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Polymer Classification: Architecture01:14

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Polymers are classified as linear or branched on the basis of their chain architecture. The polymer chains in linear polymers have a long chain-like structure with minimal to no branching at all. Even if a polymer features large substituent groups on the monomer, which appear as branches to the skeleton, it is not considered a branched polymer. A branched polymer contains secondary polymer chains that arise from the main polymer chain. The branching occurs when the polymer growth shifts from...
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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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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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Acyclic diene metathesis polymerization or ADMET polymerization involves cross-metathesis of terminal dienes, such as 1,8-nonadiene, to give linear unsaturated polymer and ethylene. As ADMET is a reversible process, the formed ethylene gas must be removed from the reaction mixture to complete the polymerization process.
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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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Chain-growth or addition polymerization is successive addition reactions of monomers with a polymer chain. In radical chain-growth polymerization, the reaction proceeds via a free-radical intermediate. The free radical is formed from radical initiators, which spontaneously generate free radicals by homolytic fission. Organic peroxides (such as dibenzoyl peroxide, as shown in Figure 1) or azo compounds are popular radical initiators. A low concentration ratio of radical initiator to monomer is...
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Circular Cross-Linked Polyethylene Enabled by In-Chain Ketones.

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This study introduces recyclable cross-linked polyethylenes (PEs) using keto-functionalization. These novel materials can be efficiently cross-linked and then de-cross-linked for up to 97% material recycling.

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Area of Science:

  • Polymer Chemistry
  • Materials Science
  • Sustainable Polymers

Background:

  • Cross-linked polyethylenes (PEs) offer enhanced properties but pose recycling challenges due to permanent cross-links.
  • Developing recyclable thermoset polymers is crucial for sustainable materials management.

Purpose of the Study:

  • To develop a method for creating recyclable cross-linked polyethylenes (PEs).
  • To investigate the efficient cross-linking and de-cross-linking of keto-functionalized PEs.
  • To assess the recyclability and properties of the novel cross-linked PEs.

Main Methods:

  • Keto-functionalization of polyethylenes (PEs) via free-radical and catalytic copolymerization.
  • Cross-linking of keto-PEs using diamines via imine formation in the melt.
  • Hydrolysis of imine cross-links at 140 °C for material recycling.

Main Results:

  • Efficient melt cross-linking of keto-PEs achieved, with gel fractions up to 85%.
  • Cross-linked PEs exhibited improved tensile properties.
  • Up to 97% of the initial thermoplastic keto-polyethylene was recycled after hydrolysis.
  • Optimal keto content of ≤1.5 mol % identified for balancing properties and recyclability.

Conclusions:

  • Imine chemistry provides an effective route for creating recyclable cross-linked polyethylenes (PEs).
  • The developed method allows for efficient cross-linking and high-yield recycling, addressing a key limitation of conventional cross-linked PEs.
  • Low keto content is essential for maintaining desirable PE properties while enabling circular recyclability.