The cloud point of copolymers of 2-ethyl-2-oxazoline and 2-n-propyl-2-oxazoline could be tuned from 25 degrees C to 100 degrees C by varying molecular weight and composition; the reversibility and concentration dependence of the cloud points were evaluated to assess the potential of these copoly(2-oxazoline)s as alternatives to poly(N-isopropylacrylamide).

Reversible addition-fragmentation chain transfer (RAFT) polymerizations have been performed on a Chemspeed Accelerator SLT100 automated synthesizer to polymerize N,N-(dimethylamino)ethyl methacrylate (DMAEMA) and poly(ethylene glycol) methyl ether methacrylate (PEGMA) at 70 °C. Azobis(isobutyronitrile) (AIBN) was used as source of radicals and 2-cyano-2-butyl dithiobenzoate (CBDB) as RAFT agent. A complete screening in composition of P(DMAEMA-stat-PEGMA) copolymers was elaborated from 0% of PEGMA to 100% of PEGMA. All polydispersity indices of the obtained copolymers are comprised between 1.11 and 1.30. The reactivity ratios have been determined by the extended Kelen-Tu ¨do ¨s method (r DMAEMA ) 0.93 and r PEGMA ) 0.66). The behavior of the pH-and temperature-sensitive copolymers was studied in aqueous solution by measuring the lower critical solution temperature (LCST) by UV/vis spectroscopy. The measurements were performed at three different pH values (4, 7, and 10). At pH 7 and pH 10 it has been observed that the LCST is increasing linearly with the wt % PEGMA in the copolymer feed. On the contrary, at pH 4, the hydrophilicity of the P(DMAEMA-stat-PEGMA) copolymers is too high due to the protonation of the DMAEMA units. Thus, no LCST has been detected for most of them. By varying the pH and the composition of the P(DMAEMA-stat-PEGMA) copolymers, the LCST can be easily tuned between 34.7 and 82.0 °C.

Homopolymers of methacrylic acid (MAA), monoethyleneglycol methyl ether methacrylate (MEOMA), diethyleneglycol methyl ether methacrylate (MEO 2 MA), oligo(ethyleneglycol) methyl ether methacrylate (OEGMA 475 and OEGMA 1100) and oligo(ethyleneglycol) ethyl ether methacrylate (OEGEMA 246) were synthesized with various chain lengths via reversible addition fragmentation chain transfer (RAFT) polymerization. The homopolymers of MAA, MEOMA and OEGMA 1100 did not show any cloud point (CP) in the range of 0-100 C, whereas at a pH value of 7, the CPs were found to be 20.6, 93.7, and 20.0 C for p(MEO 2 MA), p(OEGMA 475) and p(OEGEMA 246), respectively, with an initial monomer to initiator ratio of 50. Furthermore, statistical copolymer libraries of MAA with OEGMA 475 and OEGMA 1100 were prepared. The cloud points of the random copolymers of MAA and OEGMA 475 were found to be in the range of 20-90 C; surprisingly, even though the homopolymers of MAA and OEGMA 1100 did not exhibit any LCST behavior, the copolymers of these monomers at certain molar ratios (up to 40% OEGMA 1100) revealed a double responsive behavior for both temperature and pH. Finally, the cloud points were found to be in the range of 22-98 C, measured at pH values of 2, 4, and 7, while no cloud point was detected at pH 10. V

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The moisture uptake of several water-soluble polymers at different humidities was investigated with a thermal gravimetric analyzer equipped with a controlled humidity chamber. The water sorption of poly(acrylic acid) sodium salt, poly(ethylene glycol) and silica, which are known as super absorbers, were examined. In addition, various hydrophilic polymeric materials were selected according to their structural features. These included hydroxyl functions on the side chains (e.g. poly(2-hydroxyethyl methacrylate)), as well as acidic or basic functionalities (e.g. poly (dimethylaminoethyl methacrylate) or poly(vinylimidazole)). In addition, poly(2-methyl-2oxazoline) (P(MeOx)) and poly(2-ethyl-2-oxazoline) (P(EtOx)), which are well-known hydrophilic polymers, were also investigated in this context. More significant weight percent changes were obtained for P(MeOx) (60% at 90% relative humidity (RH)) in comparison to P(EtOx) (35% at 90% RH) as a result of the slight difference in hydrophilicity of the structures. The effect of the chain length on the ability for water uptake was also investigated for both poly(oxazolines). Finally, thermoresponsive polymers with a lower critical solution temperature (LCST) behavior (e.g. poly(N-isopropylacrylamide) and poly(dimethylaminoethyl methacrylate)) were also examined. The measurements for the latter polymers were performed below and above the LCST of each polymer whereby the humidities are varied from 0 to 90% with steps of 10%. Upon increasing humidity, the results revealed relatively high water uptake values (8% and 22% for P(NIPAM) and for P(DMAEMA), respectively) below the LCSTs of the polymers and, contrastingly, a small weight loss above their LCSTs. The present results allow a deeper insight into important structure-property relationships (e.g. the influence of the polymer backbone, functional groups, LCST behavior, etc. on the water-uptake properties), and will in subsequent steps permit the directed design of tailor-made polymers for selected applications.

We report on the first successful example of the preparation of triblock copolymers via a cationic ring-opening polymerization procedure. A library of 30 triblock copolymers was prepared from 2-methyl-, 2-ethyl-, 2-nonyl-, and 2-phenyl-2-oxazoline in a single-mode microwave reactor. The polymers exhibited narrow molecular weight distributions and showed only minor deviations from the targeted monomer ratio of 33:33:33. The glass-transition temperature of the triblock copolymers spanned the range from 50 to 100 °C depending on the incorporated monomers. The micellization behavior was investigated for some amphiphilic triblock copoly(2-oxazoline)s containing two hydrophilic and one hydrophobic blocks. The size of the micelles was larger when the hydrophobic block is located at one end of the triblock copoly(2-oxazoline)s, as measured by atomic force microscopy and dynamic light scattering.

No abstract

The microwave‐assisted statistical copolymerization of 2‐phenyl‐2‐oxazoline with 2‐methyl‐2‐oxazoline or 2‐ethyl‐2‐oxazoline is discussed in this contribution. Kinetic studies of these statistical copolymerizations as well as reactivity ratio determinations were performed to investigate the monomer distribution in these copoly(2‐oxazoline)s, demonstrating the formation of quasi‐diblock copolymers. In addition, the synthesis of copolymer series with monomer concentrations ranging from 0 to 100 mol % is described. These copolymer series were characterized with 1H NMR spectroscopy, gas chromatography, and gel permeation chromatography. Moreover, the glass‐transition temperatures and solubility of these copolymers were studied, and this revealing better mixing of poly(2‐methyl‐2‐oxazoline) (pMeOx) with poly(2‐phenyl‐2‐oxazoline) (pPhOx) than poly(2‐ethyl‐2‐oxazoline) (pEtOx) with poly(2‐phenyl‐2‐oxazoline) (pPhOx). © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 416–422, 2007.