The synthesis of 6-trifluoroethyl-l-lysine: a method to introduce functionality at C-6 of l-lysine

Described is a method of introducing trifluoroalkyl groups at C-6 of lysine. This chemistry has the potential to introduce a variety of functionality at C-6 of lysine.     

Dark cure studies of cationic photopolymerizations of epoxides: Characterization of kinetic rate constants at high conversions

The effective propagation rate constant (k_p; averaged over all the propagating active centers) was characterized for solvent‐free cationic photopolymerizations of phenyl glycidyl ether over the entire range of conversions, including the high conversion regime in which mass transfer limitations become important. The profile for the k_p as a function of conversion was found to exhibit a constant plateau value at low to intermediate conversions, followed by a monotonic increase above a threshold value of conversion. To explain this trend, it is proposed that at high conversion the diffusional mobility of the photoinitiator counterion is reduced whereas the mobility of the cationic active center remains high because of reactive diffusion. Therefore, with increasing conversion, the average distance between the active centers and counterions may increase, resulting in an increase in the propagation rate constant. The profiles for the k_p values were investigated as a function of the temperature, photoinitiator anion, and photoinitiator concentration. As the photoinitiator concentration was increased, the plateau value of the effective propagation rate constant decreased whereas the threshold conversion increased. All of the experimental trends are consistent with the proposed increase in ion separation at high conversions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4409–4416, 2004     

New functionalized polyesters to achieve controlled architectures

Following our continued interest in the production of bioerodible and biodegradable functional polymers for biomedical applications, we synthesized and characterized new unsaturated polyesters. The presence of functional groups in the polymer backbone provided sites for chemical modification, and through a variation in the structure, the physical properties, such as the hydrophilicity and solubility, could be affected. With 1,1-di-n-butyl-stanna-2,7-dioxacyclo-4-heptene as the initiator in the ring-opening polymerization of polyesters, a new set of functionalized polyesters was created. The polymerization of ϵ-caprolactone resulted in poly(ϵ-caprolactone) with a double bond incorporated into the structure. The polymers were obtained in a controlled manner with low molecular dispersities. The double bond was previously incorporated into L -lactide polymers, and the two reactions were compared in this study. The conversion of ϵ-caprolactone, with a degree of polymerization of 50, was completed within 140 min, whereas for L -lactide, only a 45% conversion took place in the same period of time. The dispersities were somewhat higher with ϵ-caprolactone because of the higher reaction rate and, therefore, lower selectivity. The incorporated CC double bond in the polyesters provided a variety of opportunities for further modifications. In this case, the double bond of the L -lactide macromonomers was oxidized into epoxides. Epoxidation was carried out with m-chloroperoxybenzoic acid as a chemical reagent. The conversion of the double bonds into epoxides was completed, and the obtained yields were good (>95%). As a result of the mild reaction conditions, the epoxidation of the double bond was carried out quantitatively without any side reactions. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 444–452, 2004     

Synthesis,characterization, and curing kinetics of novel ladder‐like polysilsesquioxanes containing side‐chain maleimide groups

Two ladder‐like polysilsesquioxanes (LPS) containing side‐chain maleimide groups have been synthesized successfully by reacting N‐(4‐hydroxyphenyl)maleimide (HPM) with LPS containing 100 mol % of chloropropyl groups (Ladder A ) and 50 mol % of each methyl and chloropropyl group (Ladder B ). HPM was synthesized by reacting maleic anhydride with 4‐aminophenol, and the resulting amic acid was imidized using p‐toluenesulfonic acid as a catalyst (Scheme 1 ). The LPSs were characterized by Fourier transform infrared (FTIR), ¹H nuclear magnetic resonance (NMR), proton‐decoupled ¹³C NMR, ²⁹Si NMR, wide‐angle X‐ray diffraction (WAXD), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). Characterization indicated that these polymers had ordered ladder‐like structures with possible defects. These polymers were soluble in common solvents at ambient temperature, which suggested that they were not crosslinked. Both the polymers and the HPM were cured, and their kinetics were followed by dynamic DSC. The Ozawa and Kissinger methods were used to calculate activation energies for curing. Curing increased the temperature at which both 5% weight loss and maximum rate of weight loss were observed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4036–4046, 2004