive polymer microspheres

2.7 CO2-responsive polymer microspheres

3 Conclusion and outlook

Key words: polymer microspheres, stimuli-responsive, fabrication strategies, particle morphology, applications
Fig.1 Schematic representation of polymer microspheres with diverse morphologies
Table 1 The fabrication strategies for polymer microspheres
Fabrication protocols Preparation system Particle size ref
Emulsification-solvent evaporation Polymer, organic-solvent, water, stabilizer 10 nm~1 μm 41
Microfluidic method Polymer, microfluidic-device 11
Spray-drying Polymer, spraying-apparatus 42
Dialysis method Polymer, organic-solvent, water, dialysis membrane 43
Conventional emulsion polymerization Monomer, water, initiator, emulsifier 10 nm~1 μm 44
Soap-free emulsion polymerization Monomer, water, initiator 100 nm~1 μm 45
Microemulsion polymerization Monomer, emulsifier, stabilizer, initiator 5 ~50 nm 46
Miniemulsion polymerization Monomer, emulsifiers, stabilizer, initiator 50~500 nm 47
Seeded emulsion polymerization Monomer, seeds, emulsifiers, initiator ≥100 nm 48
Precipitation polymerization Monomer, initiator, stabilizer 100 nm~7 μm 49
Interfacial polymerization Water-soluble monomer, oil-soluble monomer, water, organic solvent 5~650 nm 50
Fig.2 The temperature-responsive change in the catalytic performance of microspheres. (a) and (b) represent the scheme for the fabrication of microspheres, and the catalytic performance of microspheres at different temperature, re-spectively; (c) The change in UV spectra of the reaction products during the reduction reaction, at different temper-atures[60]
Fig.3 The temperature-induced release of the fluorescent dye loaded in particles. (a) Scheme for the temperature-induced release of 2,6-NDS loaded in (P2VPH+/S O 3 2 ? )-PNIPAM particles; (b) The change in dispersity of particles system in response to temperature; (c) The fluorescence spectra of 2,6-NDS released from particles at different temperatures[62]
Fig.4 Fig.4 pH-sensitive microspheres used for regulating Pickering emulsion. (a) Scheme for the preparation and the pH response of PTBAEMA microspheres; (b) pH induced change in particle size; (c) and (d) represent pH regulated formation/breakup transition of Pickering emulsion[68]
Fig.5 (a)Schematic preparation of magnetic responsive microspheres via microfluidic protocol;(b) and(c) represent the magnetic responsive transition of microspheres dispersions;(d) the magnetization curves of hollow microspheres[77]
Fig.6 CO2-regulated emulsification of polymer materials. (a) Scheme for the fabrication and CO2-responsiveness of PS latex; (b) Snapshot of CO2-induced dispersion/precipitation transition of PS latex[100]
Fig.7 The selective adsorption and release of dye, regulated by CO2. (a) Scheme for the fabrication of P(AM-DEAEMA) microspheres. (b) Scheme for the selective adsorption and release of dye in response to C O 2 [ 104 ]
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