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Related Concept Videos

Step-Growth Polymerization: Overview01:03

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Step-growth or condensation polymerization is a stepwise reaction of bi or multifunctional monomers to form long-chain polymers. As all the monomers are reactive, most of the monomers are consumed at the early stages of the reaction to form small chains of reactive oligomers, which then combine to form long polymer chains in the late stages. Hence, the reaction has to proceed for a long time to achieve high molecular weight polymers.
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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...
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Ziegler–Natta polymerization is another form of addition or chain‐growth polymerization used for synthesizing linear polymers over branched polymers. The catalyst used for polymerization is the Ziegler–Natta catalyst, named after Karl Ziegler and Giulio Natta, who developed it in 1953. This catalyst is an organometallic complex of titanium tetrachloride and triethyl aluminum, with the active form of the catalyst being an alkyl titanium compound. Using the Ziegler–Natta...
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Anionic Chain-Growth Polymerization: Overview01:20

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The polymerization process that involves carbanion as an intermediate is called anionic polymerization. It is also a type of addition or chain-growth polymerization. Anionic polymerization gets initiated by a strong nucleophile such as an organolithium or a Grignard reagent. The most commonly used initiator for anionic polymerization is butyl lithium. Monomers involved in anionic polymerization must possess a vinyl group bonded to one or two electron-withdrawing groups. For instance,...
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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.
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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...
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Directional polymer crystallisation with a fast-moving sink.

Ahana Purushothaman1, Sabin Adhikari2, Christopher Durning2

  • 1Department of Chemical Engineering, Indian Institute of Technology, Madras, 600036, India. sumesh@iitm.ac.in.

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Summary
This summary is machine-generated.

Zone annealing in polymers shows an analogy to isothermal crystallization due to low thermal conductivity. Faster sink velocities lead to partial crystallization by hindering heat dissipation, a phenomenon explained by scale separation.

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Area of Science:

  • Materials Science
  • Polymer Physics
  • Thermodynamics

Background:

  • Non-isothermal directional polymer crystallization (Zone Annealing) previously shown analogous to isothermal protocols.
  • This analogy arises from polymers' low thermal conductivity, creating scale separation between crystallization domain and thermal gradient.
  • This scale separation allows approximating crystallinity profile as a step, with temperature at the step acting as effective isothermal crystallization temperature.

Purpose of the Study:

  • Investigate directional polymer crystallization under faster moving sinks.
  • Analyze the steady-state behavior and transition to incomplete crystallization at high sink velocities.
  • Compare numerical simulations with analytical theory for heat transport and crystallization.

Main Methods:

  • Numerical simulations of directional polymer crystallization.
  • Analytical theory development using regular perturbation solutions.
  • Analysis of heat transport and crystallization dynamics between heat sink and solid-melt interface.

Main Results:

  • A steady state exists even with partial crystallization at faster sink velocities.
  • At high velocities, inefficient latent heat dissipation leads to temperature increase and incomplete crystallization.
  • Transition to incomplete crystallization occurs when sink-interface distance and crystallization interface width become comparable.

Conclusions:

  • The study validates the existence of a steady state in directional polymer crystallization under high sink velocities.
  • Scale separation remains crucial, but its limits are reached at faster processing speeds.
  • Analytical solutions agree well with numerical results, providing a theoretical framework for understanding these phenomena.