Six derivatives of poly-N-vinylcaprolactam (PNVCL) P1-P6 were synthesized via surfactant-free precipitation polymerization (SFPP) at 70 °C, with potassium persulfate (KPS) as the initiator. P5 and P6 were synthesized using the cross-linker N,N\'-Methylenebisacrylamide (MBA). The conductivity was measured to monitor the polymerization process. The hydrodynamic diameters (HDs) and polydispersity indexes (PDIs) of aqueous dispersions of P1-P6 were determined using dynamic light scattering (DLS) and zeta potential (ZP) using electrophoretic mobilities. At 18 °C for P1-P6, the HDs (nm) were 428.32 ± 81.30 and PDI 0.31 ± 0.19, 528.60 ± 84.70 (PDI 0.42 ± 0,04), 425.96 ± 115.42 (PDI 0.56 ± 0.08), 440.34 ± 106.40 (PDI 0.52 ± 0.09), 198.39 ± 225.35 (PDI 0.40 ± 0.19), and 1201.52 ± 1318.05 (PDI 0.71 ± 0.30), the and ZPs were (mV) 0.90 ± 3.23, -4.46 ± 1.22, -6.44 ± 1.82, 0.22 ± 0.48, 0.18 ± 0.79, and -0.02 ± 0.39 for P1-P6, respectively. The lower critical solution temperature ranged from 27 to 29 °C. The polymers were characterized using the ATR-FTIR method. The study concluded that the physicochemical properties of the product were significantly affected by the initial reaction parameters. Polymers P1-P4 and P6 have potential for use as drug carriers for skin applications.

Thermosensitive copolymers P1-P5 of N-isopropylacrylamide (NIPA) and poly(ethylene glycol) methyl ether methacrylates (PEGMEMs) were synthesized via surfactant-free precipitation polymerization (SFPP) using ammonium persulfate (APS) at 70 °C. The polymerization course was evaluated by the conductivity. The hydrodynamic diameters and the polydispersity indexes (PDI) of P1-P5 in the 18-45 °C range, which were assessed via dynamic light scattering (DLS), were at 18° (nm): 26.07 ± 0.54 (PDI 0.65 ± 0.03), 68.00 ± 1.10 (PDI 0.56 ± 0,02), 45.12 ± 0.57 (PDI 0.51 ± 0.03), 62.78 ± 0.40 (PDI 0.53 ± 0.003), and 92.95 ± 1.56 (PDI 0.60 ± 0.04), respectively. The lower critical solution temperatures ranged from 31 to 33 °C. The electrophoretic mobilities estimated the zeta potential in the 18-45 °C range, and at 18 °C, they were (mV): -4.64 ± 1.30, -6.91 ± 2.67, -5.85 ± 3.17, -2.28 ± 0.30, and -3.60 ± 0.96 for P1-P5, respectively. The polymers were characterized by Attenuated Total Reflectance Fourier-Transform Infrared spectroscopy (ATR-FTIR), H nuclear magnetic resonance (1H NMR), thermogravimetric analysis (TGA/DTA), Differential Scanning Calorimetry (DSC), and powder X-ray diffraction analysis (PXRD). Stable amorphous polymers were obtained. We conclude that the length of the co-monomer chain nonlinearly influences the properties of the obtained thermosensitive polymer nanostructures.

Thermosensitive polymers PS1-PS5 were synthesized via the surfactant free precipitation polymerization (SFPP) using 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPSA), and potassium persulfate (KPS) at 70 °C in aqueous environment. The effect of KPS concentrations on particle size and lower critical temperature solution (LCST) was examined by dynamic light scattering (DLS). The conductivity in the course of the synthesis and during cooling were investigated. The structural studies were performed by attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), H nuclear magnetic resonance (1H NMR), thermogravimetric analysis (TGA/DTA) and powder X-ray diffraction (PXRD). ATR-FTIR, 1H NMR and PXRD data confirmed the polymeric nature of the material. TGA/DTA curves demonstrated thermal stability up to approx. 160 °C. The effect of temperature on the hydrodynamic diameter (HD) and zeta potential (ZP) were evaluated by dynamic light scattering (DLS) and electrophoretic mobility (EM) in 18-45 °C range. The LCST values were between 30 and 34 °C. HD and polydispersity index (PDI) of aqueous dispersions of the synthesized polymers PS1-PS5 at 18 °C were found to be 226 ± 35 nm (PDI = 0.42 ± 0.04), 299 ± 145 nm (PDI = 0.49 ± 0.29), 389 ± 39 nm (PDI = 0.28 ± 0.07), 584 ± 75 nm (PDI = 0.44 ± 0.06), and 271 ± 50.00 nm (PDI = 0.26 ± 0.14), respectively. At 18 °C the ZPs of synthesized polymers suspensions were -13.14 ± 2.85 mV, -19.52 ± 2.86 mV, -7.73 ± 2.76 mV, -7.99 ± 1.70 mV, and -9.05 ± 2.60 mV for PS1-PS5, respectively. We found that the initiator concentration influences the physicochemical properties of products including the size of polymeric particles and the LCST.