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Free-Radical Chain Reaction and Polymerization of Alkenes02:35

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The conversion of alkenes to macromolecules called polymers is a reaction of high commercial importance. The structure of the polymer is defined by a repeating unit, while the terminal groups are considered insignificant. The average degree of polymerization represents the number of repeating units in the polymer molecule and is denoted by the subscript n.
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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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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 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 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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Short Aromatic Blocks Enhance Styrene Conversion in Polymer Cubosome Formation via Polymerization-Induced

Yalan Sun1, Yongbin Zhao2, Aihua Chen1

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Macromolecular Rapid Communications
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Summary

Researchers improved polymer cubosome (PC) fabrication using polymerization-induced self-assembly (PISA). Incorporating an azobenzene block enhanced styrene conversion, enabling efficient PC production with diverse functional groups.

Keywords:
aromatic interactionblock copolymerspolymer cubosomespolymerization‐induced self‐assemblystyrene conversion

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Area of Science:

  • Nanomaterials and nanotechnology
  • Polymer chemistry
  • Self-assembly

Background:

  • Polymer cubosomes (PCs) are nanomaterials with significant application potential.
  • PC fabrication via polymerization-induced self-assembly (PISA) is challenging due to low styrene conversion.
  • Improving monomer conversion is key to efficient PC synthesis.

Purpose of the Study:

  • To develop a novel strategy for enhancing styrene conversion in PC preparation via PISA.
  • To investigate the role of specific block copolymers in improving monomer conversion.
  • To facilitate the efficient synthesis of functionalized polymer cubosomes.

Main Methods:

  • Incorporation of a short azobenzene-containing block (PMAAz) into the hydrophilic macro-chain transfer agent (macro-CTA).
  • Utilizing PMAAz-tailed poly(poly(ethylene glycol) methyl ether methacrylate) in PISA.
  • Analysis of styrene conversion rates and PC formation under varied conditions.

Main Results:

  • Styrene conversion was significantly improved from 12.9-13.8% to 19.1-26.9% with the PMAAz block.
  • Reduced styrene to macro-CTA feeding ratio was achieved.
  • Aromatic interactions from short hydrophobic blocks were identified as crucial for monomer conversion and PC formation.

Conclusions:

  • A novel and efficient method for PC preparation using PISA was established.
  • The strategy allows for the synthesis of PCs with diverse functional groups.
  • This approach broadens the potential applications of polymer cubosomes in nanotechnology.