Crystal structures and polymorphism of polymers: Influence of defects and disorder

The crystal structures and the polymorphism of polymers are described on the basis of the main principles that define the conformation of polymer chains in the crystalline state and the modes of packing of macromolecules. We show that the presence of defects and disorder in the crystals influences the polymorphic behavior. The cases of polymorphism of isotactic poly(butene) (iPB) and syndiotactic poly(styrene) (sPS) are ilustrated as examples. In the case of iPB, the effect of the presence of defects of stereoregularity and of comonomeric units on the crystallization of form I and form II is described as an example of alteration of the crystallization behavior because of the modification of both thermodynamic stability and crystallization kinetics from the melt of the polymorphic forms. The case of sPS is taken as an example of a very complex polymorphic behavior arising from the presence and development of structural disorder

Polymorphism and structural disorder in melt-crystallized and fiber samples of syndiotactic copolymers of propane with 1-butene

The structural characterization of melt-crystallized samples and oriented fibers of syndiotactic copolymers between propene and 1-butene is reported. Melt-crystallized samples of copolymers are crystallized in the form I of syndiotactic polypropylene (s-PP) up to a Content of 1-butene of 60-70 mol %, although disorder in the alternation of right- and left-handed helical chains along both axes of the unit cell is present. More ordered modifications, close to the limit ordered, fully antichiral, form I of s-PP are obtained by crystallization at high temperatures only for samples containing small contents of 1-butene (1-2 mol %). The presence of 1-butene prevents that the order in the alternation of right- and left-handed helical chains develops at high crystallization temperatures. Samples with contents of 1-butene higher than 70 mol % crystallize in structures similar to that of form I of syndiotactic poly(1-butene). Fiber samples of copolymers with small content of 1-butene (1-2 mol %) present the same behavior of syndiotactic polypropylene. Stretched fibers are in the trans planar form III of s-PP,which transforms into the isochiral helical form II of s-PP upon the release of the tension. Mixtures of crystals in forms I and II of s-PP are obtained by annealing. With increasing the 1-butene content only the antichiral helical form I of s-PP is observed in the stretched fibers of the copolymers, as well as upon the release of the tension. The presence of 1-butene units, for contents higher than 4 mol %, prevents the formation of the trans planar form III of s-PP by stretching. For these samples the formation of form I of s-PP, instead of the isochiral form II, either in the stretched fibers or upon the release of the tension, is a further evidence that the isochiral helical form II of s-PP can be obtained only from fibers initially in the trans planar form III, through a cooperative conformational transformation which induce the formation of helical chains having the same chirality

Structural Analysis of Copolymers of Syndiotactic Polypropylene with 13C-Enriched Ethylene

A structural analysis of copolymers of syndiotactic polypropylene with small amounts of 13 C-enriched ethylene, in the range 0.4-2.6 mol %, is reported. X-ray diffraction and solid-state C-13 NMR CPMAS data indicate that the as-prepared copolymer samples are crystallized in the conformationally disordered modification of form II of sPP containing kink bands. The disorder corresponds to the presence of portions of chains in the trans-planar conformation in chains having a prevailing 2-fold helical conformation. A direct evidence of the partial inclusion of the ethylene units in the crystalline regions of the copolymers is provided

Microencapsulated Garcinia kola and Hunteria umbellata Seeds Aqueous Extracts – Part 1: Effect of microencapsulation process.

Objective: This study investigates microcapsulated aqueous extracts of Garcinia kola (GK) and Hunteria umbellata (HU) seeds. Method: Extracts obtained after maceration of dried powdered seeds were prepared as microcapsules with chitosan-alginate by counterion coacervation method. Microcapsules were characterized using differential scanning calorimetry (DSC), x-ray diffractometry (XRD) and fourier transform infrared (FTIR) spectroscopy. In vitro release studies were carried out at pH 1.2 for 2 h and 6.8 for a further 10 h. Results: Between 20 and 50% extract release occurred from microcapsules after 2 h while conventional tablets released 100% after 1 h at simulated gastric pH. At pH 6.8, >80% of extract was released from microcapsules after 6 h. DSC revealed the presence of complex materials. XRD and FTIR showed stable character of the plant extracts within the microcapsules. Conclusion: Controlled release of aqueous extracts derived from these plants was achieved by microencapsulation and therefore can be developed as suitable delivery devices

Chitosan-alginate microparticles of Andrographis paniculata and Annona muricata extracts for Controlled Release

This study investigates the properties of microparticles prepared from Andrographis paniculata (AP) and Annona muricata (AM) aqueous extracts for controlled release. Extracts obtained by maceration of the dried powdered plant leaves were microencapsulated by counterion coacervation method. Microcapsules were characterized using Fourier-transform infrared-spectroscopy (FTIR), x-ray difractometry (XRD) and differential scanning calorimetry (DSC).In vitro release studies were carried out at pH 1.2 for 2 h and 6.8 for a further 10 h. Release was monitored at274 and 230 nm for AM and AP, respectively. Encapsulation efficacy was less than 52% for AP and 70% for AM. In vitro drug release at pH 1.2 showed less than 40% release from the microcapsules after 2h while over 90% of extract was released after 6h at pH 6.8. Conventional capsules released the content within 1 h in simulated gastric fluid. FTIR, XRD and DSC results indicate the stable character of the extract within the microcapsules. Microencapsulation with chitosan- alginate controlled the release of Andrographis paniculata (AP) and Annona muricata (AM) aqueous extracts

Propylene–Butene Copolymers: Tailoring Mechanical Properties from Isotactic Polypropylene to Polybutene

Isotactic propylene-butene copolymers [i(P-co-B)] with precise and controlled molecular structures were synthesized with various organometallic catalysts having different stereoselectivities. Stereoregular and stereodefective samples of i(P-co-B) with 1-butene (B) content variable in the whole range of composition were synthesized. All samples crystallize regardless of composition, indicating cocrystallization of propene and 1-butene units, which are incorporated in the unit cells of polymorphic forms of isotactic poly(propylene) (iPP) and isotactic poly(1-butene) (iPB). The copolymers show a continuum change of crystal morphology with the composition, transforming from big spherulites to bundle-like and needle-like crystals, to granular crystals. The cocrystallization allows maintaining high crystallinity of copolymers for any composition and provides an opportunity to develop outstanding mechanical properties that can be tailored by changing the isotacticity and composition. This allows, ideally, combining in the same material the different properties of stiffness of iPP and flexibility of iPB. These copolymers show, indeed, mechanical properties intermediate between iPP and iPB, ranging from stiffness/brittleness and ductility/flexibility depending on the composition and isotacticity, with high strength and Young's modulus that may be regulated by the stereoregularity of the iPP and iPB sequences, which is, in turn, dictated by the catalyst structure

Isotactic and syndiotactic alternating ethylene/propylene copolymers obtained through non-catalytic hydrogenation of highly stereoregular cis-1,4 poly(1,3-diene)s

The homogeneous non-catalytic hydrogenation of cis-1,4 poly(isoprene), isotactic cis-1,4 poly(1,3-pentadiene) and syndiotactic cis-1,4 poly(1,3-pentadiene) with diimide, formed by thermal decomposition of para-toluenesulfonylhydrazide, is examined. Perfectly alternating ethylene/propylene copolymers having different tacticity (i.e., isotactic and syndiotactic), which are difficult to synthesize by stereospecific copolymerization of the corresponding monomers, are obtained. Both isotactic and syndiotactic alternating ethylene/propylene copolymers are amorphous, with very low glass transition temperatures

Morphology of Isotactic Polypropylene–Polyethylene Block Copolymers Driven by Controlled Crystallization

A study of the morphology of diblock copolymers composed of two crystalline blocks of isotactic polypropylene (iPP) and polyethylene (PE) is shown. The samples form phase-separated structures in the melt because of the incompatibility between iPP and PE blocks. Cylindrical PE microdomains are visible at room temperature in the sample with a PE volume fraction of 26%, rapidly quenched from the melt in liquid nitrogen. In the quenched sample, PE crystallizes inside the PE cylindrical microdomains, whereas crystals of iPP are not visible in the iPP domains because the quenching prevents crystallization of the lamellar α form. Less rapid cooling of the melt produces, instead, breakout crystallization, where the phase-separated structure of the melt is destroyed by the slow crystallization of the α form of iPP and of PE. The succession of crystallization of iPP and PE and the resulting final morphology have been analyzed by inducing selective and different orientations of iPP and PE crystals through epitaxial crystallization onto the benzoic acid (BA) crystal substrate. Epitaxy produces oriented crystallization of iPP and PE, with a unique alignment of PE lamellar crystals and a double orientation of iPP crystals on to the (001) exposed face of BA. Epitaxy destroys the phase-separated structure of the melt and induces the formation of ordered lamellar nanostructures with alternated layers of iPP and PE, whose orientation is defined by the alignment of PE or iPP crystals, which, in turn, is determined by epitaxy. The results indicate that crystalline block copolymers offer the opportunity to create nanoscale patterns on thin films and improve the possibility of controlling the microstructure of block copolymers and the alignment of microdomains by controlling the crystallization process

Time-resolving small angle X-Ray scattering analysis of melt crystallization of mixtures of regular and irregular isotactic polypropylene samples

The melting/crystallization properties of blends obtained by mixing two isotactic polypropylene (iPP) samples synthesized using single-site metallocene catalyst systems and containing a high and low concentration of rr triads as stereo-defects, are studied. The changes occurring at lamellar length scale during a heating/cooling cycle at constant scanning rate are followed in situ by performing time-resolved small angle X-ray scattering (SAXS) measurements. Data analysis demonstrates that the evolution of the SAXS intensity with increase/decrease of the temperature is controlled by the separate melting/crystallization of the two components, the differences in the thermal expansion (contraction) coefficient of the amorphous and crystalline phases and the role of thermal fluctuations in electron density. The two components give rise to different populations of intermixed lamellar stacks in the blends which originate from the good miscibility of the low and high stereoregular samples in the melt.info:eu-repo/semantics/publishedVersio

Nano-in-Nano Approach for Enzyme Immobilization Based on Block Copolymers

We set up a facile approach for fabrication of supports with tailored nanoporosity for immobilization of enzymes. To this aim block copolymers (BCPs) self-assembly has been used to prepare nanostructured thin films with well-defined architecture containing pores of tailorable size delimited by walls with tailorable degree of hydrophilicity. In particular, we employed a mixture of polystyrene-block-poly(l-lactide) (PS-PLLA) and polystyrene-block-poly(ethylene oxide) (PS-PEO) diblock copolymers to generate thin films with a lamellar morphology consisting of PS lamellar domains alternating with mixed PEO/PLLA blocks lamellar domains. Selective basic hydrolysis of the PLLA blocks generates thin films, patterned with nanometric channels containing hydrophilic PEO chains pending from PS walls. The shape and size of the channels and the degree of hydrophilicity of the pores depend on the relative length of the blocks, the molecular mass of the BCPs, and the composition of the mixture. The strength of our approach is demonstrated in the case of physical adsorption of the hemoprotein peroxidase from horseradish (HRP) using 2,2?-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) with H2O2 as substrate. The large surface area, the tailored pore sizes, and the functionalization with hydrophilic PEO blocks make the designed nanostructured materials suitable supports for the nanoconfinement of HRP biomolecules endowed with high catalytic performance, no mass-transfer limitations, and long-term stability