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Polymer Classification: Architecture01:14

Polymer Classification: Architecture

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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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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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Sulfides are the sulfur analog of ethers, just as thiols are the sulfur analog of alcohol. Like ethers, sulfides also consist of two hydrocarbon groups bonded to the central sulfur atom. Depending upon the type of groups present, sulfides can be symmetrical or asymmetrical. Symmetrical sulfides can be prepared via an SN2 reaction between 2 equivalents of an alkyl halide and one equivalent of sodium sulfide.
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Structure and Nomenclature of Ethers02:28

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Structure and Bonding
Ethers are organic compounds with an ether functional group which is characterized by an oxygen atom connected to two — identical or different — alkyl, aryl, or vinyl groups. The C–O–C linkage in dimethyl ether — the simplest ether — has an approximately tetrahedral bond angle of 110.3 degrees. The oxygen atom is sp3- hybridized, with the C–O distance being about 140 pm.
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The introduction of polyesters has brought major development to the textile industry. The wrinkle-free behavior of polyester blends has eliminated the need for starching and ironing clothes.
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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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Thioether-Bearing Hyperbranched Polyether Polyols with Methionine-Like Side-Chains: A Versatile Platform for

Jan Seiwert1, Jana Herzberger1,2, Daniel Leibig1,2

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|January 4, 2017
PubMed
Summary

This study introduces novel thioether-containing hyperbranched polyether polyols synthesized via ring-opening copolymerization. These versatile polymers offer tunable properties and enable orthogonal functionalization for advanced applications.

Keywords:
hyperbranchedorthogonal functionalizationpolyetherspolyglycerolspolyolsthioethers

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Area of Science:

  • Polymer Chemistry
  • Organic Synthesis
  • Materials Science

Background:

  • Hyperbranched polymers offer unique properties compared to linear analogues.
  • Polyether polyols are important building blocks in polymer synthesis.
  • Thioether functionalities can be leveraged for further chemical modifications.

Purpose of the Study:

  • To synthesize novel thioether-bearing hyperbranched polyether polyols.
  • To control polymer architecture and properties through copolymerization.
  • To demonstrate the potential for orthogonal functionalization.

Main Methods:

  • Anionic ring-opening multibranching copolymerization of glycidol and 2-(methylthio)ethyl glycidyl ether (MTEGE).
  • In situ 1H NMR for kinetic studies and reactivity ratio determination.
  • Controlled monomer addition for molecular weight and composition tuning.
  • Thioether oxidation and orthogonal functionalization reactions.

Main Results:

  • Achieved controlled synthesis of hyperbranched polyether polyols with tunable hydroxyl/thioether ratios.
  • Obtained moderate dispersities (Đ = 1.48-1.85) and controllable degrees of branching (DB = 0.36-0.48).
  • Demonstrated tunable thermal properties and aqueous cloud point temperatures (29-75 °C).
  • Successfully performed orthogonal functionalization via thioether oxidation and alcohol group reactions.

Conclusions:

  • Developed a versatile platform for synthesizing functional hyperbranched polyether polyols.
  • Showcased the ability to tailor polymer properties and solubility through chemical modification.
  • Highlighted the potential for creating advanced functional materials and polyelectrolytes.