"Living" cationic polymerization of phosphoranimines as an ambient temperature route to polyphosphazenes with controlled molecular weights

Harry R. Allcock; Chester A. Crane; Christopher T. Morrissey; James M. Nelson; Scott D. Reeves; Charles H. Honeyman; Ian Manners

doi:10.1021/ma960876j

"Living" cationic polymerization of phosphoranimines as an ambient temperature route to polyphosphazenes with controlled molecular weights

Harry R. Allcock, Chester A. Crane, Christopher T. Morrissey, James M. Nelson, Scott D. Reeves, Charles H. Honeyman, Ian Manners

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Abstract

A new method for the synthesis of poly(dichlorophosphazene) at ambient temperatures is described. It involves the initiation of Cl₃P=NSiMe₃ with small amounts of PCl₅ in CH₂Cl₂ to yield poly(dichlorophosphazene), (NPCl₂)_n, with narrow polydispersities. The molecular weight of poly(dichlorophosphazene) was 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. Integration of ¹H and ³¹P NMR spectra of these reactions revealed that the polymerization follows first-order reaction kinetics with respect to monomer concentration. Active polymer chains may be quenched or end-capped by the addition of trace quantities of Me²(CF³-CH²O)P=NSiMe³ or (CF³CH²O)³P=NSiMe³. Furthermore, PBr⁵, SbCl⁵, and Ph³C[PF⁶] were also found to be effective initiators in CH²Cl² at room temperature.

Original language	English (US)
Pages (from-to)	7740-7747
Number of pages	8
Journal	Macromolecules
Volume	29
Issue number	24
DOIs	https://doi.org/10.1021/ma960876j
State	Published - Nov 18 1996

All Science Journal Classification (ASJC) codes

Organic Chemistry
Polymers and Plastics
Inorganic Chemistry
Materials Chemistry

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title = "{"}Living{"} cationic polymerization of phosphoranimines as an ambient temperature route to polyphosphazenes with controlled molecular weights",

abstract = "A new method for the synthesis of poly(dichlorophosphazene) at ambient temperatures is described. It involves the initiation of Cl3P=NSiMe3 with small amounts of PCl5 in CH2Cl2 to yield poly(dichlorophosphazene), (NPCl2)n, with narrow polydispersities. The molecular weight of poly(dichlorophosphazene) was 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. Integration of 1H and 31P NMR spectra of these reactions revealed that the polymerization follows first-order reaction kinetics with respect to monomer concentration. Active polymer chains may be quenched or end-capped by the addition of trace quantities of Me2(CF3-CH2O)P=NSiMe3 or (CF3CH2O)3P=NSiMe3. Furthermore, PBr5, SbCl5, and Ph3C[PF6] were also found to be effective initiators in CH2Cl2 at room temperature.",

author = "Allcock, {Harry R.} and Crane, {Chester A.} and Morrissey, {Christopher T.} and Nelson, {James M.} and Reeves, {Scott D.} and Honeyman, {Charles H.} and Ian Manners",

year = "1996",

month = nov,

day = "18",

doi = "10.1021/ma960876j",

language = "English (US)",

volume = "29",

pages = "7740--7747",

journal = "Macromolecules",

issn = "0024-9297",

publisher = "American Chemical Society",

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T1 - "Living" cationic polymerization of phosphoranimines as an ambient temperature route to polyphosphazenes with controlled molecular weights

AU - Allcock, Harry R.

AU - Crane, Chester A.

AU - Morrissey, Christopher T.

AU - Nelson, James M.

AU - Reeves, Scott D.

AU - Honeyman, Charles H.

AU - Manners, Ian

PY - 1996/11/18

Y1 - 1996/11/18

N2 - A new method for the synthesis of poly(dichlorophosphazene) at ambient temperatures is described. It involves the initiation of Cl3P=NSiMe3 with small amounts of PCl5 in CH2Cl2 to yield poly(dichlorophosphazene), (NPCl2)n, with narrow polydispersities. The molecular weight of poly(dichlorophosphazene) was 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. Integration of 1H and 31P NMR spectra of these reactions revealed that the polymerization follows first-order reaction kinetics with respect to monomer concentration. Active polymer chains may be quenched or end-capped by the addition of trace quantities of Me2(CF3-CH2O)P=NSiMe3 or (CF3CH2O)3P=NSiMe3. Furthermore, PBr5, SbCl5, and Ph3C[PF6] were also found to be effective initiators in CH2Cl2 at room temperature.

AB - A new method for the synthesis of poly(dichlorophosphazene) at ambient temperatures is described. It involves the initiation of Cl3P=NSiMe3 with small amounts of PCl5 in CH2Cl2 to yield poly(dichlorophosphazene), (NPCl2)n, with narrow polydispersities. The molecular weight of poly(dichlorophosphazene) was 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. Integration of 1H and 31P NMR spectra of these reactions revealed that the polymerization follows first-order reaction kinetics with respect to monomer concentration. Active polymer chains may be quenched or end-capped by the addition of trace quantities of Me2(CF3-CH2O)P=NSiMe3 or (CF3CH2O)3P=NSiMe3. Furthermore, PBr5, SbCl5, and Ph3C[PF6] were also found to be effective initiators in CH2Cl2 at room temperature.

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DO - 10.1021/ma960876j

M3 - Article

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JO - Macromolecules

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ER -

"Living" cationic polymerization of phosphoranimines as an ambient temperature route to polyphosphazenes with controlled molecular weights

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