Synthesis and Properties of Poly(aminocarbophosphazenes)

Allcock, Harry R.; Coley, Suzanne M.; Morrissey, Christopher T.

doi:10.1021/ma00089a002

Cited by 21 publications

(10 citation statements)

References 6 publications

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“…Small amounts of residual chlorine probably arise from the formation of polymeric ammonium salts of the type RR′NH 2 + Clwhere the basic poly[(amino)thionylphosphazene] competes with excess amine as an HCl acceptor. Similar behavior has been reported during the aminolysis of poly[(halogeno)carbophosphazenes] 26 as well as the classical polyphosphazene [Cl 2 PdN] n . 27 The 31 P NMR spectra showed resonances at a significantly lower field (ca.…”

Section: Synthesis and Structural Characterization Of The Poly[(amino...supporting

confidence: 80%

Polymers with Sulfur(VI)−Nitrogen−Phosphorus Backbones: Synthesis, Characterization, and Properties of Atactic Poly[(amino)thionylphosphazenes]

Park

Liang

et al. 1996

Macromolecules

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Aminolysis of the halogenated poly(thionylphosphazene) [NSOCl(NPCl2)2]n (2a), which possesses a novel S(VI)-N-P backbone, with a series of primary amines NH2R (R ) Me, Et, n Pr, allyl, n Bu, n Hex, and Ph) afforded the hydrolytically stable poly[(aminoPh) in which both the chlorine substituents at the phosphorus center and at sulfur were replaced. Treatment of 2a with a mixture of amines, NH2R (R ) allyl and n Bu), yielded a series of mixed substituent copolymers 5a-5c of which 5a and 5b were thermally and UV cross-linkable. These new polymers were structurally characterized by 31 P, 1 H, and 13 C NMR and IR spectroscopy and by elemental analysis. The stereochemistry of the poly[(amino)thionylphosphazenes] was investigated by 31 P NMR which indicated the polymers are atactic. Molecular weights of the polymers 4a-4g and 5a-5c were in the range Mw ) 5.0 × 10 3 to 1.3 × 10 5 , Mn ) 3.3 × 10 3 to 7.4 × 10 4 according to GPC analysis in THF versus polystyrene standards. An absolute value of Mw ) 1.0 × 10 5 was obtained by low-angle laser light scattering for 4e, which was approximately double that obtained by GPC (Mw ) 4.9 × 10 4 ). The thermal transition behavior of the polymers was investigated by DSC. Glass transition temperatures (Tg's) of the poly[(amino)thionylphosphazenes] 4a-4g and 5a-5c were in the range of -40 to +82 °C. No melt transitions were detected and wide-angle X-ray scattering studies also indicated that poly[(amino)thionylphosphazenes] were amorphous. TGA analysis showed that the poly[(amino)thionylphosphazenes] were stable to weight loss up to 200-250 °C under nitrogen at a heating rate of 10 °C/min.

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Section: Synthesis and Structural Characterization Of The Poly[(amino...supporting

confidence: 80%

Polymers with Sulfur(VI)−Nitrogen−Phosphorus Backbones: Synthesis, Characterization, and Properties of Atactic Poly[(amino)thionylphosphazenes]

Park

Liang

et al. 1996

Macromolecules

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“…The aryloxy chains were further characterized by the same group in 1991, and it was found that the poly(carbophosphazene) skeleton is much less flexible than PP, probably due to the inherent differences in the π-bonding nature of CN and PN double bonds. Following these initial works, additional structures, like various aminocarbophosphazenes, have been synthesized . In addition, closely related copolymers, polythiophosphazenes 20 and polythionylphosphazene, both presenting the SNPNPN backbone sequence have been obtained by ROP.…”

Section: Introductionmentioning

confidence: 99%

“…Following these initial works, additional structures, like various aminocarbophosphazenes, have been synthesized. 19 In addition, closely related copolymers, polythiophosphazenes 20 and polythionylphosphazene, 21 both presenting the SNPNPN backbone sequence have been obtained by ROP. We refer the reader to ref 22 for a detailed review of these inorganic polymers.…”

Section: Introductionmentioning

confidence: 99%

Linear and Nonlinear Optics Properties of Polyphosphazene/Polynitrile Alternating Copolymers

Jacquemin

2005

J. Chem. Theory Comput.

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The linear and nonlinear optical properties of polyphosphazene/polynitrile alternating copolymers, -(PH2 = N - CH = N)-N, are studied, at the MP2/6-31G(d) level of approximation, by using an oligomeric approach. We report the evolution with the chain length of the geometry, charges, dipole moments, polarizabilities, and first hyperpolarizabilities of two conformers (trans-transoïd and trans-cisoïd). Comparisons with the polyphosphazene/polyacetylene and poly(thiophosphazene) structures are performed. It turns out that the polyphosphazene/polynitrile copolymers present dipole moment and polarizabilities comparable to polyphosphazene but larger (+50%) first hyperpolarizabilities. The relative response of these copolymers is comparable to the one of standard push-pull systems.

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“…Thermal ROP of a cyclic carbophosphazene was used to prepare the chlorinated polymeric species (23), which undergoes halogen replacement reactions with nucleophiles such as aryloxides and aniline to yield hydrolytically stable poly(aryloxycarbophosphazenes) (24) (M w = ca 10 5 , M n = 10 4 ) (eq. 23) (88)(89)(90)(91). The polymer backbone in these materials was found to be less flexible than in classical polyphosphazenes.…”

Section: Polycarbophosphazenesmentioning

confidence: 98%

“…The reaction of (23) with alkylamines has also been studied (91). The resulting poly(alkylaminocarbophosphazenes) are sensitive to hydrolysis.…”

Section: Polycarbophosphazenesmentioning

confidence: 99%

Inorganic Polymers

Bourke¹,

Manners²

2001

Encyclopedia of Polymer Science and Technology

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The thermal ROP route requires the synthesis and careful purification of the cyclic trimer [Cl 2 PN] 3 and the use of elevated temperatures where control of molecular weight is very difficult and cross-linking can take place at high conversion, which can limit the yield. INORGANIC POLYMERSVol. 3to phosphazene polymers, which may well facilitate more rapid and extensive commercialization.Monomer Synthesis. Both the ROP and condensation routes to poly(dichlorophosphazene) require high purity monomers. For the traditional ROP process, ultrahigh purity [NPCl 2 ] 3 is required. The most common method for its preparation is through the reaction of PCl 5 with NH 4 Cl in a high boiling halogenated solvent, such as chlorobenzene or tetrachloroethane, at 150 • C. The yields can approach 70-80% under specialized conditions, but 50% is more typical (25). The phosphoranimine most commonly used in the aforementioned condensation route to poly(dichlorophosphazene) is Cl 3 P NSi(CH 3 ) 3 . The synthesis of this compound has been described (21) and is based on a modification of an earlier procedure (26) involving the reaction of PCl 5 with LiN(Si(CH 3 ) 3 ) 2 at −78 • C in hexane. However, the purification required by this method is a challenge and leads to an overall yield of <40%.It has also been reported that the reaction of N(Si(CH 3 ) 3 ) 3 with PCl 5 can be manipulated to maximize yields of either the cyclic trimer (76%) or the pure phosphoranimine monomer (40%) through variations in reaction conditions (25). These reactions use milder conditions than previously reported methods, with higher yields. In addition, the major side product, (CH 3 ) 3 SiCl, can be recycled to form one of the starting materials, N(Si(CH 3 ) 3 ) 3 .N-Silylphosphoranimines with alkyl and aryl substituents can be synthesized by reaction of commercial starting materials such as PCl 3 , ((CH 3 ) 3 Si) 2 NH, and Grignard reagents by way of a three-step process, with typical yields of 60-70%. These precursors are also accessible via a "one-pot" synthesis, which requires only isolation of the final product with yields of about 75% (3).Uses. Some of the most useful polyphosphazene derivatives are fluoroalkoxy derivatives, and amorphous copolymers are very useful as flame-retardant, hydrocarbon-solvent, and oil-resistant elastomers and have found aerospace and automotive applications. Polymers such as the amorphous comb polymer poly[bis(methoxyethoxyethoxy)phosphazene] (8) are of considerable interest as components of polymeric electrolytes in battery technology (1). Vol. 3 INORGANIC POLYMERS 35Polyphosphazenes are also of interest as biomedical materials and bioinert, bioactive, membrane-forming, and bioerodable materials (1).

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Synthesis and Properties of Poly(aminocarbophosphazenes)

Cited by 21 publications

References 6 publications

Polymers with Sulfur(VI)−Nitrogen−Phosphorus Backbones: Synthesis, Characterization, and Properties of Atactic Poly[(amino)thionylphosphazenes]

Polymers with Sulfur(VI)−Nitrogen−Phosphorus Backbones: Synthesis, Characterization, and Properties of Atactic Poly[(amino)thionylphosphazenes]

Linear and Nonlinear Optics Properties of Polyphosphazene/Polynitrile Alternating Copolymers

Inorganic Polymers

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