Phosphonitrilic Compounds. VI. High Molecular Weight Poly(alkoxy- and aryloxyphosphazenes)

Allcock, Harry R.; Kugel, R. L.; Valan, K. J.

doi:10.1021/ic50044a016

Cited by 422 publications

(321 citation statements)

References 1 publication

(1 reference statement)

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“…As pointed out in previous papers, the polyphosphazene skeleton is one of the most flexible macromolecular backbones known and this can give rise to glass transition temperatures as lr.w as -80°C or -90*C if small or highly flexible side groups, such as F, OCH 3 , or OCH 2 CH 3 are attached to the skeleton. 3 , 4 Evidence exists that this flexibility is mainly a consequence of torsional freedom of the backbone bonds, supplemented perhaps by P-N-P bond angle distortion. Rigid, bulky side groups lower the torsional mobility of the chain segments and raise the Tg ='1% accordingly, Also listed in Table II are the as an ionic conductor dissolved in polymer 7 or 8, the conductivity at room temperature is three orders of magnitude higher than has been found for complexes of poly(ethylene oxide).…”

Section: Imentioning

confidence: 99%

“…This is a consequence of the substitutive mode of synthesis used for these polymers, as described in a number of earlier publications. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17] The method involves the prior synthesis of a reactive, high polymeric poly(dihalophosphazene) intermediate, such as 1, by a ring-opening polymerization of the corresponding cyclic trimer, followed by replacement of the halogen atoms by one or more of a wide variety of organic or organometallic nucleophiles.…”

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confidence: 99%

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Polyphosphazenes with etheric side groups: prospective biomedical and solid electrolyte polymers

Allcock¹,

Austin²,

Neenan³

et al. 1986

Macromolecules

154

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Section: Imentioning

confidence: 99%

mentioning

confidence: 99%

Polyphosphazenes with etheric side groups: prospective biomedical and solid electrolyte polymers

Allcock¹,

Austin²,

Neenan³

et al. 1986

Macromolecules

154

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“…The most widely used synthesis route to stable poly(organophosphazenes), first developed in our program, is illustrated in Scheme 1 (1)(2)(3)(4). The ring-opening polymerization of hexachlorocyclotriphosphazene (2) [or its fluoro-analogue (NPF 2 ) 3 )] leads to the formation of a high molecular weight poly(di-halogenophosphazene) such as 3.…”

Section: Introduction To Polvnhosnhazenesmentioning

confidence: 99%

“…The ring-opening polymerization of hexachlorocyclotriphosphazene (2) [or its fluoro-analogue (NPF 2 ) 3 )] leads to the formation of a high molecular weight poly(di-halogenophosphazene) such as 3. This polymerization takes place in the molten trimer or in solution.…”

Section: Introduction To Polvnhosnhazenesmentioning

confidence: 99%

Macromolecular and Materials Design Using Polyphosphazenes

Allcock

1994

ACS Symposium Series

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A 279 781 .ENTAT0704N0188I ~ ~ut qf q~c fl~ D~Cu~m q tle IMO tOE r.. nq -flhtfli cisoet s Saeeci nq *%.Sungq eatsa vn LA7 a ma *qtte tro COII."IIOA ou tnst iO .ree, iM W aralq but* oM tm ate OC 4ft Ottwsl a 0oe l o s tp4.% ou'et onto vv41n*qton meoooo-Aat-r $4"voee, otrectorate for infformatiOqN O{4WI49M•AeI, •t$ 1&04 "00"sl~r "te cfficeIt mf anaqqm" t aa s get. 0 -100twOtt Retf tn Pr la`tt (0 ?04. Reproduction in whole or in part is permitted for any purpose of the United States Government. This document has been approved for public release; distribution is unlimited. ABSTRACT (Maximum 200 words)Polyphosphazenes are among the most versatile of all polymers. This is a consequence of the unique properties of the phosphorus-nitrogen backbone and the ease with which a wide range of different side groups can be introduced mainly by macromolecular substitution, but also by the polymerization of different "monomers". This field has reached a stage where the fundamental chemistry now allows the design and synthesis of a broad range of new materials that are valuable for properties such as elasticity, high refractive index, liquid crystallinity, ferroelectric-, NLO-, and photochromic attributes, and for uses as solid ionic conductors, biomedical microencapsulation polymers, and materials with controlled surface properties. Polyphosphazenes are among the most versatile of all polymers. This is a consequence of the unique properties of the phosphorus-nitrogen backbone and the ease with which a wide range of different side groups can be introduced mainly by macromolecular substitution, but also by the polymerization of different "monomers". This field has reached a stage where the fundamental chemistry now allows the design and synthesis of a broad range of new materials that are valuable for properties such as elasticity, high refractive index, liquid crystallinity, ferroelectric-, NLO-, and photochromic attributes, and for uses as solid ionic conductors, biomedical microencapsulation polymers, and materials with controlled surface properties. Inorganic-Organic Polymers as Components of New MaterialsMaterials science covers a very broad range of substances within the four main classical categories of ceramics, metals, semiconductors/electro-optical solids, and petrochemical polymers.Most of the examples in the first three categories are inorganic ip composition, while the last is mainly organic.All four have advantages and disadvanges. For example, the totally inorganic materials are heavy, often britttle, and difficult to fabricate. On the other hand, conventional polymers are tough and easy to fabricate but are unstable at elevated temperatures and lack many of the interesting electrical and optical properties of the inorganic materials.The main concept behind the current interest in inorganic or inorganic-organic polymers is that they may provide a means for the preparation of new materials that combine the advantages and minimize the disadvantages of the classical materials. Thus, the long term interest lies in the d...

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“…1) involving the replacement of halogen atoms of polydichlorophosphazenes by alkyl, aryl, amino, alkoxy, and aryloxy groups. [1][2][3][4] 'Hydrolysis of the hexachlorocyclotriphosphazene trimer to the oxophosphazane (Fig. 2, . \ ref.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and thermal stability of carborane‐containing phosphazenes

Fewell

Basi

Parker

1983

J of Applied Polymer Sci

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SynopsisCarborane substituted polyphosphazenes were prepared by the thermal polymerization of phenyl-carboranyl penta chlorocyclotriphosphazene. Successive isothermal vacuum pyrolyses were conducted on the polymer and examined for structural changes by infrared spectroscopy.The degradation products were ascertained by gas chromatography-mass . . spectrometric analysis. It was found that the presence of the carborane group improves the thermal stability of the polymer by retarding the ring-chain equilibrium processes of decomposition. The alternating phosphorus and nitrogen atoms in the backbone of phosphazene polymers is responsible for the high degree of torsional mobility and accounts for the low glass transition temperature (Tg) values and the transparency of the polymer to ultraviolet radiation. lThe susceptibility of the phosphorus-chlorine bond to hydrolysis has been surmounted by nucleophilic substitution reactions ( Fig. 1) involving the replacement of halogen atoms of polydichlorophosphazenes by alkyl, aryl, amino, alkoxy, and aryloxy groups. 1-4 'Hydrolysis of the hexachlorocyclotriphosphazene trimer to the oxophosphazane (Fig. 2, . \ ref. 5), which is thermally unstable due to its P-N-P type bonding.The addition of the phenylcarborane group on thehexachlorocyclotriphosphazene ring followed by thermal polymerization and the replacement of remaining chlorine atoms with trifluoroethoxy groups (Fig. 3) result in an enhancement of the thermal stability of phosphazene polymers. Analytical EquipmentInfrared spectra were recorded on a Nicolet MX-l, Fourier Transform Infrared spectrometer. Gas chromatograp~y-mass spectrometric analysis of the polymer's decomposition products was accomplished using a Hewlett-Packard model #57l0A gas chromatograph with a 6-ft column packed with 3% OV 101 on 80/100 mesh Supelcoport AWDC and interfaced with an all-glass jet separator to a Hewlett-Packard model #5980A massspectrometer computer system. Successive pyrolyses of the polymer were conducted using a Chemical Data Systems model #120 Pyroprobe by heating the identical sample (2 mg) for 40 sec at ,the desired pyrolysis temperature. After analysis of the pyrolysis products the probe was allowed to cool before subjecting the polymeric residue to the next'pyrolysis temperature for the same time period. To the freshly prepared phenyl-lithiocarborane solution, the trimer (I) (2.2 gm, 6.3 mmoles) which was dissolved in 15 m1 anhydrous ether was added by drops with vigorous stirring at DoC within approximately 15 min. The mixture was allowed to warm slowly to ambient temperature and stirred for an additional 12 hr. The solvents were removed and the solid material,placed in a vacuum sublimator (60°C, evacuated to 0.05 rnm) after which the sublimable solid compounds were removed. The temperature of the oil bath was then increased to 5 l300e to yield a crystalline sublimate which was further purified by recrystallization from hexane (m.p. was l33°e) and confirmed by infrared spectroscopy (Fig. 5). Polymerization of Phenylcarboranyl-p...

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Phosphonitrilic Compounds. VI. High Molecular Weight Poly(alkoxy- and aryloxyphosphazenes)

Cited by 422 publications

References 1 publication

Polyphosphazenes with etheric side groups: prospective biomedical and solid electrolyte polymers

Polyphosphazenes with etheric side groups: prospective biomedical and solid electrolyte polymers

Macromolecular and Materials Design Using Polyphosphazenes

Synthesis and thermal stability of carborane‐containing phosphazenes

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