Novel Polyimide-block-poly(dimethyl siloxane) copolymers: Effect of time on the synthesis and thermal properties

Polyimide-block-poly(dimethyl siloxane) copolymer was synthesized by a two-step process, initiated by coupling anhydride terminated poly(amic acid), AT-PAA with amino terminated poly(dimethyl siloxane), (NH2)2-PDMS to form poly(amic acid)-block-poly(dimethyl siloxane). The resulting copolymer is then thermally treated to produce polyimide-block-poly(dimethyl siloxane), PI-PDMS. Because of the high glass transition temperature, Tg of polyimide, it is usually cured at a high temperature of about 300°C for over 2.5 h. Copolymerization of polyimide with polysiloxane, reduces the imidization temperature while maintaining high thermomechanical properties. A series of instruments were used to monitor the progress of copolymerization. The time-based analysis of the product of copolymerization enables the optimization of the structure and properties of the copolymers. The chemical structure and composition of the copolymer were studied by Fourier Transform Infrared Spectroscopy, (FT-IR). The incorporation of PDMS blocks into the copolymer and the degree of imidization of the polyimide block increased with increasing reaction time. The change in the viscosity of the copolymerizing solution was monitored by simple shear viscometry conducted with the Brookfield Viscometer. The reported increase in solution viscosity with increasing copolymerization time is associated with increasing molecular weight of the copolymer. The intrinsic viscosity of the copolymer solution was measured as a function of copolymerization time and it was found that the intrinsic viscosity of the copolymer solution increased with increasing reaction time. The glass transition temperature (Tg) and the thermal stability of the copolymer were determined by differential scanning calorimetry, DSC and thermogravimetric analysis, and TGA, respectively. Between 25°C and 420°C, the copolymers synthesized in this study show two glass transition temperatures due to the polyimide, PI block at around 380°C and another peak associated with PDMS plasticized polyimide at about 290–300°C. The two Tg peaks observed in the DSC thermogram are believed to be indicative of the structure of a block copolymer. TGA analysis shows that the thermoxidative stability of the copolymers increased with increasing reaction time, due to the incorporation of increased amount of PDMS unit into the copolymer. The combination of increasing molecular weight of copolymer, higher degree of imidization of polyimide blocks and enhanced thermoxidative stability may translate into improved flame retardancy of copolymers. This suggested enhancement in flame retardancy in air atmosphere, is believed to be due the incorporated PDMS blocks, which can be converted into silica, SiO2, a recognized thermally stable material.

Electrospun VDF-TeFE Scaffolds Modified by Copper and Titanium in Magnetron Plasma and Their Antibacterial Activity against MRSA

Copolymer solution of vinylidene fluoride with tetrafluoroethylene (VDF-TeFE) was used for electrospinning of fluoropolymer scaffolds. Magnetron co-sputtering of titanium and copper targets in the argon atmosphere was used for VDF-TeFE scaffolds modification. Scanning electron microscopy (SEM) showed that scaffolds have a nonwoven structure with mean fiber diameter 0.77 ± 0.40 μm, mean porosity 58 ± 7%. The wetting angle of the original (unmodified) hydrophobic fluoropolymer scaffold after modification by titanium begins to possess hydrophilic properties. VDF-TeFE scaffold modification by titanium/copper leads to the appearance of strong antibacterial properties. The obtained fluoropolymer samples can be successfully used in tissue engineering.

Graft Copolymerization of Cinnamic Acid to Cassava Starch and its Viscosity Measurements

In this study, the modification of starch was conducted through graft copolymerization of cinnamic acid to result in starch-g-poly(cinnamic acid). The cinnamic acid polymerization was carried out via radical polymerization using cerium ammonium nitrate (CAN) as an initiator. The viscosity of the graft copolymer 10000 ppm dissolved in 16% NaOH solution was measured at a temperature range of 25-75 °C. The results showed that the higher the temperature the lower the viscosity. The activation energy of viscous flow for the copolymer was 18.4 kJ.mol-1. The viscosity values of the copolymer solutions were also measured in saline solutions with NaCl contents of 3−20%(w/v). For the measurements in these saline solutions, the highest viscosity was 3.39 cP at room temperature for the copolymer solution containing 5%(w/v) NaCl.

Spraying of Ultrathin Isoporous Block Copolymer Membranes—A Story about Challenges and Limitations

Isoporous membranes can be prepared by a combination of self-assembly of amphiphilic block copolymers and the non-solvent induced phase separation process. As the general doctor-blade technique suffers from high consumption of expensive block copolymer, other methods to reduce its concentration in the casting solution are sought after. Decreasing the block copolymer concentration during membrane casting and applying the block copolymer solution on a support membrane to obtain ultrathin isoporous membrane layers with e.g., spraying techniques, can be an answer. In this work we focused on the question if upscaling of thin block copolymer membranes produced by spraying techniques is feasible. To upscale the spray coating process, three different approaches were pursued, namely air-brush, 1-fluid nozzles and 2-fluid nozzles as generally used in the coating industry. The different spraying systems were implemented successfully in a membrane casting machine. Thinking about future development of isoporous block copolymer membranes in application it was significant that a continuous preparation process can be realised combining spraying of thin layers and immersion of the thin block copolymer layers in water to ensure phase-separation. The system was tested using a solution of polystyrene-block-poly(4-vinylpyridine) diblock copolymer. A detailed examination of the spray pattern and its homogeneity was carried out. The limitations of this method are discussed.

Preparation of Fluorine-Free Superhydrophobic Paper with Dual-Response of Temperature and pH

Although various superhydrophobic materials have been manufactured and effectively used for oil–water separation, it is still highly desirable to explore materials which are eco-friendly, low-cost, and multifunctional. In this paper, a stable copolymer solution was prepared from the fluorine-free superhydrophobic copolymer with dual-responsiveness of temperature and pH. The functional superhydrophobic paper was prepared by immersing paper in copolymer solution by the dip-coating method. The surface element and structure analysis of the prepared superhydrophobic paper shows that the dual-responsive copolymer adheres successfully to the surface of the paper without destroying the fiber structure of the paper. At pH ≥ 7 and T > 25 °C, the paper has a good superhydrophobic performance, while under the conditions of pH < 7 and T < 25 °C, the paper comes into a hydrophilic state. Therefore, the dual-responsive superhydrophobic paper is more likely to adapt to the complicated oil-water separation environment than the single-response.

Synthesis, Structure, Hydrodynamics and Thermoresponsiveness of Graft Copolymer with Aromatic Polyester Backbone at Poly(2-isopropyl-2-oxazoline) Side Chains

New thermoresponsive graft copolymers with an aromatic polyester backbone and poly(2-isopropyl-2-oxazoline) (PiPrOx) side chains are synthesized and characterized by NMR and GPC. The grafting density of side chains is 0.49. The molar masses of the graft-copolymer, its backbone, side chains, and the modeling poly-2-isopropyl-2-oxaziline are 74,000, 19,000, 4300, and 16,600 g·mol−1, respectively. Their conformational properties in nitropropane as well as thermoresponsiveness in aqueous solutions are studied and compared with that of free side chains, i.e., linear PiPrOx with a hydrophobic terminal group. In nitropropane, the graft-copolymer adopts conformation of a 13-arm star with a core of a collapsed main chain and a PiPrOx corona. Similarly, a linear PiPrOx chain protects its bulky terminal group by wrapping around it in a selective solvent. In aqueous solutions at low temperatures, graft copolymers form aggregates due to interaction of hydrophobic backbones, which contrasts to molecular solutions of the model linear PiPrOx. The lower critical solution temperature (LCST) for the graft copolymer is around 20 °C. The phase separation temperatures of the copolymer solution were lower than that of the linear chain counterpart, decreasing with concentration for both polymers.