Preparation and testing of a solid secondary plasticizer for PVC produced by chemical degradation of post-consumer PET.

Post-consumer poly(ethylene therephthalate) (PET) obtained from milled water bottles was chemically degraded by glycolysis, using suitable amounts of diethylene glycol (DEG) and Ca/Zn stearate as catalyst system. The process was carried out by employing a melt mixer as the chemical reactor, which is the facility generally used for plastic compounding. The degraded PET products were first characterized from structural and thermal point of view by Fourier transform infrared spectroscopy (FTIR), Proton nuclear magnetic resonance ((1)H NMR), Size exclusion chromatography (SEC) Differential scanning calorimetry (DSC) and Thermogravimetric analysis (TGA), and thereafter used alone or together with di(2-ethylhexyl) phthalate (DEHP) in poly(vinyl chloride) PVC formulations. The plasticization was, in fact, accomplished by using a binary system consisting of DEHP as primary plasticizer and a degraded PET product as secondary plasticizer (SP). The obtained materials were characterized through the main methods used to assess flexible PVC compounds: hardness in Shore A scale, thermal properties and quantitative migration of the plasticizer. The solid secondary plasticizer obtained from post-consumer PET improves both the processing characteristics and the thermal stability of the final flexible PVC compounds while maintaining their hardness within the top values of the Shore A scale. In addition, a considerable reduction of the plasticizers migration (23%) was obtained by optimizing the formulation.

Effect of osteopathic manipulative treatment on length of stay in a population of preterm infants: a randomized controlled trial.

BACKGROUND: The use of osteopathic manipulative treatment (OMT) in preterm infants has been documented and results from previous studies suggest the association between OMT and length of stay (LOS) reduction, as well as significant improvements in several clinical outcomes. The aim of the present study is to investigate the effect of OMT on LOS in premature infants. METHODS: A randomized controlled trial was conducted on preterm newborns admitted to a single NICU between 2008-2009. N=110 subjects free of medical complications and with gestational age >28 and < 38 weeks were enrolled and randomized in two groups: study group (N=55) and control group (N=55). All subjects received routine pediatric care and OMT was performed to the study group for the entire period of hospitalization. Endpoints of the study included differences in LOS and daily weight gain. RESULTS: Results showed a significant association between OMT and LOS reduction (mean difference between treated and control group: -5.906; 95% C.I. -7.944, -3.869; p<0.001). OMT was not associated to any change in daily weight gain. CONCLUSIONS: The present study suggests that OMT may have an important role in the management of preterm infants hospitalization. TRIAL REGISTRATION: ClinicalTrials.gov, NCT01544257.

Dye-containing polymers: methods for preparation of mechanochromic materials.

The detection of mechanical stress in polymeric materials through optical variations has attracted considerable interest over the past ten years. In this tutorial review, the current state of knowledge concerning the preparation of polymers with mechanochromic features is summarized. Two types of procedures are illustrated and thoroughly discussed along with their respective structure-property relationships: the first resides in the physical dispersion of the dye in the form of supramolecular aggregates in a preformed polymer matrix; the second involves the covalent insertion of chromophoric units into the macromolecule backbone or side chains. Herein we review the simplicity of the preparative routes available, and their influence over the properties of the resulting dye-polymer systems, by focussing on the most illustrative examples described in the literature. Special reference is made to stimuli-responsiveness as a mechanical means towards innovative smart and intelligent materials.

Morphology development and stability of polypropylene/organoclay nanocomposites.

A series of polypropylene (PP)/organoclay nanocomposites with varied concentrations of clay, from 1 to 7 wt%, was successfully prepared via melt intercalation using a PP functionalized with maleic anhydride as compatibilizer. The morphology/property relationships of the nanocomposites were investigated by XRD, TGA and DSC analyses. Two distinct groups of composites, from a quasi-exfoliated to an intercalated/flocculated morphology, were identified. In particular, intercalated/flocculated morphologies were obtained for those composites with an organoclay concentration beyond the threshold (3 wt%), as evidenced by XRD analysis and confirmed by the increase of the glass transition temperature. This last effect was related to the confinement of polymer chains between the silicate layers, generating a reduction of the chain mobility. The variable increase of the thermal stability of the nanocomposites was also likely related to the different degree of exfoliation/intercalation of the samples. The toluene extraction of composites was used as a powerful methodology to distinguish between polymer phases differently interacting with the inorganic surface: composites having a semi-exfoliated structure were split into two fractions having a similar morphology. For those samples having the higher organoclay concentration and intercalated morphology, a toluene-residue fraction was obtained containing almost all the clay present in the pristine composite. Furthermore, in this case the morphological analysis of the residue fraction evidenced a collapse of the inorganic structure compared to that of the unextracted composite. A careful characterization of both soluble and residue fractions is reported and the results are discussed considering the interactions at the interface between the functionalized PP chains and silicate layers and their effects on the organoclay dispersion degree and stability.

The relevance of the collaborative effect in determining the performances of photorefractive polymer materials.

A derivative of 2-methylindole, 3-[2-(4-nitrophenyl)ethenyl]-1-allyl-2-methylindole, NPEMI-A, is studied for its photoconductivity and photorefractivity behaviour. Its blends with the organic polymer poly-(2,3-dimethyl-N-vinylindole), PVDMI, are also investigated. Due to the expected and devised mutual solubility of the two components of the blends, it is possible to carry out measurements with the weight percent of the chromophore NPEMI-A changing from zero to 100. Films were produced by a squeezing process between two ITO-covered glass sheets. No opacity phenomena, that are so common for many other organic blends due to the segregation of the dissolved chromophore, are observed. The photorefractive optical gain Gamma(2) is obtained as a function of the chromophore content. Differential scanning calorimetry measurements (DSC) are also carried out to obtain the whole change of the glass transition temperature T(g) as a function of the amount of chromophore contained in the blends. From the experimental trend of T(g) a meaningful quantitative estimate of the value of the electrostatic interactions acting in the studied blends, is obtained. The importance of the value of T(g), and of the electrostatic interactions, in determining the extent of the photorefractivity is clearly evident. The results are compared for NPEMI-A (Gamma(2) = 210 cm(-1)) and for NPEMI-E (Gamma(2) approximately = 2000 cm(-1)) that has a N-2-ethylhexyl group instead of a N-allyl group. The Pockels and Kerr contributions and--for the first time--a "collaborative effect" of the photorefractivity of NPEMI-A are distinguished and quantitatively evaluated.

Unconditionally stable indole-derived glass blends having very high photorefractive gain: the role of intermolecular interactions.

The photorefractivity of an indole derivative and of its polymer blends has been studied at room temperature. The indole derivative 3-[2-(4-nitrophenyl)ethenyl]-1-(2-ethylhexyl)-2-methylindole (NPEMI-E) is a typical low-molecular-weight glass-forming molecule having peculiar nonlinear optics characteristics. It is unconditionally soluble in the photoconductive poly-(N-vinyl-2,3-dimethylindole) so that all the possible blends can be studied for a weight percent (wt. %) content of NPEMI-E ranging from zero to 100. A very high and sharp maximum of the photorefractive optical gain Gamma(2) approximately 2000 cm(-1) was obtained for a NPEMI-E wt. % content of about 90. On the basis of recently published theoretical calculations, we have made the hypothesis that the rapid change of Gamma(2) can also be ascribed to a correspondingly quick variation of the molecular electro-optic parameters of the dissolved chromophore for some well distinguished values of its concentration in the polymer matrix. Differential scanning calorimetry measurements were made and the results carefully analyzed with the aim of obtaining information on the intermolecular interactions. These last measurements also allowed rationalizing the unconditionally stable glass appearance of the obtained blends. Measurements of spectroscopic ellipsometry were also made on blends with different NPEMI-E content.

High-resolution poly(ethylene terephthalate) (PET) hot embossing at low temperature: thermal, mechanical, and optical analysis of nanopatterned films.

In this work we present controlled, low-damage nanotopographic surface modification of poly(ethylene terephthalate) (PET). High-resolution nanopatterning over macroscopic areas was performed by " low-temperature" hot embossing lithography (HEL). While for standard HEL the temperature is typically raised up to many tens of Celsius degrees above the polymer glass transition temperature (Tg), we demonstrate optimal results at a temperature very close to the bulk Tg of PET (72 degrees C). Nanopits and nanobarcodes were transferred onto the surface of PET commercial sheets, demonstrating reliable sub-100 nm resolution over macroscopic areas. Sample optical, mechanical, and thermal characteristics were systematically analyzed before and after embossing at low (75 degrees C) and high (150 degrees C) temperature by attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy, tensile tests, and differential scanning calorimetry (DSC). We show that, while conventional high-temperature HEL can lead to dramatic degradation of the polymer in terms of transparency, flexibility, and crystallinity content, our low-temperature process fully maintains original surface and bulk substrate properties.

Organophilic Boehmite nanoparticles by ATRP methacrylates polymerization: synthesis, characterization and dispersion in polypropylene.

Boehmite nanoparticles covered with a polymer shell enhancing the organophilicity of the surface were prepared by physical adsorption of a polyelectrolyte atom transfer radical polymerization (ATRP) macroinitiator followed by graft-polymerization of methyl methacrylate or 2-hydroxyethyl methacrylate. The presence of polymer chains adsorbed/grafted on the Boehmite was confirmed by attenuated total reflection infrared (ATR-IR) spectroscopy and by thermo-gravimetric analysis (TGA), which showed a significant amount of polymer covering the particles. The methodology of polymerization and the kinetics suggested the possibility to modulate the amount, type and thickness of grafted polymer shell. These organic-inorganic hybrid materials were melt compounded in a Brabender mixer with isotactic polypropylene in the presence of functionalized polypropylene. The dispersion degree of Boehmite nanoparticles in the polypropylene matrix as well as their reinforcing effect were studied by morphology characterization [scanning electron microscopy (SEM) and X-ray diffraction (XRD)], whereas thermal and thermo-mechanical properties were assessed by differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA).

Modification of gelatin by reaction with 1,6-diisocyanatohexane.

1,6-Diisocyanatohexane and dimethyl sulfoxide were exploited as crosslinking agent and reaction solvent, respectively, for gelatin modification. Crosslinked samples were fractionated and analyzed by thermogravimetric analysis, infrared spectroscopy, acid and base titrations, and swelling measurements. The yield of crosslinking was found to increase with increasing diisocyanate and gelatin concentrations and the amount of bound crosslinker was evaluated. The chemical analysis of the reaction products allowed the process parameters to be related to the properties of the textile/gelatin composites. For this purpose poly(propylene)-, poly(ethylene terephthalate)-, and cotton-based textiles were treated to prepare soft and dimensionally stable supported materials with a gel phase composed of gelatin.

Photorefractivity of poly-N-vinylindole-based materials as compared with that of poly-N-vinylcarbazole-based blends.

The asymmetric two-beam coupling technique has been employed to measure the photorefractivity of thin films of polymer blends containing 2,5-dimethyl-4-(p-nitrophenylazo)anisole as the nonlinear optical component. Poly-(1-vinylindole) and poly-(2,3-dimethyl-1-vinylindole) were the photoconductive polymer counterparts. The values of the photorefractivity are reported. It appears that they are comparable with those of similar blends based on the well-known poly-(9-vinylcarbazole) (PVK), here considered as a reference standard. Careful differential scanning calorimetry analyses have been accomplished on the different blends taken into account to rationalize the significantly longer shelf lifetime of the indolyl-based films with respect to the PVK-based blends.

Nanoparticles from polylactide and polyether block copolymers: formation, properties, encapsulation, and release of pyrene--fluorescent model of hydrophobic drug.

Polylactide-b-polyglycidol-b-poly(ethylene oxide) terpolymers and their derivatives with carboxyl and 4-(phenylazo)phenyl labels in polyglycidol blocks were used for formation of nanoparticles. Nanoparticles were produced by self assembly of terpolymer macromolecules in water above the critical aggregation concentration and by dialysis of terpolymer solutions in 1,4-dioxane against water. For terpolymers with 4-(phenylazo)phenyl labels critical aggregation concentrations increased after irradiation with UV light (300 < lambda < 400 nm) inducing conformational change of the label from trans- to cis-conformation. Diameters of nanoparticles obtained by self-assembly of macromolecules ranged from 20 to 44 nm. Dialysis yielded nanoparticles with bimodal diameter distribution. One fraction had diameters below 35 nm and diameters of the second fraction were in a range from 350 to 2300 nm, depending on terpolymer structure. Mixtures of terpolymers with poly(L,L-lactide) and poly(D,D-lactide) blocks yielded nanoparticles with diameters from 350 to 440 nm. Pyrene was incorporated into nanoparticles by partition between solution and nanoparticles or directly during particle formation by dialysis. Monitoring of pyrene release from nanoparticles suggests that a fraction of this compound was entrapped into the polylactide core whereas the remaining one was located in the polyether rich shell. The release from shells is faster for nanoparticles made from copolymers with carboxyl labels in polyglycidol blocks.

Structure of an associating polymer melt in a narrow slit by molecular dynamics simulation.

Molecular dynamics simulation has been used to study the equilibrium properties of a generic coarse-grained polymer melt with associating terminal groups, confined in a narrow slit by two atomically smooth walls. Simulations were carried out as a function of wall separation and attracting strength as well as polymer end-end interaction strength. We find that confinement has an important effect on the melt properties. In particular, strongly attracting walls can produce radical changes in chain conformation, the nature of the transient network, and the structure of the aggregates formed by the associating terminals.