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Related Concept Videos

Radical Chain-Growth Polymerization: Overview01:10

Radical Chain-Growth Polymerization: Overview

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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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Radical Chain-Growth Polymerization: Mechanism01:09

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The radical chain-growth polymerization mechanism consists of three steps: initiation, propagation, and termination of polymerization. The polymerization initiates when a free radical generated from the radical initiator adds to the unsaturated bond in the monomer. The unpaired electron of the free radical and one π electron in the unsaturated bond creates a σ bond between the free radical and the monomer. As a result, the other π electron in the unsaturated bond converts this...
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Ziegler–Natta Chain-Growth Polymerization: Overview01:17

Ziegler–Natta Chain-Growth Polymerization: Overview

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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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Radical Chain-Growth Polymerization: Chain Branching01:17

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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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Olefin Metathesis Polymerization: Overview01:13

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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.
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists of a...
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Cationic Chain-Growth Polymerization: Mechanism00:57

Cationic Chain-Growth Polymerization: Mechanism

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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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3D Printing and In Situ Surface Modification via Type I Photoinitiated Reversible Addition-Fragmentation Chain Transfer Polymerization
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Sieving polymer synthesis by reversible addition fragmentation chain transfer polymerization.

Yi Heng Nai1, Roderick C Jones, Michael C Breadmore

  • 1Australia Centre of Research on Separation Science (ACROSS), School of Chemistry, University of Tasmania, Hobart, Australia.

Electrophoresis
|October 10, 2013
PubMed
Summary

High molecular weight poly(N,N-dimethylacrylamide) (PDMA) was synthesized using reversible addition fragmentation chain transfer (RAFT) polymerization for enhanced nucleic acid separation in capillary electrophoresis (CE). This novel PDMA demonstrates superior performance compared to commercial alternatives.

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Area of Science:

  • Polymer Chemistry
  • Analytical Chemistry
  • Biotechnology

Background:

  • Replaceable sieving polymers are crucial for high-resolution nucleic acid separation in capillary electrophoresis (CE).
  • Conventional free radical polymerization has limitations in producing well-defined polymers for this application.
  • Reversible addition fragmentation chain transfer (RAFT) polymerization offers a versatile approach for synthesizing tailored polymers.

Purpose of the Study:

  • To synthesize high molecular weight poly(N,N-dimethylacrylamide) (PDMA) using RAFT polymerization for nucleic acid separation.
  • To investigate the influence of pH control on RAFT polymerization of PDMA.
  • To evaluate the separation performance of the synthesized PDMA.

Main Methods:

  • Multi-step sequential RAFT polymerization using 2-propionic acidyl butyl trithiocarbonate (PABTC) as the chain transfer agent.
  • Synthesis of high molecular weight PDMA (765,000 g/mol) with a low polydispersity index (PDI) of 1.55.
  • Controlled pH conditions during polymerization to minimize hydrolysis and aminolysis of the trithiocarbonate chain transfer agent.

Main Results:

  • Successful synthesis of high molecular weight PDMA via RAFT polymerization, suitable for sieving electrophoresis.
  • Demonstrated the critical role of pH adjustment in achieving high molecular weight polymer synthesis.
  • The synthesized PABTC-PDMA exhibited marginally superior separation efficiency compared to a commercial PDMA (POP™-CAP).

Conclusions:

  • RAFT polymerization is a viable method for producing high molecular weight PDMA for high-resolution DNA separation.
  • Optimized pH conditions are essential for successful RAFT polymerization of PDMA.
  • The novel PABTC-PDMA offers a promising alternative to existing sieving polymers in CE.