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Polymers are classified as linear or branched on the basis of their chain architecture. The polymer chains in linear polymers have a long chain-like structure with minimal to no branching at all. Even if a polymer features large substituent groups on the monomer, which appear as branches to the skeleton, it is not considered a branched polymer. A branched polymer contains secondary polymer chains that arise from the main polymer chain. The branching occurs when the polymer growth shifts from...
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Step growth polymerization involves bi or multifunctional monomers. Bifunctional monomers react to form linear step growth polymers, whereas multifunctional monomers react to form non-linear or branched polymers.
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Dual Covalent Cross-Linking Networks in Polynorbornene: Comparison of Shape Memory Performance.

Haotian Zhao1, Qinghong Zhang1, Xinlong Wen1

  • 1Key Laboratory of Rubber-Plastics, Ministry of Education, College of Polymer Science and Engineering, Qingdao University of Science and Technology, Qingdao 266045, China.

Materials (Basel, Switzerland)
|July 2, 2021
PubMed
Summary

Dual crosslinking of polynorbornene (PNB) with sulfur and dicumyl peroxide enhances shape memory performance. Sulfur-rich PNB shows superior mechanical properties and shape recovery due to flexible polysulfide bonds.

Keywords:
dual covalent cross-linking networkspolynorborneneshape memory performance

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Area of Science:

  • Polymer Science
  • Materials Science
  • Organic Chemistry

Background:

  • Polynorbornene (PNB) is a versatile polymer with potential applications in shape memory materials.
  • Developing effective crosslinking strategies is crucial for optimizing PNB's mechanical and shape memory properties.

Purpose of the Study:

  • To investigate the dual covalent crosslinking of tetrakis(dimethyllamino)ethylene (TDAE) plasticized PNB using sulfur (S) and dicumyl peroxide (DCP).
  • To evaluate the impact of varying crosslinker amounts on crosslinking degree, mechanical properties, glass transition temperature, and shape memory performance.
  • To elucidate the distinct reaction mechanisms of sulfur and DCP in PNB crosslinking.

Main Methods:

  • Simultaneous crosslinking of PNB using sulfur and dicumyl peroxide.
  • Characterization of crosslinking degree, mechanical properties (tensile strength), and glass transition temperature.
  • Assessment of shape memory performance, including shape fixation and shape recovery ratios.
  • Analysis of crosslinking mechanisms using Fourier transform infrared (FTIR) spectroscopy and Raman spectroscopy.

Main Results:

  • Sulfur-rich crosslinked PNB exhibited higher crosslinking density, tensile strength, and a slightly elevated glass transition temperature compared to DCP-rich systems.
  • Both sulfur and DCP crosslinking significantly improved PNB's shape memory performance over the uncrosslinked polymer.
  • Sulfur-rich PNB demonstrated superior shape memory behavior, achieving shape fixation ratios >99% and shape recovery ratios >90%.
  • Sulfur crosslinking formed monosulfide, disulfide, and polysulfide bonds, with increased polysulfide content correlating with higher sulfur amounts.
  • DCP crosslinking formed C-C covalent bonds via reaction with PNB double bonds.

Conclusions:

  • Dual covalent crosslinking with sulfur and DCP effectively enhances PNB's mechanical properties and shape memory capabilities.
  • The formation of flexible polysulfide bonds from sulfur crosslinking is key to achieving excellent mechanical properties and high elastic recovery.
  • Sulfur-rich crosslinked PNB offers superior shape memory performance, making it a promising material for advanced applications requiring high shape fidelity and recovery.