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Ring-opening metathesis polymerization or ROMP involves strained cycloalkenes as starting materials. The mechanism of ROMP proceeds by reacting cycloalkene with Grubbs catalyst to give metallacyclobutane intermediate which undergoes a ring-opening reaction to form new carbene. The new carbene reacts with another molecule of cycloalkene. Repetition of these steps leads to the formation of an unsaturated open-chain polymer product. All these steps are reversible, however, relieving the ring...
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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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Ion exchange chromatography separates charged molecules from a solution by reversibly exchanging them with mobile, or 'active', ions associated with the oppositely charged stationary phase. This method can be used to separate ions, soften and deionize water, and purify solutions. The polymers comprising the ion-exchange column are high-molecular-weight and chemically stable polymers, crosslinked to be porous and essentially insoluble. They are also functionalized with either acidic or...
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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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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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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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Self-assembling Morphologies Obtained from Helical Polycarbodiimide Copolymers and Their Triazole Derivatives
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Alternating ROMP copolymers containing charge-transfer units.

Joy Romulus1, Li Tan, Marcus Weck

  • 1Department of Chemistry and Molecular Design Institute, New York University, New York, NY 10003.

ACS Macro Letters
|October 26, 2013
PubMed
Summary
This summary is machine-generated.

New alternating copolymers synthesized via ring-opening metathesis polymerization (ROMP) show enhanced charge-transfer properties. Bulky side-chains improve polymerization control compared to linear analogs.

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Area of Science:

  • Polymer Chemistry
  • Materials Science
  • Organic Synthesis

Background:

  • Alternating copolymers offer unique electronic and optical properties.
  • Ring-opening metathesis polymerization (ROMP) is a versatile method for polymer synthesis.
  • Functionalized cyclobutene esters (CBE) and cyclohexenes (CH) are key monomers.

Purpose of the Study:

  • To synthesize and characterize novel alternating copolymers with specific side-chains.
  • To investigate the impact of bulky side-chains on polymerization control.
  • To evaluate the charge-transfer properties of the resulting copolymers.

Main Methods:

  • Ring-opening metathesis polymerization (ROMP) of functionalized CBE and CH.
  • Incorporation of dialcoxynaphthalene (DAN) and pyromellitic dianhydride (PDI) side-chains.
  • UV-Vis spectroscopy for characterization of charge-transfer intensity.

Main Results:

  • Successful synthesis of alternating copolymers poly(CBE-alt-CH)n with DAN and PDI side-chains.
  • Observed increase in charge-transfer intensity compared to previous alternating copolymers.
  • Bulky side-chains effectively inhibited backbiting, leading to enhanced polymerization control.

Conclusions:

  • The developed ROMP strategy yields copolymers with improved charge-transfer characteristics.
  • Bulky side-chains are crucial for achieving controlled polymerization and preventing side reactions.
  • These novel copolymers hold potential for applications requiring specific optoelectronic properties.