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Related Concept Videos

Molecular Weight of Step-Growth Polymers01:08

Molecular Weight of Step-Growth Polymers

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Step growth polymerization involves bi or multifunctional monomers. Bifunctional monomers react to form linear step growth polymers, whereas multifunctional monomers react to form non-linear or branched polymers.
As the step-growth polymerization involves step-wise condensation of monomers, the molecular weight also builds up eventually. Consequently, high molecular weight polymers are obtained at the late stages of the polymerization, where 99% of monomers have been consumed.
The extent of the...
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Characteristics and Nomenclature of Copolymers01:24

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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 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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Ziegler–Natta Chain-Growth Polymerization: Overview01:17

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Ziegler–Natta polymerization is another form of addition or chain‐growth polymerization used for synthesizing linear polymers over branched polymers. The catalyst used for polymerization is the Ziegler–Natta catalyst, named after Karl Ziegler and Giulio Natta, who developed it in 1953. This catalyst is an organometallic complex of titanium tetrachloride and triethyl aluminum, with the active form of the catalyst being an alkyl titanium compound. Using the Ziegler–Natta...
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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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Anionic Chain-Growth Polymerization: Overview01:20

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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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Characteristic System Time Scales Can Influence the Collective Sequence Development of Nematically Ordered

Ryan L Hamblin1, Zhongmin Zhang2, Kateri H DuBay1

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Controlling copolymer sequences is difficult. This study shows stiff polymers self-align during polymerization, creating characteristic block lengths and influencing material properties.

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Area of Science:

  • Polymer Chemistry
  • Materials Science
  • Chemical Engineering

Background:

  • Copolymer sequence critically influences material properties, posing a significant control challenge.
  • Previous work demonstrated emergent nematic alignment in stiff polymers during step-growth polymerization.
  • Alignment extent and timing impact polymerization kinetics and sequence development.

Purpose of the Study:

  • To explore the emergence of characteristic block lengths over time in stiff copolymers.
  • To investigate how activation energy, viscosity, and monomer density affect sequence and block length distributions.
  • To understand the influence of emergent aggregation and nematic ordering on chain reactivity and sequence formation.

Main Methods:

  • Investigated stiff copolymers undergoing step-growth polymerization.
  • Analyzed the impact of varying activation energy, solution viscosity, and monomer density.
  • Studied the relationship between reaction kinetics, reactant diffusion, and emergent block lengths.

Main Results:

  • Emergent aggregation and nematic ordering restrict longer chain bonding, favoring characteristic lengths.
  • Block length distributions become unusually peaked due to length-dependent reaction propensities.
  • Characteristic length scales are sensitive to the interplay of reaction kinetics and diffusion.

Conclusions:

  • Nematic ordering in stiff copolymers leads to characteristic block lengths, influencing sequence distributions.
  • Reaction conditions (activation energy, viscosity) can tune these characteristic lengths.
  • Potential exists to control sequence repeats in stiff/semiflexible copolymers via nonbonded interactions and kinetics.