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The homogeneous non-catalytic hydrogenation of several types of iso- and syndiotactic cis-1,4 poly(1,3-diene)s with diimide, formed by thermal decomposition of p-toluene-sulfonyl-hydrazide, was examined. Perfectly alternating ethylene/1-alkene copolymers having different tacticity (i.e., isotactic and syndiotactic), which in some cases are difficult to synthesize by simple stereospecific co-polymerization of the corresponding monomers, were obtained. All the copolymers synthesized were fully characterized from a structural, morphological, and rheological point of view through different analytical techniques (FT-IR, NMR, GPC, DSC, RX). [ABSTRACT FROM AUTHOR]

The low percentage of recyclability of the polymeric materials obtained by olefin transition metal (TM) polymerization catalysis has increased the interest in their substitution with more eco-friendly materials with reliable physical and mechanical properties. Among the variety of known biodegradable polymers, linear aliphatic polyesters produced by ring-opening polymerization (ROP) of cyclic esters occupy a prominent position. The polymer properties are highly dependent on the macromolecule microstructure, and the control of stereoselectivity is necessary for providing materials with precise and finely tuned properties. In this review, we aim to outline the main synthetic routes, the physical properties and also the applications of three commercially available biodegradable materials: Polylactic acid (PLA), Poly(Lactic-co-Glycolic Acid) (PLGA), and Poly(3-hydroxybutyrate) (P3HB), all of three easily accessible via ROP. In this framework, understanding the origin of enantioselectivity and the factors that determine it is then crucial for the development of materials with suitable thermal and mechanical properties. [ABSTRACT FROM AUTHOR]

A density functional theory (DFT) study combined with the steric maps of buried volume (%VBur) as molecular descriptors and an energy decomposition analysis through the ASM (activation strain model)–NEDA (natural energy decomposition analysis) approach were applied to investigate the origins of stereoselectivity for propene polymerization promoted by pyridylamido-type nonmetallocene systems. The relationships between the fine tuning of the ligand and the propene stereoregularity were rationalized (e.g., the metallacycle size, chemical nature of the bridge, and substituents at the ortho-position on the aniline moieties). The DFT calculations and %VBur steric maps reproduced the experimental trend: substituents on the bridge and on the ortho-positions of aniline fragments enhance the stereoselectivity. The ASM–NEDA analysis enabled the separation of the steric and electronic effects and revealed how subtle ligand modification may affect the stereoselectivity of the process. [ABSTRACT FROM AUTHOR]

The crystallization behavior of random propene-octene isotactic copolymers (iPPC8) prepared with a homogeneous metallocene catalyst has been studied. Samples of iPPC8 with low octene content up to about 7 mol% were isothermally crystallized from the melt at various crystallization temperatures. The samples crystallize in mixtures of the α and γ forms of isotactic polypropylene (iPP). The relative amount of γ form increases with increasing crystallization temperature, and a maximum amount of γ form (fγ(max)) is achieved for each sample. The crystallization behavior of iPPC8 copolymers is compared with the crystallization from the melt of propene–ethylene, propene–butene, propene–pentene, and propene–hexene copolymers. The results show that the behavior of iPPC8 copolymers is completely different from those described in the literature for the other copolymers of iPP. In fact, the maximum amount of γ form achieved in samples of different copolymers of iPP generally increases with increasing comonomer content, while in iPPC8 copolymers the maximum amount of γ form decreases with increasing octene content. The different behaviors are discussed based on the inclusion of co-monomeric units in the crystals of α and γ forms of iPP or their exclusion from the crystals. In iPPC8 copolymers, octene units are excluded from the crystals giving only the interruption effect that shortens the length of regular propene sequences, inducing crystallization of the γ form at low octene concentrations, lower than 2 mol%. At higher octene concentration, the crystallization of the kinetically favored α form prevails. [ABSTRACT FROM AUTHOR]

Random isotactic propene-butene copolymers (iPPC4) of different stereoregularity have been synthesized with three different homogeneous single center metallocene catalysts having different stereoselectivity. All samples crystallize from the polymerization solution in mixtures of α and γ forms, and the relative amount of γ form increases with increasing concentrations of butene and of rr stereodefects. All samples crystallize from the melt in mixtures of α and γ forms and the fraction of γ form increases with decreasing cooling rate. At high cooling rates, the crystallization of the α form is always favored, even for samples that contain high total concentration of defects that should crystallize in the γ form. The results demonstrate that in iPPs containing significant concentrations of defects, such as stereodefects and comonomeric units, the γ form is the thermodynamically stable form of iPP and crystallizes in selective conditions of very slow crystallization, whereas the α form is the kinetically favored form and crystallizes in conditions of fast crystallization. [ABSTRACT FROM AUTHOR]

A study of the structure and morphology of diblock copolymers composed of crystallizable blocks of polyethylene (PE) and syndiotactic polypropylene (sPP) having different lengths is reported. In both analyzed samples, the PE block crystallizes first by cooling from the melt (at 130 °C) and the sPP block crystallizes after at a lower temperature. Small angle X-ray scattering (SAXS) recorded during cooling showed three correlation peaks at values of the scattering vector, q1 = 0.12 nm−1, q2 = 0.24 nm−1 and q3 = 0.4 nm−1, indicating development of a lamellar morphology, where lamellar domains of PE and sPP alternate, each domain containing stacks of crystalline lamellae of PE or sPP sandwiched by their own amorphous phase of PE or sPP. At temperatures higher than 120 °C, when only PE crystals are formed, the morphology is defined by the formation of stacks of PE lamellae (17 nm thick) alternating with amorphous layers and with a long period of nearly 52 nm. At lower temperatures, when crystals of sPP are also well-formed, the morphology is more complex. A model of the morphology at room temperature is proposed based on the correlation distances determined from the self-correlation functions extracted from the SAXS data. Lamellar domains of PE (41.5 nm thick) and sPP (8.2 nm thick) alternate, each domain containing stacks of crystalline lamellae sandwiched by their own amorphous phase, forming a global morphology having a total lamellar periodicity of 49.7 nm, characterized by alternating amorphous and crystalline layers, where the crystalline layers are alternatively made of stacks of PE lamellae (22 nm thick) and thinner sPP lamellae (only 3.5 nm thick). [ABSTRACT FROM AUTHOR]

The development of a highly oriented fiber morphology by effect of tensile deformation of stereodefective isotactic polypropylene (iPP) samples, starting from the unoriented form, is studied by following the transformation in real time during stretching through wide angle X-ray scattering (WAXS) measurements. In the stretching process, after yielding, the initial form transforms into the mesomorphic form of iPP through mechanical melting and re-crystallization. The analysis of the scattering invariant measured in theWAXS region highlights that the size of the mesomorphic domains included in the well oriented fiber morphology obtained at high deformations increases through a process which involves the coalescence of the small fragments formed by effect of tensile stress during lamellar destruction with the domain of higher dimensions. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Crystallization and phase separation in the melt in semicrystalline block copolymers (BCPs) compete in defining the final solid state structure and morphology. In crystalline–crystalline di-block copolymers the sequence of crystallization of the two blocks plays a definitive role. In this work we show that the use of epitaxial crystallization on selected crystalline substrates allows achieving of a control over the crystallization of the blocks by inducing crystal orientations of the different crystalline phases and a final control over the global morphology. A sample of polyethylene-block-syndiotactic polypropylene (PE-b-sPP) block copolymers has been synthesized with a stereoselective living organometallic catalyst and epitaxially crystallized onto crystals of two different crystalline substrates, p-terphenyl (3Ph) and benzoic acid (BA). The epitaxial crystallization on both substrates produces formation of highly ordered morphologies with crystalline lamellae of sPP and PE highly oriented along one direction. However, the epitaxial crystallization onto 3Ph should generate a single orientation of sPP crystalline lamellae highly aligned along one direction and a double orientation of PE lamellae, whereas BA crystals should induce high orientation of only PE crystalline lamellae. Thanks to the use of the two selective substrates, the final morphology reveals the sequence of crystallization events during cooling from the melt and what is the dominant event that drives the final morphology. The observed single orientation of both crystalline PE and sPP phases on both substrates, indeed, indicates that sPP crystallizes first onto 3Ph defining the overall morphology and PE crystallizes after sPP in the confined interlamellar sPP regions. Instead, PE crystallizes first onto BA defining the overall morphology and sPP crystallizes after PE in the confined interlamellar PE regions. This allows for discriminating between the different crystalline phases and defining the final morphology, which depends on which polymer block crystallizes first on the substrate. This work also shows that the use of epitaxial crystallization and the choice of suitable substrate offer a means to produce oriented nanostructures and morphologies of block copolymers depending on the composition and the substrates. [ABSTRACT FROM AUTHOR]

Ethylene-co-norbornene copolymers were synthesized by a dual catalyst system at three concentrations of norbornene in the feed and variable amounts of ZnEt2, as a possible chain transfer agent. The dual catalyst system consists of two ansa-metallocenes, isopropyliden(η5-cyclopentadienyl)(η5-indenyl)zirconium dichloride (1) and isopropyliden(η5-3-methylcyclopentadienyl)(η5-fluorenyl)zirconium dichloride (2), activated with dimethylanilinium tetrakis(pentafluorophenyl)borate, in presence of TIBA. Values of norbornene content, molecular mass, glass transition temperature, and reactivity ratios r11 and r21 of copolymers prepared in the presence of 1+2 are intermediate between those of reference copolymers. The study of tensile and elastic properties of ethylene-co-norbornene copolymers (poly(E-co-N)s) gave evidence that copolymers were obtained in part through transfer of polymer chains between different transition metal sites. Mechanical properties are clearly different from those expected from a blend of the parent samples and reveal that copolymers obtained in the presence of 1+2 and ZnEt2 consist of a reactor blend of segmented chains produced by exchange from 2 to 1 and 1 to 2 acting as the ideal compatibilizer of chains produced by the chain transfer from 1 to 1, and from 2 to 2. [ABSTRACT FROM AUTHOR]