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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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Polymerization generates chiral centers along the entire backbone of a polymer chain. Accordingly, the stereochemistry of the substituent group has a significant effect on polymer properties. Polymers formed from monosubstituted alkene monomers feature chiral carbons at every alternate position in the polymer backbone. Relative to the predominant orientation of substituents at the adjacent chiral carbons, the polymer can exist in three different configurations: isotactic, syndiotactic, and...
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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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Recently, the development of olefin metathesis polymerization advanced the field of polymer synthesis. Simply put, the reorganization of substituents on their double bonds between two olefins in the presence of a catalyst is known as the olefin metathesis reaction. The use of metathesis reaction for polymer synthesis is called olefin metathesis polymerization.
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Polymers that are made up of identical monomer units are called homopolymers. Only one repeating unit is involved in the construction of the homopolymer structure. For example, as depicted in Figure 1, polypropylene is a homopolymer constituted of propylene monomers. Here, the only repeating unit in the polymer chain is propylene.
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Sequence-controlled supramolecular terpolymerization directed by specific molecular recognitions.

Takehiro Hirao1,2, Hiroaki Kudo1, Tomoko Amimoto3

  • 1Department of Chemistry, Graduate School of Science, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, 739-8526, Japan.

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Researchers developed sequence-controlled supramolecular terpolymerization using self-sorting host-guest chemistry. This breakthrough enables precise engineering of synthetic polymer sequences, mimicking nature's control over biopolymers for advanced material functions.

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Area of Science:

  • Polymer Chemistry
  • Supramolecular Chemistry
  • Materials Science

Background:

  • Nature exhibits precise control over monomer sequencing in biopolymers.
  • Synthetic polymer synthesis has lacked precise control over primary monomer sequences.
  • Engineering polymer main-chain sequences is a significant challenge in polymer science.

Purpose of the Study:

  • To develop a method for sequence-controlled supramolecular terpolymerization.
  • To enable precise engineering of synthetic polymer sequences.
  • To create polymers with tailored sequences for advanced functions.

Main Methods:

  • Utilized self-sorting behavior among three sets of monomers with mismatched host-guest pairs.
  • Incorporated complementary host-guest complexes (biscalix[5]arene-C60, bisporphyrin-trinitrofluorenone (TNF), and hydrogen-bonding complexes) into heteroditopic monomers.
  • Generated ABC sequence-controlled supramolecular terpolymers.

Main Results:

  • Successfully demonstrated sequence-controlled supramolecular terpolymerization.
  • Confirmed the polymeric nature of the synthesized terpolymers in solution and solid states.
  • Established a novel synthetic methodology for precise polymer sequence control.

Conclusions:

  • The developed method allows for the creation of synthetic polymers with precisely controlled monomer sequences.
  • This approach mimics the sequence precision found in natural biopolymers.
  • The methodology opens avenues for constructing polymers with advanced, tailored functions.