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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 word polymer is derived from the Greek words “poly” which means “many” and “mer” which means “parts”. Polymers are long chains of molecules composed of repeating units of smaller molecules, known as monomers. They either occur naturally, such as DNA and proteins, or can be constructed synthetically, like plastics. They have varied structural characteristics, such as linear chains, branched chains, or complex networks, that contribute to the...
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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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Copolymers are the products obtained from the polymerization of multiple monomer species. So, in a polymer chain itself, there can be multiple repeating units that come from different monomers. The process of synthesizing a polymer from different monomer species is called copolymerization. When two monomers are involved, the polymer is known as a bipolymer. Polymers with three and four monomers are termed terpolymers and quaterpolymers, respectively. Figure 1 depicts the copolymerization of...
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Layer-by-Layer Self-Assembly of Polymers with Pairing Interactions.

Gervasio Zaldivar1, Mario Tagliazucchi1

  • 1INQUIMAE-CONICET and DQIAQF, University of Buenos Aires, School of Sciences, Ciudad Universitaria, Pabellón 2, Ciudad Autónoma de Buenos Aires C1428EHA, Argentina.

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|May 26, 2022
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Summary
This summary is machine-generated.

A new molecular theory models polymer self-assembly (LbL-SA) using pairing interactions. It explains key LbL-SA behaviors like phase separation and linear thickness growth, highlighting the balance between attraction and repulsion.

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Area of Science:

  • Polymer Science
  • Materials Science
  • Physical Chemistry

Background:

  • Layer-by-layer self-assembly (LbL-SA) is a versatile technique for fabricating thin films.
  • Understanding the fundamental interactions governing LbL-SA is crucial for controlling film properties.
  • Existing models often focus on electrostatic interactions, limiting their applicability to nonelectrostatic systems.

Purpose of the Study:

  • To introduce a molecular theory for nonelectrostatic layer-by-layer self-assembly (LbL-SA) driven by pairing interactions.
  • To provide a general framework applicable to various non-covalent bonding chemistries.
  • To identify the minimal requirements for achieving nonelectrostatic LbL-SA.

Main Methods:

  • Development of a molecular theory to model polymer self-assembly.
  • Simulation of polymer behavior in bulk solution and during layer deposition.
  • Formulation of a simplified analytical model based on competing interactions.

Main Results:

  • The theory successfully models phase separation in polymer mixtures with pairing interactions.
  • It predicts a linear relationship between film thickness and the number of adsorption steps.
  • Key phenomena such as stoichiometry overcompensation and layer interpenetration are explained.
  • The minimal requirement for nonelectrostatic LbL-SA was identified as the competition between pairing interactions and excluded-volume repulsion.

Conclusions:

  • The molecular theory offers a robust framework for understanding nonelectrostatic LbL-SA.
  • The competition between attractive pairing forces and repulsive excluded-volume forces is fundamental to this assembly process.
  • A simple analytical model based on these competing forces accurately predicts layer volume fractions, validating the molecular theory.