RESUMEN
An 80-membered library of gels composed of monofunctional 2-ethyl-2-oxazoline and 2-nonyl-2-oxazoline and one of four selected difunctional 2-oxazolines (containing either ether or ester bonds) were synthesized by microwave-assisted ring-opening polymerizations. The difunctional 2-oxazolines were prepared from the thiol-ene reaction of glycol dimercaptoacetate or 2,2'-(ethylenedioxy)diethanethiol and 2-but-3'-enyl-2-oxazoline or 2-dec-9'-enyl-2-oxazoline. 53 of the gels exhibited glass-transition temperatures, which ranged from -5.9 to 45.3 °C. 13 Derivatives exhibited glass-transition temperatures in the range from 20 to 30 °C, which renders them stiff at room temperature and flexible at body temperature. The gels that did not contain any 2-ethyl-2-oxazoline acted as lipogels, whereas the gels that did not contain any 2-nonyl-2-oxazoline acted as hydrogels; all other gels may be classified as amphigels. The swelling degrees were measured by gravimetry and maximum swelling degrees of 6 (in water) were observed for the gels with the lowest degrees of crosslinking. In a second approach, the synthesis of crosslinked networks had been achieved by performing the polymeranalogous thiol-ene reaction of copoly(2-oxazoline)s containing olefinic side-chains and glycol dimercaptoacetate. This soft strategy enabled the straightforward loading of such gels with active pharmaceutical ingredients without altering them. This method delivered gels with selected composition exhibiting a targeted disc-shape and loaded with active pharmaceutical ingredients from one-step syntheses. The maximum swelling degrees of these specimens were found to be in accordance with the ones from the first route investigated. Preliminary degradation studies were performed at 25 °C; these types of gels were found to be degraded in alkaline media as well as by esterases.
RESUMEN
Unlike any other polymer class, the (co-)poly(2-oxazoline)s have tremendously benefited from the introduction of microwave reactors into chemical laboratories. This review focuses on the research activities in the area of (co-)poly(2-oxazoline)s prepared by microwave-assisted syntheses and, correspondingly, summarizes the current-state-of the-art of the microwave-assisted synthesis of 2-oxazoline monomers and the microwave-assisted ring-opening (co-)polymerization of 2-oxazolines as well as prominent examples of post-polymerization modification of (co-)poly(2-oxazoline)s. Special attention is attributed to the kinetic analysis of the microwave-assisted polymerization of 2-oxazolines and the discussion of non-thermal microwave effects.
RESUMEN
The single crystal X-ray analysis of the ester-functionalized 2-oxazoline, methyl 3-(4,5-dihydrooxazol-2-yl)propanoate, revealed π-electron delocalization along the N-C-O segment in the 2-oxazoline pentacycle to significant extent, which is comparable to its counterpart along the O-C-O segment in the ester. Quantum chemical calculations based on the experimental X-ray geometry of the molecule supported the conjecture that the N-C-O segment has a delocalized electronic structure similar to an ester group. The calculated bond orders were 1.97 and 1.10 for the N=C and C-O bonds, and the computed partial charges for the nitrogen and oxygen atoms of -0.43 and -0.44 were almost identical. In the ester group, the bond orders were 1.94 and 1.18 for the C-O bonds, while the partial charges of the oxygen atom are -0.49 and -0.41, which demonstrates the similar electronic structure of the N-C-O and O-C-O segments. In 2-oxazolines, despite the higher electronegativity of the oxygen atom (compared to the nitrogen atom), the charges of the hetero atoms oxygen and nitrogen are equalized due to the delocalization, and it also means that a cationic attack on the nitrogen is possible, enabling regioselectivity during the initiation of the cationic ring-opening polymerization of 2-oxazoline monomers, which is a prerequisite for the synthesis of materials with well-defined structures.
RESUMEN
The copoly(2-oxazoline) pNonOx80 -stat-pDc(=) Ox20 can be synthesized from the cationic ring-opening copolymerization of 2-nonyl-2-oxazoline NonOx and 2-dec-9'-enyl-2-oxazoline Dc(=) Ox in the ionic liquid n-hexyl methylimidazolium tetrafluoroborate under microwave irradiation in 250â g/batch quantities. The polymer precipitates upon cooling, enabling easy recovery of the polymer and the ionic liquid. Both monomers can be obtained from fatty acids from renewable resources. pNonOx80 -stat-pDc(=) Ox20 can be used as polymer in a photoresist (resolution of 1â µm) based on UV-induced thiol-ene reactions.