Copper‐mediated initiators for continuous activator regeneration atom transfer radical polymerization of acrylonitrile

Abstract

Initiators for continuous activator regeneration atom transfer radical polymerization technique was first accessed to acrylonitrile by using CuBr 2 /2,2 0 -bipyridine as the catalyst, ethyl 2-bromoisobutyrate as the halogen initiator, and azobis(isobutyronitrile) as the free radical initiator. The key to success is ascribed to the facile achievement of the rapid equilibrium between active species and dormant species. Effects of ligand, catalyst concentration, free radical initiator concentration, and reaction temperature on the polymerization reaction and molecular weight (MW) as well as polydispersity index (PDI) were investigated in detail. The polymerization proceeded in a controlled/living fashion even though the concentration of copper catalyst decreased to 50 ppm, which is evident in pseudo first-order kinetics of polymerization, linear increase of molecular weight, low PDI, and high chain-end functionality of the generated polymer. V C 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 50: [4358][4359][4360][4361][4362][4363][4364] 2012

“Nascent” Cu(0) nanoparticles‐mediated single electron transfer living radical polymerization of acrylonitrile at ambient temperature

“…The molecular weight was determined to be about 2010 by comparing the peak intensity ratios between the methylene protons in main‐chain repeated units (d) and the methine proton at the ω‐end (g), which approached the theoretical one ( M n,th = 1692). The results prove that the EBiB moiety was successfully attached to the PAN chain ends, and the PAN obtained possessed high chain‐capped fidelity 21, 22, 61…”

“Nascent” Cu(0) nanoparticles‐mediated single electron transfer living radical polymerization of acrylonitrile at ambient temperature

“…The molecular weight was determined to be about 2010 by comparing the peak intensity ratios between the methylene protons in main‐chain repeated units (d) and the methine proton at the ω‐end (g), which approached the theoretical one ( M n,th = 1692). The results prove that the EBiB moiety was successfully attached to the PAN chain ends, and the PAN obtained possessed high chain‐capped fidelity 21, 22, 61…”

Young women with family history of breast cancer and their risk factors for benign breast disease

“…The molecular weight was determined to be about 2010 by comparing the peak intensity ratios between the methylene protons in main‐chain repeated units (d) and the methine proton at the ω‐end (g), which approached the theoretical one ( M n,th = 1692). The results prove that the EBiB moiety was successfully attached to the PAN chain ends, and the PAN obtained possessed high chain‐capped fidelity 21, 22, 61…”

Synthesis of Polyacrylonitrile by ARGET Atom Transfer Radical Polymerization in the Presence of Zinc Powder and Its Adsorption Properties after Modification

“…Figure illustrated the plots of M n and M w / M n of PAN versus monomer conversion. Though use of a PMMA standard may caused the departure between the determined M n values and the absolute M n values of PAN due to the difference of the hydrodynamic volume between PAN and PMMA, the determined M n values could relatively illustrate the absolute M n values to a certain extent according to Matyjaszewski and Liu . As shown in Figure , M n increased linearly with monomer conversion and M w / M n was narrow in the range of 1.09–1.19.…”

“Nascent” Cu(0) nanoparticles‐mediated single electron transfer living radical polymerization of acrylonitrile at ambient temperature

“…The molecular weight was determined to be about 2010 by comparing the peak intensity ratios between the methylene protons in main‐chain repeated units (d) and the methine proton at the ω‐end (g), which approached the theoretical one ( M n,th = 1692). The results prove that the EBiB moiety was successfully attached to the PAN chain ends, and the PAN obtained possessed high chain‐capped fidelity 21, 22, 61…”

Young women with family history of breast cancer and their risk factors for benign breast disease

“…The molecular weight was determined to be about 2010 by comparing the peak intensity ratios between the methylene protons in main‐chain repeated units (d) and the methine proton at the ω‐end (g), which approached the theoretical one ( M n,th = 1692). The results prove that the EBiB moiety was successfully attached to the PAN chain ends, and the PAN obtained possessed high chain‐capped fidelity 21, 22, 61…”

Synthesis of Polyacrylonitrile by ARGET Atom Transfer Radical Polymerization in the Presence of Zinc Powder and Its Adsorption Properties after Modification

“…Figure illustrated the plots of M n and M w / M n of PAN versus monomer conversion. Though use of a PMMA standard may caused the departure between the determined M n values and the absolute M n values of PAN due to the difference of the hydrodynamic volume between PAN and PMMA, the determined M n values could relatively illustrate the absolute M n values to a certain extent according to Matyjaszewski and Liu . As shown in Figure , M n increased linearly with monomer conversion and M w / M n was narrow in the range of 1.09–1.19.…”

“Nascent” Cu(0) nanoparticles‐mediated single electron transfer living radical polymerization of acrylonitrile at ambient temperature

“…The molecular weight was determined to be about 2010 by comparing the peak intensity ratios between the methylene protons in main‐chain repeated units (d) and the methine proton at the ω‐end (g), which approached the theoretical one ( M n,th = 1692). The results prove that the EBiB moiety was successfully attached to the PAN chain ends, and the PAN obtained possessed high chain‐capped fidelity 21, 22, 61…”

Young women with family history of breast cancer and their risk factors for benign breast disease

“…The molecular weight was determined to be about 2010 by comparing the peak intensity ratios between the methylene protons in main‐chain repeated units (d) and the methine proton at the ω‐end (g), which approached the theoretical one ( M n,th = 1692). The results prove that the EBiB moiety was successfully attached to the PAN chain ends, and the PAN obtained possessed high chain‐capped fidelity 21, 22, 61…”

Synthesis of Polyacrylonitrile by ARGET Atom Transfer Radical Polymerization in the Presence of Zinc Powder and Its Adsorption Properties after Modification

“…Figure illustrated the plots of M n and M w / M n of PAN versus monomer conversion. Though use of a PMMA standard may caused the departure between the determined M n values and the absolute M n values of PAN due to the difference of the hydrodynamic volume between PAN and PMMA, the determined M n values could relatively illustrate the absolute M n values to a certain extent according to Matyjaszewski and Liu . As shown in Figure , M n increased linearly with monomer conversion and M w / M n was narrow in the range of 1.09–1.19.…”