The Relationship between Catalyst Precursors and Chain End Groups in Homogeneous Propene Polymerization Catalysis

The chain transfer to monomer reactions promoted by primary and secondary growing chains in the propene polymerization promoted by ansa-zirconocenes and postmetallocene precursors are studied by using DFT methods. From the theoretical results it comes out that the prevalence of propene insertion over b-hydrogen transfer to the monomer decreases drastically in the presence of a secondary chain. Furthermore, we explained the reason why C2-symmetric metallocene catalysts promote the selective formation of cis but-2-enyls end group after a 2,1 inserted unit whereas for octahedral bis(phenoxy- imine)titanium-based catalysts, chain release promotes exclusively the formation of allyl terminated chain end. These results might be useful to design ligand precursors able to obtain not only high Mn PP polymers but also tuned chain end groups to build new polymer architectures. Overall, a more general picture of the enantioselectivity of the chain transfer to monomer processes is reported

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

Structural characterization of syndiotactic propylene-styrene-ethylene terpolymers

The structural features of propylene-styrene-ethylene terpolymer (sP/(S-E)) prepd. using syndiospecific Cs-sym. metallocene catalyst, isopropylidene(cyclopentadienyl)-(9-fluorenyl)zirconium dichloride with MAO co-catalyst were studied. The polymorphism studies of as-prepd., melt-crystd., and fiber sP/(S-E) confirmed that ethylene units are mainly bound to styrene units arising from catalyst reactivation after the secondary insertion of styrene. Styrene-ethylene units are mainly segregated in the amorphous phase. The bulky styrene units, bound to ethylene, prevent the inclusion of ethylene units in the crystals of syndiotactic polypropylene (sPP), as generally occurs for copolymers of sPP with ethylene. This explains the fact that the effect of styrene-ethylene units on polymorphism of sPP is smaller than that obsd. in copolymers of sPP contg. only ethylene or butene comonomer units

NNLO Logarithmic Expansions and High Precision Determinations of the QCD background at the LHC: The case of the Z resonance

New methods of solutions of the DGLAP equation and their implementation through NNLO in QCD are briefly reviewed. We organize the perturbative expansion that describes in $x$-space the evolved parton distributions in terms of scale invariant functions, which are determined recursively, and logarithms of the ratio of the running couplings at the initial and final evolution scales. Resummed solutions are constructed within the same approach and involve logarithms of more complex functions, which are given in the non-singlet case. Differences in the evolution schemes are shown to be numerically sizeable and intrinsic to perturbation theory. We illustrate these points in the case of Drell-Yan lepton pair production near the Z resonance, analysis that can be extended to searches of extra $Z^{\prime}$. We show that the reduction of the NNLO cross section compared to the NLO prediction may be attributed to the NNLO evolution.Comment: 5 pages, 2 figures. Talk given at QCD@work 2007, Martina Franca, Italy, 16-20 June 2007. To be published in the American Institute of Physics (AIP) conference proceeding

Crystal structure of the clathrate form of syndiotactic poly(p-methylstyrene) containing o-dichlorobenzene

The crystal structure of the clathrate form of syndiotactic poly(p-methylstyrene) (s-PPMS) containing o-dichlorobenzene (o-DCB) is presented. The structure is characterized by polymer chains in s(2/1)2 helical conformation and o-dichlorobenzene molecules packed in a monoclinic unit cell with axes a = 23.4 Å, b = 11.8 Å, c = 7.7 Å, and γ = 115°, according to the space group P21/a. The calculated crystalline density is 1.07 g/cm3 for two polymer chains (eight monomer units) and two o-DCB molecules included in the unit cell. The o-DCB molecules occupy cavities delimited by the phenyl rings of two enantiomorphic polymer chains. A disorder in the positioning of the o-DCB molecules inside the cavity is present. A comparison with the crystal structure of the clathrate form of s-PPMS containing tetrahydrofuran is presented. Remarkable differences were found, confirming the previous hypothesis that two different types of crystal structures (α and β class) are presented by the clathrate forms of s-PPMS depending on the guest molecule

Polymorphic Behavior of Copolymers of Syndiotactic Polystyrene with m-Methylstyrene.

The influence of the presence of different amounts m-methylstyrene (m-MS), in the composition range 4−21 mol %, on the polymorphic behavior of syndiotactic polystyrene (s-PS) is presented. A comparison with the effect of the presence of p-methylstyrene is also presented. The behavior of copolymers subjected to solvent extraction or annealing procedures indicates that the presence of m-MS stabilizes the γ form of s-PS, which remains stable in a large temperature range, up to 210−220 °C. The helical mesoporous δ form of s-PS has not been observed in copolymers with m-MS. The presence of low contents of m-MS induces crystallization of the β form from polymer solution (by casting at high temperatures), whereas high concentrations of m-MS tend to stabilize the γ form. The copolymer samples crystallize from the melt in α and β forms depending on the concentration of m-MS, which stabilizes the β form for composition around 11 mol %, and induces crystallization in the α form for lower (4 mol %) and higher (21 mol %) concentration. Moreover, even when the memory of the α form is maintained in the melt, the presence of m-MS in a concentration around 11 mol % induces the crystallization of the β form, whereas, even though no memory of the α form is present in the melt, samples with 4 and 21 mol % of m-MS crystallize in the α form. The α form obtained in these copolymers, by melt-crystallization or annealing of the γ form, does not correspond to neither the disordered α‘, nor the ordered α‘ ‘ modifications observed in s-PS. The presence of m-MS comonomeric units induces structural variation in the crystal packing of the trans-planar chains, and a new crystalline form is obtained

The Search for Extra Neutral Currents at the LHC: QCD and Anomalous Gauge Interactions

Extensions of the Standard Model with extra neutral currents due to additional anomalous abelian gauge factors are considered. We summarize the main features of the effective action associated to these theories. They are characterized by an axion-like particle (the {\em axi-higgs}) which can be (almost) massless, with its mass generated non-perturbatively in the QCD vacuum as for an ordinary Peccei-Quinn axion, but that can also mix with the scalars of the Higgs sector, becoming a heavy axion. We briefly describe the interplay between the electroweak and the QCD sectors in these types of theories, which emerge either from special vacua of string/brane theory; from partial decoupling of a heavier fermion sector or from an anomaly inflow in the context of models with extra dimensions.Comment: Talk given at QCD@work 2007, Martina Franca, Italy, 16-20 June 2007, 5 pages, 2 figures. To be published in the American Institute of Physics (AIP) conference proceeding

Leptin: Role of metabolism in the regulation of inflammation

Over the last few years the intricate interaction between immune system and adipose tissue has been recognized. Indeed, it has been suggested that adipose tissue is not only a mere site of lipid and energy storage but can be considered as an "immune-related" organ producing a series of molecules named adipokines. Among these, leptin, an adipocyte-derived cytokine-like hormone, seems to play a pivotal role in the regulation of several neuroendocrine and immune functions. In this review, we describe the effects of leptin in inflammation and immunity, and speculate on the possible modulation of the leptin axis in novel adipopharmacotherapeutic settings.Biomedical Reviews 2006; 17: 53-62

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

Melt-Crystallizations of α and γ Forms of Isotactic Polypropylene in Propene-Butene Copolymers

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