Ambient-temperature direct synthesis of poly(organophosphazenes) via the "living" cationic polymerization of organo-substituted phosphoranimines

Harry R. Allcock, James M. Nelson, Scott D. Reeves, Charles H. Honeyman, Ian Manners

Research output: Contribution to journalArticle

109 Citations (Scopus)

Abstract

A new, ambient-temperature method for the direct synthesis of organo-substituted polyphosphazenes is described. It involves the initiation of a series of organophosphoranimines R(R′)-XP=NSiMe3 (3, R = Ph, R′ = X = Cl; 5, R = R′ = Ph, X = Cl; 7, R = Me, R′ = Et, X = Cl; 9, R = R′ = CF3CH2O, X = Br) with catalytic amounts of PCl5 in CH2Cl2 to yield (after treatment with NaOCH2CF3 in the case of 3) the corresponding polyphosphazene species (N=PRR′)., (4, R = Ph, R′ = OCH2CF3; 6, R = R′ = Ph; 8, R = Me, R′ = Et; 10, R = R′ = OCH2CF3) with narrow polydispersities. The molecular weights of the polyphosphazenes were controlled by altering the ratio of monomer to initiator. The polymer chains were found to be active after chain propagation since further addition of monomer resulted in the formation of higher molecular weight polymer. For monomers 7 and 9 optimum polymerization behavior was found to occur at 35°C in the absence of solvent in the presence of catalytic quantities of PCl5. These reactions proceeded to 100% completion, while maintaining molecular weight control and narrow polydispersites. In the case of polymers 4, 8, and 10, which were synthesized with a 10:1 monomer to initiator ratio in CH2Cl2, the resultant polymers were analyzed by gel permeation chromatography (GPC) (4, Mn = 2.9 × 103, polydispersity (PDI = Mw/Mn) = 1.07); 8, Mn = 2.2 × 103, PDI = 1.31; 10, Mn = 7.8 × 103, PDI = 1.23). Poly(diphenylphosphazene), (N=PPh2)n (6), was insoluble in common organic solvents and was characterized by magic angle spinning (MAS) solid state 31P NMR spectroscopy. The effects of side group steric bulk, electron-withdrawing or -donating properties, and leaving group types on the ambient-temperature cationic induced polymerizations are discussed.

Original languageEnglish (US)
Pages (from-to)50-56
Number of pages7
JournalMacromolecules
Volume30
Issue number1
DOIs
StatePublished - Jan 13 1997

Fingerprint

Cationic polymerization
Living polymerization
Polymers
Monomers
Molecular weight
Polydispersity
Polymerization
Weight control
Temperature
Magic angle spinning
Gel permeation chromatography
Organic solvents
Nuclear magnetic resonance spectroscopy
Electrons

All Science Journal Classification (ASJC) codes

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

Allcock, Harry R. ; Nelson, James M. ; Reeves, Scott D. ; Honeyman, Charles H. ; Manners, Ian. / Ambient-temperature direct synthesis of poly(organophosphazenes) via the "living" cationic polymerization of organo-substituted phosphoranimines. In: Macromolecules. 1997 ; Vol. 30, No. 1. pp. 50-56.
@article{20a6cab689f74e61a5a1d079cb24467b,
title = "Ambient-temperature direct synthesis of poly(organophosphazenes) via the {"}living{"} cationic polymerization of organo-substituted phosphoranimines",
abstract = "A new, ambient-temperature method for the direct synthesis of organo-substituted polyphosphazenes is described. It involves the initiation of a series of organophosphoranimines R(R′)-XP=NSiMe3 (3, R = Ph, R′ = X = Cl; 5, R = R′ = Ph, X = Cl; 7, R = Me, R′ = Et, X = Cl; 9, R = R′ = CF3CH2O, X = Br) with catalytic amounts of PCl5 in CH2Cl2 to yield (after treatment with NaOCH2CF3 in the case of 3) the corresponding polyphosphazene species (N=PRR′)., (4, R = Ph, R′ = OCH2CF3; 6, R = R′ = Ph; 8, R = Me, R′ = Et; 10, R = R′ = OCH2CF3) with narrow polydispersities. The molecular weights of the polyphosphazenes were controlled by altering the ratio of monomer to initiator. The polymer chains were found to be active after chain propagation since further addition of monomer resulted in the formation of higher molecular weight polymer. For monomers 7 and 9 optimum polymerization behavior was found to occur at 35°C in the absence of solvent in the presence of catalytic quantities of PCl5. These reactions proceeded to 100{\%} completion, while maintaining molecular weight control and narrow polydispersites. In the case of polymers 4, 8, and 10, which were synthesized with a 10:1 monomer to initiator ratio in CH2Cl2, the resultant polymers were analyzed by gel permeation chromatography (GPC) (4, Mn = 2.9 × 103, polydispersity (PDI = Mw/Mn) = 1.07); 8, Mn = 2.2 × 103, PDI = 1.31; 10, Mn = 7.8 × 103, PDI = 1.23). Poly(diphenylphosphazene), (N=PPh2)n (6), was insoluble in common organic solvents and was characterized by magic angle spinning (MAS) solid state 31P NMR spectroscopy. The effects of side group steric bulk, electron-withdrawing or -donating properties, and leaving group types on the ambient-temperature cationic induced polymerizations are discussed.",
author = "Allcock, {Harry R.} and Nelson, {James M.} and Reeves, {Scott D.} and Honeyman, {Charles H.} and Ian Manners",
year = "1997",
month = "1",
day = "13",
doi = "10.1021/ma961215p",
language = "English (US)",
volume = "30",
pages = "50--56",
journal = "Macromolecules",
issn = "0024-9297",
publisher = "American Chemical Society",
number = "1",

}

Ambient-temperature direct synthesis of poly(organophosphazenes) via the "living" cationic polymerization of organo-substituted phosphoranimines. / Allcock, Harry R.; Nelson, James M.; Reeves, Scott D.; Honeyman, Charles H.; Manners, Ian.

In: Macromolecules, Vol. 30, No. 1, 13.01.1997, p. 50-56.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Ambient-temperature direct synthesis of poly(organophosphazenes) via the "living" cationic polymerization of organo-substituted phosphoranimines

AU - Allcock, Harry R.

AU - Nelson, James M.

AU - Reeves, Scott D.

AU - Honeyman, Charles H.

AU - Manners, Ian

PY - 1997/1/13

Y1 - 1997/1/13

N2 - A new, ambient-temperature method for the direct synthesis of organo-substituted polyphosphazenes is described. It involves the initiation of a series of organophosphoranimines R(R′)-XP=NSiMe3 (3, R = Ph, R′ = X = Cl; 5, R = R′ = Ph, X = Cl; 7, R = Me, R′ = Et, X = Cl; 9, R = R′ = CF3CH2O, X = Br) with catalytic amounts of PCl5 in CH2Cl2 to yield (after treatment with NaOCH2CF3 in the case of 3) the corresponding polyphosphazene species (N=PRR′)., (4, R = Ph, R′ = OCH2CF3; 6, R = R′ = Ph; 8, R = Me, R′ = Et; 10, R = R′ = OCH2CF3) with narrow polydispersities. The molecular weights of the polyphosphazenes were controlled by altering the ratio of monomer to initiator. The polymer chains were found to be active after chain propagation since further addition of monomer resulted in the formation of higher molecular weight polymer. For monomers 7 and 9 optimum polymerization behavior was found to occur at 35°C in the absence of solvent in the presence of catalytic quantities of PCl5. These reactions proceeded to 100% completion, while maintaining molecular weight control and narrow polydispersites. In the case of polymers 4, 8, and 10, which were synthesized with a 10:1 monomer to initiator ratio in CH2Cl2, the resultant polymers were analyzed by gel permeation chromatography (GPC) (4, Mn = 2.9 × 103, polydispersity (PDI = Mw/Mn) = 1.07); 8, Mn = 2.2 × 103, PDI = 1.31; 10, Mn = 7.8 × 103, PDI = 1.23). Poly(diphenylphosphazene), (N=PPh2)n (6), was insoluble in common organic solvents and was characterized by magic angle spinning (MAS) solid state 31P NMR spectroscopy. The effects of side group steric bulk, electron-withdrawing or -donating properties, and leaving group types on the ambient-temperature cationic induced polymerizations are discussed.

AB - A new, ambient-temperature method for the direct synthesis of organo-substituted polyphosphazenes is described. It involves the initiation of a series of organophosphoranimines R(R′)-XP=NSiMe3 (3, R = Ph, R′ = X = Cl; 5, R = R′ = Ph, X = Cl; 7, R = Me, R′ = Et, X = Cl; 9, R = R′ = CF3CH2O, X = Br) with catalytic amounts of PCl5 in CH2Cl2 to yield (after treatment with NaOCH2CF3 in the case of 3) the corresponding polyphosphazene species (N=PRR′)., (4, R = Ph, R′ = OCH2CF3; 6, R = R′ = Ph; 8, R = Me, R′ = Et; 10, R = R′ = OCH2CF3) with narrow polydispersities. The molecular weights of the polyphosphazenes were controlled by altering the ratio of monomer to initiator. The polymer chains were found to be active after chain propagation since further addition of monomer resulted in the formation of higher molecular weight polymer. For monomers 7 and 9 optimum polymerization behavior was found to occur at 35°C in the absence of solvent in the presence of catalytic quantities of PCl5. These reactions proceeded to 100% completion, while maintaining molecular weight control and narrow polydispersites. In the case of polymers 4, 8, and 10, which were synthesized with a 10:1 monomer to initiator ratio in CH2Cl2, the resultant polymers were analyzed by gel permeation chromatography (GPC) (4, Mn = 2.9 × 103, polydispersity (PDI = Mw/Mn) = 1.07); 8, Mn = 2.2 × 103, PDI = 1.31; 10, Mn = 7.8 × 103, PDI = 1.23). Poly(diphenylphosphazene), (N=PPh2)n (6), was insoluble in common organic solvents and was characterized by magic angle spinning (MAS) solid state 31P NMR spectroscopy. The effects of side group steric bulk, electron-withdrawing or -donating properties, and leaving group types on the ambient-temperature cationic induced polymerizations are discussed.

UR - http://www.scopus.com/inward/record.url?scp=0030818945&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0030818945&partnerID=8YFLogxK

U2 - 10.1021/ma961215p

DO - 10.1021/ma961215p

M3 - Article

AN - SCOPUS:0030818945

VL - 30

SP - 50

EP - 56

JO - Macromolecules

JF - Macromolecules

SN - 0024-9297

IS - 1

ER -