Biodegradable synthetic and semisynthetic polymers

As a part of our continuing interest in the preparation of multifunctional polymeric materials and evaluation of their potential in pharmaceutical, medical and environmental fields, a survey on new polymeric systems of synthetic and semisynthetic origin, susceptible to bioerosion and/or biodegradation attack is presented. In particular, attention has been focused on the design, preparation and characterization of the following classes of hydrophilic and/or water-soluble polymeric materials: hydroxyl-containing poly(ester)s, hydroxyl-containing poly(amide)s, hydrophilic polymers containing carboxylic groups, perhydroxylated oligo- and poly(saccharide)s, oxidized poly(saccharide)s, and hybrid polymeric materials based on blends of carboxyl-containing synthetic polymers and proteins. The rationale of the research activity undertaken over the years is illustrated by focusing on some specific achievements of practical significance.     

Factorial design in optimization of PHAs processing

Poly(hydroxyalkanoate)s (PHA)s, as all melt-processed polymers, may undergo thermal degradation at temperatures close to the melting point. The primary purpose of the present study is to screen out process variables on the basis of a factorial design for two variables at two levels. The investigated parameters for PHA polymer samples processed in a torque rheometer were structure of PHA, processing temperature, and rotor speed. For polymers processed by compression molding, only the first two variables were considered and purification. The main effects and possible interactions were verified by the changes of molecular weight and thermal properties, as detected by DSC and TGA. It was observed that molecular weight decreased up to about 50% while the thermal properties did not appreciably change.     

A simple method suitable to test the ultimate biodegradability of environmentally degradable polymers

A straightforward experimental set-up derived from the Biometer Flask previously utilized for experiments of pesticides biodegradation, has been adopted for testing the ultimate biodegradability of natural, synthetic and semi-synthetic polymeric materials on solid substrates such as soil and mature compost. The use of these whole substrates as incubation media in respirometric experiments, may negatively affect the accuracy of the test due to the large amount of carbon dioxide developed from the blanks, especially in the presence of specimen degrading at low or moderate rates. In the present test procedure soil and compost samples are diluted with perlite, a naturally occurring inert aluminum silicate widely utilized in horticultural applications, in order to ensure optimal conditions for the microbial growth while reducing the carbon dioxide emissions from the blanks. The results so far reported clearly indicate that the adopted procedure is extremely valuable and versatile for the appreciation of even subtle differences in the biodegradation rate of different polymeric materials, as well as for long-term degradation experiments.     

Phase and orientational behaviors in liquid crystalline main-chain/side-group block copolymers

The phase and orientational behaviors of a series of liquid crystalline (LC) AB-type diblock copolymers comprising thermotropic main-chain (MC) polyester and side-group (SG) polymethacrylate blocks were investigated by X-ray diffraction. The MC and SG blocks were phase separated and gave rise to their individual mesophases that coexisted at equilibrium. The samples were oriented by using either a magnetic field or a mechanical field. In magnetically aligned samples both the MC and SG microphases were oriented with their smectic planes orthogonal to the magnetic field direction, independent of the copolymer composition. Mechanically aligned, fiber samples showed different orientations of the MC and SG smectic planes for different sample compositions. In this case the disposition of the smectic planes of the MC and SG blocks was driven by the relative length of the two blocks. Some features of the X-ray patterns of the copolymers were compared to those of the MC and SG homopolymers. In addition, the MC smectic domains crystallized on annealing without affecting the orientation that had been achieved by applying a magnetic field. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36 : 21–29, 1998     

Nanostructured films of amphiphilic fluorinated block copolymers for fouling release application

New amphiphilic block copolymers S nSz m consisting of blocks with varied degrees of polymerization, n and m, of polystyrene, S, and polystyrene carrying an amphiphilic polyoxyethylene-polytetrafluoroethylene chain side-group, Sz, were prepared by controlled atom transfer radical polymerization (ATRP). The block copolymers, either alone or in a blend with commercial SEBS (10 wt% SEBS), were spin-coated in thinner films (200-400 nm) on glass and spray-coated in thicker films ( approximately 500 nm) on a SEBS underlayer (150-200 microm). Angle-resolved X-ray photoelectron spectroscopy (XPS) measurements proved that at any photoemission angle, varphi, the atomic ratio F/C was larger than that expected from the known stoichiometry. Consistent with the enrichment of the outer film surface (3-10 nm) in F content, the measured contact angles, theta, with water (theta w > or = 107 degrees ) and n-hexadecane (theta h > or = 64 degrees ) pointed to the simultaneous hydrophobic and lipophobic character of the films. The film surface tension gamma S calculated from the theta values was in the range 13-15 mN/m. However, the XPS measurements on the "wet" films after immersion in water demonstrated that the film surface underwent reconstruction owing to its amphiphilic nature, thereby giving rise to a more chemically heterogeneous structure. The atomic force microscopy (AFM) images (tapping mode/AC mode) revealed well-defined morphological features of the nanostructured films. Depending on the chemical composition of the block copolymers, spherical (ca. 20 nm diameter) and lying cylindrical (24-29 nm periodicity) nanodomains of the S discrete phase were segregated from the Sz continuous matrix (root-mean-square, rms, roughness approximately 1 nm). After immersion in water, the underwater AFM patterns evidenced a transformation to a mixed surface structure, in which the nanoscale heterogeneity and topography (rms = 1-6 nm) were increased. The coatings were subjected to laboratory bioassays to explore their intrinsic ability to resist the settlement and reduce the adhesion strength of two marine algae, viz., the macroalga (seaweed) Ulva linza and the unicellular diatom Navicula perminuta. The amphiphilic nature of the copolymer coatings resulted in distinctly different performances against these two organisms. Ulva adhered less strongly to the coatings richer in the amphiphilic polystyrene component, percentage removal being maximal at intermediate weight contents. In contrast, Navicula cells adhered less strongly to coatings with a lower weight percentage of the amphiphilic side chains. The results are discussed in terms of the changes in surface structure caused by immersion and the effects such changes may have on the adhesion of the test organisms.     

Poly‐(ε‐caprolactone) (PCL) and poly(hydroxy‐butyrate) (PHB) blends containing seaweed fibers: Morphology and thermal‐mechanical properties

Massive quantities of marine seaweed, Ulva armoricana are washed onto shores of many European countries and accumulates as waste. Attempts were made to utilize this renewable resource in hybrid composites by blending the algal biomass with biodegradable polymers such as poly(hydroxy‐butyrate) and poly‐(ε‐caprolactone). Compression‐molded films were developed and examined for their morphological, thermal and mechanical property. The Ulva fibers were well dispersed throughout the continous matrix exhibiting considerable cohesion with both polymers. Occasionally, regions with exposed fibres or aggregates were visible. About 50% algal content seemed to be an ideal concentration, thereafter, thermal stability was impacted. A progressive decrease in melting heat (ΔH_m) was observed with increased algal content as well as a decrease in the crystallinity of the polymer matrix due to the presence of the organic filler. The addition of algal fibres improved the Young modulus of the blends, creating a concomitant loss in percent elongation (El) and ultimate tensile strength. Fiber content above 40% impacted tensile property negatively and composites with over 70% fiber contents composites were too fragile. Data suggest that macro algae are compatible with both polymers and processable as fillers in hybrid blends. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Stereoelective polymerization of racemic α-olefins: Influence of conversion and of nature of catalyst components

The dependence of stereoelectivity on conversion has been investigated by polymerizing racemic 4-methyl-1-hexene (I) and 3,7-dimethyl-1-octene (II) in the presence of catalysts prepared from TiCl₄ and bis[(S)-2-methylbutyl]-zinc(III) or tris [(S)-2-methylbutyl]aluminum (IV). The influence of the nature of transition metal halide has also been examined by polymerization of racemic I and II with catalysts obtained from III and transition metal halides as well as from TiCl₄ and optically active organometallic compounds containing phenyl groups. Stereoelectivity remains practically constant or increases slightly with increasing conversion, but it is affected by the nature of transition metal halide. Moreover a detectable variation of stereoelectivity was observed by changing the chemical structure of the alkyl group in the optically active organometallic component of the catalyst. In any case, however, stereoelectivity is not higher than 5–10%. Evidence in favor of asymmetric induction by the catalytic complex is reported and discussed.     

ɛ-nets and simplex range queries

We demonstrate the existence of data structures for half-space and simplex range queries on finite point sets ind-dimensional space,d≥2, with linear storage andO(n ^α ) query time, $$\alpha = \frac{{d(d - 1)}}{{d(d - 1) + 1}} + \gamma for all \gamma > 0$$ . These bounds are better than those previously published for alld≥2. Based on ideas due to Vapnik and Chervonenkis, we introduce the concept of an ?-net of a set of points for an abstract set of ranges and give sufficient conditions that a random sample is an ?-net with any desired probability. Using these results, we demonstrate how random samples can be used to build a partition-tree structure that achieves the above query time.