Lignin-Based Polyurethanes from the Blocked Isocyanate Approach: Synthesis and Characterization.

Lignin, the world's second most abundant biopolymer, has been investigated as a precursor of polyurethanes due to its high availability and large amount of hydroxyls present in its structure. Lignin-based polyurethanes (LPUs) are usually synthesized from the reaction between lignin, previously modified or not, and diisocyanates. In the present work, LPUs were prepared, for the first time, using the blocked isocyanate approach. For that, unmodified and hydroxypropylated Kraft lignins were reacted with 4,4'-methylene diphenyl diisocyanate in the presence of diisopropylamine (blocking agent). Castor oil was employed as a second polyol. The chemical modification was confirmed by 31P nuclear magnetic resonance (31P NMR) analysis, and the structure of both lignins was elucidated by a bidimensional NMR technique. The LPUs' prepolymerization kinetics was investigated by temperature-modulated optical refractometry and Fourier-transform infrared spectroscopy. The positive effect of hydroxypropylation on the reactivity of the Kraft lignin was verified. The structure of LPU prepolymers was accessed by bidimensional NMR. The formation of hindered urea-terminated LPU prepolymers was confirmed. From the results, the feasibility of the blocked isocyanate approach to obtain LPUs was proven. Lastly, single-lap shear tests were performed and revealed the potential of LPU prepolymers as monocomponent adhesives.

Mechanism and Kinetics of Lipase-Catalyzed Polycondensation of Glycerol and Sebacic Acid: Influence of Solvent and Temperature.

The mechanism for theCandida antacticalipase B (CALB)-catalyzed polycondensation of glycerol and sebacic acid in polar solvents was proposed based on the profile of formation and consumption of the glyceridic species in the reaction media and on the occurrence of the acyl migration reaction. The acyl migration is mainly responsible for the esterification of the secondary hydroxyl of glycerol and in an opposite way to the regioselective CALB-catalyzed esterification of primary hydroxyls. The enzymatic esterification of glycerol primary hydroxyls occurs preferentially up to carboxylic acid conversions of approximately 0.60-0.75 with rate constants in the range of 0.07-1.44 L mol-1 h-1, depending on the solvent. Above carboxylic acid conversions of 0.60-0.75, acyl migration occurs in parallel to enzymatic esterification with rate constants of approximately 0.04-0.12 h-1 and is the rate-limiting step of the polymerization. The hydrogen bonding accepting ability of the solvents is the main parameter that dictates the enzymatic catalysis rate. However, the magnitude of the polymer-solvent interaction governs the polymer chain growth. Acetonitrile has a lower hydrogen bonding accepting ability and a less favorable polymer-solvent interaction compared with the other polymer-solvent pairs, and polycondensation achieves the highest enzymatic rate constant of approximately 0.84-1.44 L mol-1 h-1; however, low molar mass polymers with Mn = 1.4 kDa were formed. On the other hand, acetone has intermediate hydrogen bonding accepting ability and optimal intermediate polymer-solvent interactions and, therefore, an intermediate enzymatic rate constant of approximately 0.41-0.52 L mol-1 h-1, and the highest molar mass polymers with Mn = 4.9-9.4 kDa were obtained.

Plasticization of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with an Oligomeric Polyester: Miscibility and Effect of the Microstructure and Plasticizer Distribution on Thermal and Mechanical Properties.

In the last few decades, many efforts have been made to make poly(3-hydroxybutyrate) (PHB) and its copolymers more suitable for industrial production and large-scale use. Plasticization, especially using biodegradable oligomeric plasticizers, has been one of the strategies for this purpose. However, PHB and its copolymers generally present low miscibility with plasticizers. An understanding of the plasticizer distribution between the mobile and rigid amorphous phases and how this influences thermal, mechanical, and morphological properties remains a challenge. Herein, formulations of poly(hydroxybutyrate-co-valerate) (PHBV) plasticized with an oligomeric polyester based on lactic acid, adipic acid, and 1,2-propanediol (PLAP) were prepared by melt extrusion. The effects of the PLAP content on the processability, miscibility, and microstructure of the semicrystalline PHBV and on the thermal, morphological, and mechanical properties of the formulations were investigated. The compositions of the mobile and rigid amorphous phases of the PHBV/PLAP formulations were easily estimated by combining dynamic mechanical data and the Fox equation, which showed a heterogeneous distribution of PLAP in these two phases. An increase in the PLAP mass fraction in the formulations led to progressive changes in the composition of the amorphous phases, an increase of both crystalline lamellae and interlamellar layer thickness, and a decrease in the melting and glass transition temperatures as well as the PHBV stiffness. The Flory-Huggins interaction parameter varied with the formulation composition in the range of -0.299 to -0.081. The critical PLAP mass fraction of 0.37 obtained from thermodynamic data is close to the value estimated from dynamic mechanical analysis (DMA) data and the Fox equation. The mechanical properties showed a close relationship with the distribution of PLAP in the rigid and mobile amorphous phases as well as with the microstructure of the crystalline phase of PHBV in the formulations.

Colloidal Behavior of Cellulose Nanocrystals Grafted with Poly(2-alkyl-2-oxazoline)s.

Polymer grafting onto cellulose nanocrystals (CNCs) has been used as a tool to improve CNC dispersion in nonpolar solvents or polymeric matrixes. The grafting of flexible polymer chains onto rigid particle surfaces leads to significant modifications in colloidal behavior. Here, poly(2-alkyl-2-oxazoline)s of well-defined molar mass and narrow molar mass distribution were synthesized by cationic ring-opening polymerization and grafted onto CNC surfaces, where the coupling reaction was favored when partially hydrolyzed polymers were used (reaching 64% reaction yield). The particles grafted with polymer chains could be redispersed in water after freeze-drying, producing stable dispersions, and they were not cell-toxic up to 10 wt % aqueous dispersion. Colloidal stability, nanostructure organization, and rheological behavior of grafted CNC and CNC-grafted CNC mixtures were evaluated. The rheological behavior of grafted nanoparticles, meanwhile, showed new features when compared to original CNC dispersions. Aqueous CNC dispersions showed a liquid crystal nematic organization and rheological behavior characteristic of true gel (at 5 wt %) prior to drying. On the other hand, nanoparticle dispersions behaved as weak gels upon the addition of 10 wt % of CNC-g-(PEtOx95-s-Ei5) under the same conditions. Dispersions of CNC-g-P(PEtOx-s-Ei) particles obtained by redispersion of freeze-dried particles behaved as a fluid, without the presence of the nematic organization. Through oscillatory rheology and time-domain NMR results, it can be concluded that polymer-water interactions are dominant over CNC-water interactions, being responsible for CNC nematic phase disruption. By introducing polymer chains, the introduction of isotropic character modifies water organization, changing the flow behavior of CNC-grafted with poly(oxazoline)s.

Amphiphilic polyurethane hydrogels as smart carriers for acidic hydrophobic drugs.

Amphiphilic hydrogels are widely reported as systems with great potential for controlled drug release. Nevertheless, the majority of studies make use of functionalization or attachment of drugs to the polymer chains. In this study, we propose a strategy of combining amphiphilic polyurethanes with pH-responsive drugs to develop smart drug carriers. While the amphiphilic character of the polymer imparts an efficient load of hydrophobic and hydrophilic drugs, the drug's characteristics determine the selectivity of the medium delivery. Drug loading and release behavior as well as hydrolytic degradation of chemically crosslinked polyurethane hydrogels based on PEG and PCL-triol (PU (polyurethane) hydrogels) synthesized by an easy one-pot route were studied. PU hydrogels have been shown to successfully load the hydrophobic acidic drug sodium diclofenac, reaching a partition coefficient of 8 between the most hydrophobic PU and diclofenac/ethanol solutions. Moreover, an oral administration simulation was conducted by changing the environment from an acidic to a neutral medium. PU hydrogels release less than 5% of the drug in an acidic medium; however, in a PBS pH 7.4 solution, diclofenac is delivered in a sustained fashion for up to 40 h, achieving 80% of cumulative release.

Electrospun nanofibrous scaffolds of segmented polyurethanes based on PEG, PLLA and PTMC blocks: Physico-chemical properties and morphology.

Biocompatible polymeric scaffolds are crucial for successful tissue engineering. Biomedical segmented polyurethanes (SPUs) are an important and versatile class of polymers characterized by a broad spectrum of compositions, molecular architectures, properties and applications. Although SPUs are versatile materials that can be designed by different routes to cover a wide range of properties, they have been infrequently used for the preparation of electrospun nanofibrous scaffolds. This study reports the preparation of new electrospun polyurethane scaffolds. The segmented polyurethanes were synthesized using low molar masses macrodyols (poly(ethylene glycol), poly(l-lactide) and poly(trimethylene carbonate)) and 1,6-hexane diisocyanate and 1,4-butanodiol as isocyanate and chain extensor, respectively. Different electrospinning parameters such as solution properties and processing conditions were evaluated to achieve smooth, uniform bead-free fibers. Electrospun micro/nanofibrous structures with mean fiber diameters ranging from 600nm to 770nm were obtained by varying the processing conditions. They were characterized in terms of thermal and dynamical mechanical properties, swelling degree and morphology. The elastomeric polyurethane scaffolds exhibit interesting properties that could be appropriate as biomimetic matrices for soft tissue engineering applications.

Amphiphilic copolymers of sucrose methacrylate and acrylic monomers: bio-based materials from renewable resource.

Regioselective sucrose 1'-O-methacrylate obtained by transesterification catalyzed by Proteinase-N was copolymerized with hydrophilic N-isopropylacrylamide and hydrophobic methyl methacrylate in different molar ratios by free radical polymerization. The copolymers were characterized by (13)C nuclear magnetic resonance spectroscopy, gel permeation chromatography, differential scanning calorimetry and thermogravimetry. Solubility and phase behavior of aqueous solutions were also investigated. The glass transition of the copolymers presents a positive deviation from the values of the homopolymers due to the high density of inter and intramolecular hydrogen bonding. Their solubility is strongly dependent on the composition. Copolymers poor in methyl methacrylate are water soluble, while copolymers richer in methyl methacrylate behaves as hydrogel. These hydrogels are not chemically crosslinked and their form can be design prior swelling by the conventional processing methods, such as solvent casting and extrusion for instance. Copolymers of N-isopropylacrylamide are water soluble and their aqueous solutions present a lower critical solution temperature behavior forming thermoreversible hydrogels.

Supramolecular interactions between inorganic and organic blocks of pentacyanoferrate/poly(4-vinylpyridine) hybrid metallopolymer.

The combination of organic and inorganic molecular building blocks gives rise to hybrid supramolecular materials showing properties from both chemical domains. This work presents the synthesis of metallopolymers made from poly(4-vinylpyridine) (P4VP) and pentacyanoferrate(II) at various polymer repeating unit/[Fe(CN)(5)](3-) ratios (py/Fe) and focuses on the influence of each block on the properties of the other. The solvatochromic shift of the [Fe(CN)(5)](3-) moiety was investigated as a function of the py/Fe ratio and the water molar fraction (X(H(2)O)) of the ethanol/water medium. Asymmetric solvation favoring ethanol was enhanced as the py/Fe ratio increased. The results lead to a modification of the well-established thermodynamical model for asymmetrical solvation and suggest the formation of water-rich domains within the polymer coils with a large number of [Fe(CN)(5)](3-) units. From the macromolecular perspective, the increase of [Fe(CN)(5)](3-) units resulted in higher values of intrinsic viscosity, which is rationalized by the increase of the polymer coil charge density and therefore the increase in hydrodynamic volume due to repulsive electrical forces. Evaluating the intrinsic viscosity of a sample with py/Fe = 25 in solvent mixtures with different water molar fractions, it was found that the hydrodynamic volume is maximized at intermediate X(H(2)O) values, where both the ethanol-soluble uncomplexed polymer block and the water-soluble [Fe(CN)(5)](3-)-pendant units can be suitably solvated, preventing coil shrinkage.