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Endo-norbornene derivatives are much cheaper and more accessible. However, it is difficult to prepare endo-polynorbornenes with ultra-high molecular weight (UHMW) by ring opening metathesis polymerization (ROMP) owing to the low activity. The molecular weight of poly(endo-NB-2OH)n could only reach to 309.1 kg mol−1 for 24 h via ROMP. While, UHMW poly(endo-NB-2OH)m was prepared by combining ROMP and acyclic metathesis reaction in much shorter time. The effects of residual monomer, amount of H2SO4, concentration, temperature and reaction time were investigated in depth. The UHMW P(endo-NB-2OH)m (Mn=2645.5 kg mol−1, PDI = 1.74) could be obtained at 80 °C for 5 min with H2SO4/G3 as 10/1 and concentration of 0.1 M. Moreover, UHMW P(endo-NBI-OH)m(Mn=1114.2 kg mol−1, PDI = 1.95) was also successfully prepared by this method. However, the H2SO4/G3 should increase to 30/1, and reacted for 45 min owing to the steric resistance of the cyclic dicarboximide. For P(exo-NBI-OH)n with lower activity, reaction time should prolong to 3 h to obtain UHMW P(exo-NBI-OH)m(Mn=1716.7 kg mol−1, PDI = 1.93). Finally, UHMW P(endo-NB-2alkyne)m, P(endo-NBI-alkyne)m, and P(exo-NBI-alkyne)m were successfully prepared via post-modification. Acyclic metathesis reaction is a robust and universal reaction to prepare other functional UHMW polynorbornenes, especially for the UHMW endo-polynorbornenes, which could not be prepared by ROMP efficiently. [ABSTRACT FROM AUTHOR]

Highlights In this paper, the reasons for the improved wear resistance of irradiation‐modified Polytetrafluoroethylene (RM‐PTFE) and its composites above the melting point were investigated from the microcrystalline point of view by using methods such as crystallization kinetics, and it was found that the linear wear rate of RM‐PTFE was only 0.3 um/km, with a 1000 times increase in wear resistance, which was due to the transformation of its crystals from flake crystals that were easily dislodged to spherical crystals that were more resistant to abrasion. It was also found that the linear wear rate of Polytetrafluoroethylene (PTFE) with coke and graphite was 0.2 and 0.1 μm/km, respectively, and the abrasion resistance was further improved, which was attributed to the lowering of spherical crystal grain size by coke and graphite, which had better mechanical properties. These studies lay the foundation for future research on the frictional wear mechanism of RM‐PTFE above the melting point. Irradiation‐modified PTFE above the melting point Wear resistance of PTFE increases 1000 times Changes in crystal morphology dramatically increase wear resistance Use of crystallization kinetics to study the crystalline form of PTFE Small grain size improves wear resistance [ABSTRACT FROM AUTHOR]

Ring opening metathesis polymerization (ROMP) is widely used to prepare functional materials with various topological structures. However, it is difficult to prepare polymers with ultra‐high molecular weight (UHMW) directly. We found a new method to prepare UHMW polymers by combining ROMP and acyclic metathesis reaction. First, monomer NB‐2OH was polymerized by ROMP with different feed ratio of NB‐2OH/G3, and obtained well‐defined polymers P(NB‐2OH)n (n = 50, 200, and 463). Then acyclic metathesis reaction was used to synthesize UHMW polymers. The results indicated that polymer P(NB‐2OH)z with higher molecular weight (Mw = 6067.3 kg mol−1) and narrower distribution (PDI = 1.58) could be obtained at 80°C for 5 min, when P(NB‐2OH)463 was used as raw material with H2SO4/G3 = 10/1. Compared with polymer P(NB‐2OH)1990 (Mw = 5343.1 kg mol−1, PDI = 1.61) prepared by ROMP directly, the new method tremendously shortens reaction time, lowers the requirement for the purity of monomer and produces UHMW polymers with narrower distribution. The compositions of prepared polymers were also confirmed clearly by post‐modification and 1H NMR characterization. [ABSTRACT FROM AUTHOR]