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Polymer Classification: Crystallinity01:21

Polymer Classification: Crystallinity

Unlike ionic or small covalent molecules, polymers do not form crystalline solids due to the diffusion limitations of their long-chain structures. However, polymers contain microscopic crystalline domains separated by amorphous domains.
Crystalline domains are the regions where polymer chains are aligned in an orderly manner and held together in proximity by intermolecular forces. For example, chains in the crystalline domains of polyethylene and nylon are bound together by van der Waals...
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The skeletal structure of polymers synthesized via radical polymerization is always branched. For example, the polymerization of ethylene by radical polymerization results in a low-density grade of polyethylene with a heavily branched skeletal structure. Here, the radical site abstracts hydrogen from the growing chain, and the radical site shifts from the end (a primary carbon center) to anywhere within the growing chain (a secondary carbon center). Consequently, the part of the chain from the...
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The mechanism for anionic chain-growth polymerization involves initiation, propagation, and termination steps. In the initiation step, a nucleophilic anion, such as butyl lithium, initiates the polymerization process by attacking the π bond of the vinylic monomer. As a result, a carbanion, stabilized by the electron‐withdrawing group, is generated. The resulting carbanion acts as a Michael donor in the propagation step and attacks the second vinylic monomer, which acts as a Michael acceptor.
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Molecular Weight of Step-Growth Polymers

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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The extent of the...
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Radical Chain-Growth Polymerization: Mechanism

The radical chain-growth polymerization mechanism consists of three steps: initiation, propagation, and termination of polymerization. The polymerization initiates when a free radical generated from the radical initiator adds to the unsaturated bond in the monomer. The unpaired electron of the free radical and one π electron in the unsaturated bond creates a σ bond between the free radical and the monomer. As a result, the other π electron in the unsaturated bond converts this species into the...
Cationic Chain-Growth Polymerization: Mechanism00:57

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The cationic polymerization mechanism consists of three steps: initiation, propagation, and termination. In the initiation step of the polymerization process, the π bond of a monomer gets protonated by the Lewis acid catalyst, which is formed from boron trifluoride and water. The protonation of the π bond generates a carbocation stabilized by the electron‐donating group. In the propagation step, the π bond of the second monomer acts as a nucleophile and attacks the generated carbocation,...

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DNA Nanotubes as a Versatile Tool to Study Semiflexible Polymers
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Phase behavior of semiflexible polymer chains.

Venkat Padmanabhan1, Sanat K Kumar, Arun Yethiraj

  • 1Department of Chemical Engineering, Columbia University, New York, New York 10027, USA.

The Journal of Chemical Physics
|April 2, 2008
PubMed
Summary

Computer simulations reveal how semiflexible polymer chains transition between isotropic-nematic phases. Chain length influences phase behavior, with density peaking for intermediate lengths before decreasing for longer polymer chains.

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Area of Science:

  • Polymer Physics
  • Statistical Mechanics
  • Computational Chemistry

Background:

  • Understanding phase transitions in polymers is crucial for materials science.
  • Semiflexible polymers exhibit complex behaviors influenced by chain stiffness and length.
  • Previous studies have explored polymer phase diagrams, but detailed simulation data for semiflexible chains is needed.

Purpose of the Study:

  • To delineate the isotropic-nematic (IN) and gas-liquid coexistence envelopes for semiflexible polymer chains.
  • To investigate the effect of chain length (N(b)) on phase transition densities.
  • To compare simulation results with theoretical predictions for polymer behavior.

Main Methods:

  • Monte Carlo simulations were employed to model polymer chains.
  • A square-well potential was used for inter-monomer interactions.
  • A specific potential controlled chain stiffness by restricting distances between non-bonded monomers separated by two bonds.

Main Results:

  • An isotropic-nematic (IN) transition was observed for chains with 10 <= N(b) < 30.
  • Both IN transition density and gas-liquid coexistence density initially increased with N(b), reaching a maximum.
  • For longer chains (N(b) >= 30), these densities decreased with increasing chain length, aligning with theoretical expectations.

Conclusions:

  • The study successfully mapped the phase behavior of semiflexible polymer chains.
  • Chain length plays a critical role in determining phase transition densities, exhibiting non-monotonic behavior.
  • Simulation results provide valuable data for validating theoretical models of polymer physics.