RESUMO
The polycondensation of diamines and dialdehydes promoted by an N-heterocyclic carbene (NHC) catalyst in the presence of a quinone oxidant and hexafluoro-2-propanol (HFIP) is herein presented for the synthesis of oligomeric polyamides (PAs), which are obtained with a number-average molecular weight (Mn ) in the range of 1.7-3.6â kg mol-1 as determined by NMR analysis. In particular, the utilization of furanic dialdehyde monomers (2,5-diformylfuran, DFF; 5,5'-[oxybis(methylene)]bis[2-furaldehyde], OBFA) to access known and previously unreported biobased PAs is illustrated. The synthesis of higher molecular weight PAs (poly(decamethylene terephthalamide, PA10T, Mn = 62.8â kg mol-1 ; poly(decamethylene 2,5-furandicarboxylamide, PA10F, Mn = 6.5â kg mol-1 ) by a two-step polycondensation approach is also described. The thermal properties (TGA and DSC analyses) of the synthesized PAs are reported.
RESUMO
In this work, the rheological behavior of stable poly(lactic acid) (PLA) dispersions in water, intended for coating applications, was investigated. The newly prepared dispersion consists of PLA particles with an average diameter of 222 ± 2 nm based on dynamic light scattering (DLS) and scanning electron microscopy (SEM) analyses, at concentrations varying in the 5-22 wt % range. Xanthan gum (XG), a bacterial polysaccharide, was used as a thickening agent to modulate the viscosity of the formulations. The rheological properties of the PLA dispersions with different XG and PLA contents were studied in steady shear, amplitude sweep, and frequency sweep experiments. Under steady shear conditions, the viscosity of all the formulations showed a shear-thinning behavior similar to XG solutions in the whole investigated 1-1000 s-1 range, with values dependent on both PLA particles and XG concentrations. Amplitude and frequency sweep data revealed a weak-gel behavior except in the case of the most diluted sample, with moduli dependent on both PLA and XG contents. A unified scaling parameter was identified in the volume fraction (Ï) of the PLA particles, calculated by considering the dependence of the continuous phase density on the XG concentration. Accordingly, a master curve at different volume fractions was built using the time-concentration-superposition approach. The master curve describes the rheological response of the system over a wider frequency window than the experimentally accessible one and reveals the presence of a superimposed ß relaxation process in the high-frequency region.
RESUMO
Rigid semi-Interpenetrated Polymer Network (semi-IPN) foam based on poly(vinyl chloride) (PVC) and crosslinked polyurea/isocyanurate are complex materials that at present are not recyclable. They are used in many fields, including wind blade cores. In this work we studied the depolymerization of the crosslinked portion of the foam under glycolysis conditions for the separation and reuse of the individual components. Reaction products were characterized by FT-IR, NMR, solvent solubility, DSC, elemental analysis, titration of amine and hydroxyl groups and rheology measurements. Triisocyanurates and urea moieties were synthesized and used as model compounds. Glycolysis conditions were optimized to maximize depolymerization while minimizing PVC degradation. The parameters studied were reaction time (8 min to 3 h), temperature (155 to 200 °C), catalyst (potassium acetate or dibutyl tin dilaurate (DBTL)), glycol (ethylene glycol, 1,4 butanediol, diethylene glycol, dipropylene glycol, polyethylene glycol), as well as the effect of PVC thermal stabilizers such as hindered phenols and organo-phosphites. The results showed that the optimal reaction condition for foam glycolysis is 165-175 °C for 20-30 min, using DBTL as catalyst and including thermal stabilizers. No drastic difference was noticed by the kind of glycol used, except for PEG that led to greater PVC degradation. The greatest part of the crosslinked portion (≥90 %) was depolymerized and the result were mainly hydroxyl- and in minor amount amine- terminated oligomers. The recovered PVC (purity roughly 90 %) had a low degree of degradation and a viscosity suitable for its processing as thermoplastic material, i.e. by injection moulding.
Assuntos
Glicólise , Cloreto de Polivinila , Cloreto de Vinil , Aminas , Butileno Glicóis , Etilenoglicóis , Fenóis , Polietilenoglicóis/química , Polímeros/química , Cloreto de Polivinila/química , Acetato de Potássio , Solventes , Espectroscopia de Infravermelho com Transformada de Fourier , Estanho , UreiaRESUMO
A green, effective methodology for the preparation of water-based dispersions of poly(lactic acid) (PLA) for coating purposes is herein presented. The procedure consists of two steps: in the first one, an oil-in-water emulsion is obtained by mixing a solution of PLA in ethyl acetate with a water phase containing surfactant and stabilizer. Different homogenization methods as well as oil/water phase ratio, surfactant and stabilizer combinations were screened. In the second step, the quantitative evaporation of the organic provides water dispersions of PLA that are stable, at least, over several weeks at room temperature or at 4 °C. Particle size was in the 200-500 nm range, depending on the preparation conditions, as confirmed by scanning electron microscope (SEM) analysis. PLA was found not to suffer significant molecular weight degradation by gel permeation chromatography (GPC) analysis. Furthermore, two selected formulations with glass transition temperature (Tg) of 51 °C and 34 °C were tested for the preparation of PLA films by drying in PTFE capsules. In both cases, continuous films that are homogeneous by Fourier-transform infrared spectroscopy (FT-IR) and SEM observation were obtained only when drying was performed above 60 °C. The formulation with lower Tg results in films which are more flexible and transparent.
RESUMO
A novel vinylogous aldol addition of alkylidene oxindole with 1-trifluoromethyl-3-alkylidene-propan-2-ones is presented. The reaction, catalyzed by a bifunctional tertiary amine, provides an efficient application of the vinylogous reactivity of oxindoles for the preparation of enantioenriched trifluoromethylated allylic alcohols.
RESUMO
BACKGROUND: Patients are showing an increasing interest in the use of complementary and alternative medicine (CAM). Most nurses are open to the adoption of CAM into clinical nursing practice, but they may experience a lack of knowledge about the safe and effective use of these therapies. Several studies concerning nurses' knowledge and attitudes toward CAM have been published, but only in one, the authors (Shorofi and Arbon) used a validated questionnaire. In Italy, there are no validated questionnaires to investigate this aspect of nursing practice. PURPOSE: To test the psychometric properties of the Italian Shorofi and Arbon questionnaire for use with Italian nurses. METHODS: A forward-backward translation method was used to translate the questionnaire from English to Italian. Content validity, face validity and reliability were established. RESULTS AND CONCLUSIONS: This study examined the potential usefulness of the Shorofi and Arbon questionnaire for the evaluation of CAM knowledge of Italian speaking nurses, which showed good content validity and good reliability.