Reversible radical ring-crossover polymerization of an alkoxyamine-containing dynamic covalent macrocycle

Go Yamaguchi; Yuji Higaki; Hideyuki Otsuka; Atsushi Takahara

doi:10.1021/ma0503209

Reversible radical ring-crossover polymerization of an alkoxyamine-containing dynamic covalent macrocycle

Go Yamaguchi, Yuji Higaki, Hideyuki Otsuka, Atsushi Takahara

Department of Applied Molecular Chemistry

Research output: Contribution to journal › Article › peer-review

75 Citations (Scopus)

Abstract

The synthesis of a macrocycle with alkoxyamine-based dynamic covalent bonds and its dynamic polymerization behavior are described. The macrocyclic alkoxyamine was synthesized by condensation of an alkoxyamine-based diol with adipoyl chloride under high-dilution conditions. Spectroscopic measurements revealed that one of the obtained macrocyclic compounds was a [2 + 2] adduct. The [2 + 2] macrocyclic compound acted as a monomer for "ring-crossover" polymerization to afford the corresponding polymer with M_n = 2000-18 000 due to the intermolecular radical crossover reaction. The polymerization behavior strongly depended on concentration, time, and temperature. Furthermore, under high-dilution conditions, the obtained poly(alkoxyamine) depolymerized to the monomer or oligomers mainly by the intramolecular radical exchange process.

Original language	English
Pages (from-to)	6316-6320
Number of pages	5
Journal	Macromolecules
Volume	38
Issue number	15
DOIs	https://doi.org/10.1021/ma0503209
Publication status	Published - Jul 26 2005

All Science Journal Classification (ASJC) codes

Organic Chemistry
Polymers and Plastics
Inorganic Chemistry
Materials Chemistry

Access to Document

10.1021/ma0503209

Cite this

@article{06f4faea217343a7a50b56019ac05ded,

title = "Reversible radical ring-crossover polymerization of an alkoxyamine-containing dynamic covalent macrocycle",

abstract = "The synthesis of a macrocycle with alkoxyamine-based dynamic covalent bonds and its dynamic polymerization behavior are described. The macrocyclic alkoxyamine was synthesized by condensation of an alkoxyamine-based diol with adipoyl chloride under high-dilution conditions. Spectroscopic measurements revealed that one of the obtained macrocyclic compounds was a [2 + 2] adduct. The [2 + 2] macrocyclic compound acted as a monomer for {"}ring-crossover{"} polymerization to afford the corresponding polymer with Mn = 2000-18 000 due to the intermolecular radical crossover reaction. The polymerization behavior strongly depended on concentration, time, and temperature. Furthermore, under high-dilution conditions, the obtained poly(alkoxyamine) depolymerized to the monomer or oligomers mainly by the intramolecular radical exchange process.",

author = "Go Yamaguchi and Yuji Higaki and Hideyuki Otsuka and Atsushi Takahara",

year = "2005",

month = jul,

day = "26",

doi = "10.1021/ma0503209",

language = "English",

volume = "38",

pages = "6316--6320",

journal = "Macromolecules",

issn = "0024-9297",

publisher = "American Chemical Society",

number = "15",

}

TY - JOUR

T1 - Reversible radical ring-crossover polymerization of an alkoxyamine-containing dynamic covalent macrocycle

AU - Yamaguchi, Go

AU - Higaki, Yuji

AU - Otsuka, Hideyuki

AU - Takahara, Atsushi

PY - 2005/7/26

Y1 - 2005/7/26

N2 - The synthesis of a macrocycle with alkoxyamine-based dynamic covalent bonds and its dynamic polymerization behavior are described. The macrocyclic alkoxyamine was synthesized by condensation of an alkoxyamine-based diol with adipoyl chloride under high-dilution conditions. Spectroscopic measurements revealed that one of the obtained macrocyclic compounds was a [2 + 2] adduct. The [2 + 2] macrocyclic compound acted as a monomer for "ring-crossover" polymerization to afford the corresponding polymer with Mn = 2000-18 000 due to the intermolecular radical crossover reaction. The polymerization behavior strongly depended on concentration, time, and temperature. Furthermore, under high-dilution conditions, the obtained poly(alkoxyamine) depolymerized to the monomer or oligomers mainly by the intramolecular radical exchange process.

AB - The synthesis of a macrocycle with alkoxyamine-based dynamic covalent bonds and its dynamic polymerization behavior are described. The macrocyclic alkoxyamine was synthesized by condensation of an alkoxyamine-based diol with adipoyl chloride under high-dilution conditions. Spectroscopic measurements revealed that one of the obtained macrocyclic compounds was a [2 + 2] adduct. The [2 + 2] macrocyclic compound acted as a monomer for "ring-crossover" polymerization to afford the corresponding polymer with Mn = 2000-18 000 due to the intermolecular radical crossover reaction. The polymerization behavior strongly depended on concentration, time, and temperature. Furthermore, under high-dilution conditions, the obtained poly(alkoxyamine) depolymerized to the monomer or oligomers mainly by the intramolecular radical exchange process.

UR - http://www.scopus.com/inward/record.url?scp=23744478889&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=23744478889&partnerID=8YFLogxK

U2 - 10.1021/ma0503209

DO - 10.1021/ma0503209

M3 - Article

AN - SCOPUS:23744478889

SN - 0024-9297

VL - 38

SP - 6316

EP - 6320

JO - Macromolecules

JF - Macromolecules

IS - 15

ER -

Reversible radical ring-crossover polymerization of an alkoxyamine-containing dynamic covalent macrocycle

Abstract

All Science Journal Classification (ASJC) codes

Access to Document

Other files and links

Fingerprint

Cite this