The Synthesis of Associative Copolymers with Both Amphoteric and Hydrophobic Groups and the Effect of the Degree of Association on the Instability of Emulsions

The acrylamide (AM)/methacryloyl ethyl sulfobetaine (SPE)/behenyl polyoxyethylene ether methacrylate (BEM) terpolymer (PASB) was synthesized by soap-free emulsion polymerization. Four types of PASBs were synthesized by adjusting the moles of AM and BEM with constant total moles of monomers. The synthesized copolymers were characterized by Fourier-transform infrared spectroscopy, thermogravimetry, molecular weight, and viscosity. By measuring the microscopic morphology and backscattered light intensity of the emulsions, the instability process of the emulsions prepared by PASBs was investigated in detail. The main instability processes of the emulsions prepared from PASBs within 45 min were flocculation and coalescence. The intermolecular association of copolymer PASBs was dominated by the behenyl functional groups on the molecular chains. The stability of the emulsions, which were prepared from isoviscosity aqueous solutions controlled by the concentration of the associative copolymers, was increased with the degree of association of copolymers. The hydrophobic association between the copolymer molecules can further slow down the flocculation and coalescence of the emulsion droplets on the basis of the same aqueous solution viscosity, which is one of the reasons for improving the stability of the emulsion.

Preparation, Structure, and Properties of Polystyrene-Microsphere-Reinforced PEG-Based Hydrogels

To improve the mechanical strength and practicability of hydrogels, polystyrene microspheres with core–shell structure were prepared by the soap-free emulsion polymerization, polyethylene glycol hydrogels with polystyrene microspheres by the in-situ polymerization. The structure, morphology, roughness, swelling property, surface energy, and mechanical properties of the microspheres and hydrogels were investigated by Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, confocal laser microscopy, swelling test, contact angle measurement, and compression test. The results showed that they have certain swelling capacity and excellent mechanical properties, and can change from hydrophobic to hydrophilic surface. The reason is that the hydrophilic chain segment can migrate, enrich, and form a hydration layer on the surface after soaking for a certain time. Introducing proper content of polystyrene microspheres into the hydrogel, the compressive strength and swelling degree improved obviously. Increasing the content of polystyrene microspheres, the surface energy of the hydrogels decreased gradually.

Morphological Analysis of PSMA/PEI Core–Shell Nanoparticles Synthesized by Soap-Free Emulsion Polymerization

Emulsion polymerization presents the disadvantage that the physical properties of polymer particles are altered by surfactant adsorption. Therefore, in the soap-free emulsion polymerization method, a hydrophilic initiator is utilized while inducing repulsion among particles on the polymer particle surface, resulting in stable polymer particle production. In this study, we developed a methodology wherein spherical and uniform poly(styrene-co-maleic anhydride) (PSMA)/polyethyleneimine (PEI) core–shell nanoparticles were prepared. Further, their morphology was analyzed. During PSMA polymerization, the addition of up to 30% maleic anhydride (MA) resulted in stable polymerization. In PSMA/PEI nanoparticle fabrication, the number of reactants increased with increased initial monomer feed amounts; consequently, the particle size increased, and as the complete monomer consumption time increased, the particle distribution widened. The styrene (St) copolymer acted as a stabilizer, reducing particle size and narrowing particle distribution. Furthermore, the monomers were more rapidly consumed at high initiator concentrations, irrespective of the initiator used, resulting in increased particle stability and narrowed particle distribution. The shell thickness and particle size were PEI feed ratio dependent, with 0.08 being the optimal PEI-to-MA ratio. The fabricated nanoparticles possess immense potential for application in environmental science and in chemical and health care industries.

Synthesis of Selenium-Containing Polystyrene Microspheres and Using as Catalyst for Oxidation of Acrolein

Selenium-containing polystyrene (DSe-PS) microspheres were synthesized by soap-free emulsion polymerization using 1,2-bis(2,3,5,6-tetrafluoro-4-vinylphenyl)diselane (FVPDSe) and divinylbenzene (DVB) as crosslinking agents. The particle size of the obtained DSe-PS was characterized by a scanning electron microscope and dynamic light scattering. The results showed that the diameter of the obtained DSe-PS microspheres could be adjusted by changing the ratio of the monomer and crosslinker/water. The diselenide moiety in the obtained DSe-PS microspheres could be oxidized to seleninic acid by H2O2 which can catalyze the oxidation of acrolein. The oxidized DSe-PS microspheres exhibited higher catalytic activity and selectivity to methyl acrylate in a model oxidation of acrolein.

Effect of Graphene Encapsulated Styrene-butyl Acrylate Copolymer Microspheres on Enhancing the Dielectric Properties of Polymethyl Methacrylate

In this work, the dielectric properties of polymethyl methacrylate (PMMA) were obviously improved by using graphene encapsulated microspheres through soap-free emulsion polymerization technique. Scanning electron microscope (SEM) observation implied that styrene-butyl acrylate copolymer (SBA) microspheres and reduced graphene oxide encapsulated SBA microspheres (rGO@SBA) was successfully obtained through using soap-free emulsion polymerization. The dielectric constant of PMMA/rGO@SBA could reach 46.64 at 1000 Hz by incorporating only 0.26 wt% rGO. On the other hand, three different PMMA based composites were also prepared by adding rGO and SBA through conventional emulsion polymerization and simple physical blending. The dielectric constant results revealed that all these composites presented low dielectric constant compared with composites through soap-free emulsion polymerization technique. The possible reason was that the isolated rGO sheets can interconnect with each other to from three-dimensional segregated network structure through hot pressing technique. SEM results demonstrated that the rGO encapsulated SBA structure could be retained after hot pressing. Therefore, soap-free emulsion polymerization technique can favorably fabricated rGO encapsulated polymer microspheres with high dielectric properties.

ICG/5-Fu coencapsulated temperature stimulus response nanogel drug delivery platform for chemo-photothermal/photodynamic synergetic therapy

The multiple diagnosis and treatment mechanisms of chemotherapy combined with photothermal/photodynamic therapy have very large application prospects in the field of cancer treatment. Therefore, in order to achieve effective and safe antitumour treatment, it is necessary to design an intelligent responsive polymer nanoplatform as a drug delivery system. Herein, the thermosensitive poly-N-isopropylacrylamide (PNIPAM) nanogel particles were prepared by soap-free emulsion polymerization and loaded with a large amount of photosensitizer indocyanine green (ICG) and anticarcinogen 5-fluorouracil (5-Fu), which effectively to realize the cooperative chemotherapy and photothermal/photodynamic therapy for tumours. The 5-Fu@ICG-PNIPAM nanogels significantly improved the bioavailability of the drug and achieved controlled release. In addition, under near-infrared laser (NIR) irradiation at 808 nm, 5-Fu@ICG-PNIPAM nanogels generated lots of heat and reactive oxygen, which significantly enhanced cellular uptake and in vitro antitumour treatment effects. The results showed that 5-Fu@ICG-PNIPAM nanogels were effectively endocytosed by HeLa cells, which also enhanced the drug’s entrance into the nucleus. Moreover, compared with alone chemotherapy or photothermal/photodynamic therapy, 5-Fu@ICG-PNIPAM nanogels significantly increased cytotoxicity under NIR irradiation, suggesting that chemotherapy and photothermal/photodynamic synergistic therapy had excellent antitumour properties. Therefore, this temperature-responsive nanogel platform probably has great application prospects in clinical antitumour treatment.