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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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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.
Many natural and synthetic polymers are produced by...
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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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Anionic Chain-Growth Polymerization: Mechanism01:04

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The mechanism for anionic chain-growth polymerization involves initiation, propagation, and termination steps. In the initiation step, a nucleophilic anion, such as butyl lithium, initiates the polymerization process by attacking the π bond of the vinylic monomer. As a result, a carbanion, stabilized by the electron‐withdrawing group, is generated. The resulting carbanion acts as a Michael donor in the propagation step and attacks the second vinylic monomer, which acts as a Michael...
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Cationic Chain-Growth Polymerization: Mechanism00:57

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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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Increasing Molecular Mass in Enzymatic Lactone Polymerizations.

Santanu Kundu1, Peter M Johnson1, Kathryn L Beers1

  • 1Polymers Division, National Institute of Standards and Technology, Gaithersburg, Maryland 20899, United States.

ACS Macro Letters
|May 17, 2022
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This summary is machine-generated.

Researchers improved poly(caprolactone) molecular mass using enzyme-catalyzed ring-opening polymerization. By controlling water equilibrium with molecular sieves, they achieved higher molecular weights and validated their kinetic model.

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Area of Science:

  • Polymer Chemistry
  • Biocatalysis
  • Materials Science

Background:

  • Enzyme-catalyzed ring-opening polymerization (e.g., of ε-caprolactone) is a key method for producing biodegradable polymers like poly(caprolactone).
  • Controlling polymer molecular mass is crucial for tailoring material properties, but achieving high molecular weights can be challenging due to equilibrium limitations.

Purpose of the Study:

  • To develop and validate a method for improving the molecular mass of poly(caprolactone) produced via enzyme-catalyzed ring-opening polymerization.
  • To investigate the kinetic mechanisms governing polymerization and degradation, focusing on equilibrium control.

Main Methods:

  • Development of a kinetic model for enzyme-catalyzed poly(caprolactone) polymerization and degradation.
  • Experimental control of the water/linear chain equilibrium using water-trapping molecular sieves during batch polymerization of ε-caprolactone.
  • Comparison of experimental results with model predictions.

Main Results:

  • Addition of molecular sieves effectively shifted the equilibrium, leading to higher poly(caprolactone) molecular masses after complete conversion.
  • Ring-opening rates were largely unaffected by the molecular sieves.
  • Experimental data showed good agreement with the developed kinetic model, validating the approach.

Conclusions:

  • Manipulating equilibrium reactions in the kinetic pathway is an effective strategy to enhance molecular mass in enzyme-catalyzed lactone polymerization.
  • The developed kinetic model provides a framework for understanding and optimizing such polymerization processes.
  • This work offers a practical method for improving the molecular weight of biodegradable polymers produced through biocatalysis.