The synthesis of linear ultra high molecular weight polyethylene, with a "pseudoliving" catalyst in various conditions results in samples of different molecular weights (M w ranging between 2 to 35 million g/mol), all having a reduced number of entanglements to an extent that allows the solid-state uniaxial deformation of such high molar masses without melting. The solid-state processing of these materials shows a clear relationship between mechanical properties and molecular weight. For the adopted polymerization conditions, stretching forces required for the uniaxial deformation increase with the increasing molar mass, ultimately limiting the achievable maximum draw ratio in the polymers having M w > 10 million g/mol. The increase in the stretching force is attributed to the increasing number of entanglements between the crystals with the molar mass. The estimation of entanglements is established with the help of melting kinetics involved in the "disentangled" crystals, and rheological response of the polymer melt obtained just after melting of the crystals. In spite of the increase in the stretching forces with the increasing molar mass, tensile modulus increases with the increasing draw ratio and the molecular weight. However, above the molar mass of 10 million g/mol, the stretching force required increases to the level that the uniaxial deformation becomes difficult−thus limiting the tensile strength.

Recently, the influence of reduced graphene oxide nanoplatelets (rGON) on the rheological response of polymers has been a subject of interest. In the case of disentangled UHMWPE, it has been shown that the chain-filler interaction in the UHMWPE/rGON composite results into an everlasting non-equilibrium melt state having heterogeneous distribution in entanglement density. In this study, a thermal analysis protocol is used to follow the influence of the non-equilibrium polymer melt on the crystallization kinetics of disentangled UHMWPE with, and without, rGON. The analysis is carried out by means of differential scanning calorimetry (DSC) and the results are supported by rheology. When the disentangled UHMWPE sample, without the filler rGON, is left to crystallize under isothermal condition after melting, two endothermic peaks are observed: the high temperature peak (close to the equilibrium melting point, 141.5 °C) is related to the melting of crystals obtained on crystallization from the disentangled domains of the heterogeneous (nonequilibrium) polymer melt, whereas the low melting temperature peak is related to the melting of crystals formed from entangled domains of the melt. On increasing the annealing time in melt (160 °C), the enthalpy of the lower melting temperature peak increases at the expense of the high melting temperature peak, confirming a transformation of the nonequilibrium polymer melt to a fully entangled equilibrium melt state. However, independent of the equilibrium or non-equilibrium melt state, the recurrence of the high melting temperature peak is observed when the samples synthesized using the single-site catalytic system are left to isothermal crystallization at a specific temperature. The recurrence of the high melting temperature, close to the equilibrium melting point of the polymer, questions the differences in entanglements formed before and after polymerization in these high molar masses. The differences in the topological constraints are likely to influence the difference in melting temperatures of the isothermally crystallized samples. In the presence of rGON, the melting response of disentangled UHMWPE crystallized from its heterogeneous melt state changes; at a specific filler concentration, it is observed that the high endothermic peak remains independent of the annealing time in melt. This observation strengthens the concept that in the presence of the filler, chain dynamics is arrested to an extent that the nonequilibrium melt state having lower entanglement density is retained, facilitating the formation of crystals having high melting temperature. IntroductionThe topology of methylene segments in the non-crystalline region of the semi-crystalline polymer Ultrahigh Molecular Weight Polyethylene (UHMWPE), has a profound influence on the mechanical deformation either uniaxially or biaxially [1]. The topology can be tailored by controlling the crystallization kinetics either by dissolution and crystallization or controlled polymerization [2,3,4,5]. The influence of mo...

The use of a hindered phenol to trap free trimethylaluminum (TMA) in methylaluminoxane (MAO) solutions has been reported to improve the performance of single-site, homogeneous catalysts for olefin polymerization. In the present study, with the help of rheological analyses, we have investigated and compared the molecular weight, molecular weight distribution and entanglement density of ultrahigh molecular weight polyethylene synthesized with a single-site catalyst activated by MAO and phenol-modified MAO. While the number average molecular weight (M n ) of the obtained polymers remains the same for both activations, a higher yield and a higher entanglement density are found in the initial stages of polymerization on using phenolmodified MAO as the cocatalyst. These results suggest that on using the phenol-modified MAO as activator, a higher number of active sites are obtained. Surprisingly in the presence of untreated MAO, a tail in the higher molecular mass region is produced.

Recently, it has been shown that by using a single-site catalytic system having titanium as a metallic center, it is possible to tailor the entanglement density in the amorphous region of a semi-crystalline ultra-high molecular weight polyethylene (UHMWPE). This route provides the possibility to make high-modulus, high-strength uniaxially and biaxially drawn tapes and films, without using any solvent during processing. In this publication, it is shown that a single-site catalyst having chromium as metallic center, proposed by Enders and co-workers, can also be tuned to provide control on the entanglement density during synthesis of the UHMWPE. However, to achieve the goal some modifications during the synthesis are required. The synthesized polymers can be processed in the solid state below the equilibrium melting temperature, resulting in uniaxially drawn tapes having tensile strength and modulus greater than 3.5 N/tex and 200 N/tex, respectively. Rheological studies have been performed to follow the increase in entanglement density in melt state with time.