Thermoresponsive Molecular Brushes with a Rigid-Chain Aromatic Polyester Backbone and Poly-2-alkyl-2-oxazoline Side Chains

A new polycondensation aromatic rigid-chain polyester macroinitiator was synthesized and used to graft linear poly-2-ethyl-2-oxazoline as well as poly-2-isopropyl-2-oxazoline by cationic polymerization. The prepared copolymers and the macroinitiator were characterized by NMR, GPC, AFM, turbidimetry, static, and dynamic light scattering. The molar masses of the polyester main chain and the grafted copolymers with poly-2-ethyl-2-oxazoline and poly-2-isopropyl-2-oxazoline side chains were 26,500, 208,000, and 67,900, respectively. The molar masses of the side chains of poly-2-ethyl-2-oxazoline and poly-2-isopropyl-2-oxazoline and their grafting densities were 7400 and 3400 and 0.53 and 0.27, respectively. In chloroform, the copolymers conformation can be considered as a cylinder wormlike chain, the diameter of which depends on the side chain length. In water at low temperatures, the macromolecules of the poly-2-ethyl-2-oxazoline copolymer assume a wormlike conformation because their backbones are well shielded by side chains, whereas the copolymer with short side chains and low grafting density strongly aggregates, which was visualized by AFM. The phase separation temperatures of the copolymers were lower than those of linear analogs of the side chains and decreased with the concentration for both samples. The LCST were estimated to be around 45 °C for the poly-2-ethyl-2-oxazoline graft copolymer, and below 20 °C for the poly-2-isopropyl-2-oxazoline graft copolymer.

Synthesis of Mono (Ethylene Glycol)-Based Polyurethane and Effect of Chain Extender on Its Associated Properties

This study depicts the investigations of the effect of composition of aromatic polyester polyol produced from terephthalic acid (TPA) and different concentrations of monoethylene glycol (mEG) as a chain extender on the mechanical properties of polyurethane (PU) elastomer. Aromatic polyester polyols are prepared via the poly-esterification of adipic acid, terephthalic acid, catalyst, and mono ethylene glycol; while a polyurethane elastomer is formulated via the pre-polymerization of polyol with pure monomeric Methylene diphenyl diisocyanate (MDI.) Mechanical properties of polyurethane elastomers are examined, such as hardness via shore A hardness, apparent density via ASTM (American Society for Testing and Materials) D1622–08, and abrasion wear resistance via a Deutches Institut fur Normung (DIN) abrasion wear resistance tester. Structural properties are investigated through Fourier-transform infrared spectroscopy (FTIR) analysis. Results reveal that the shore A hardness of the PU elastomer increases with an increasing concentration of mEG from 4g to 12g. Nevertheless, the elastomer’s density depicts a reduction with an increasing extender content. The abrasion wear resistance of polyurethane, however, increases with an increasing concentration of glycol. A structural analysis through FTIR confirms the formation of polyurethane elastomer through the characteristic peaks demonstrated.

Temperature-Modulated Scanning Calorimetry of Melting–Recrystallization of Poly(butylene terephthalate)

The melting and recrystallization behaviors of poly(butylene terephthalate) (PBT) were investigated using temperature-modulated scanning calorimetry in both fast- and conventional slow-scan modes. With this method, the response of multiple transition kinetics, such as melting and recrystallization, can be differentiated by utilizing the difference in the time constants of the kinetics. In addition to the previous result of temperature-modulated fast-scan calorimetry of polyethylene terephthalate (PET), the supporting evidence of another aromatic polyester, PBT, confirmed the behavior of the exothermic process of recrystallization, which proceeds simultaneously with melting on heating scan in the temperature range of double melting peaks starting just above the crystallization temperature up to the main melting peak. Because the crystallization of PBT is much more pronounced than that of PET, similar behavior of recrystallization was obtained by the conventional temperature-modulated differential scanning calorimetry at a slow-scan rate.

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.