Abstract
Polyphosphazenes are inorganic-organic high polymers with a backbone of alternating phosphorus and nitrogen atoms and two organic or organometallic side groups attached to each phosphorus. Most of these polymers are synthesized by macromolecular substitution reactions carried out on poly(dichlorophosphazene), (NPCl2)n. The chlorine substitution reactions involve alkoxides, aryloxides, primary or secondary amines, or a range of organometallic reagents. Structural variations are accomplished via the use of one, two, or more different nucleophiles and substituents along the polymer chain and by the employment of reagent size and reactivity to control polymer properties and emphasize specific uses. Applications have been developed for these polymers as elastomers, thermoplastics, biostable or bioerodible medical materials, fire-resistant lithium battery electrolytes, films, or foams, and gas and liquid separation membranes.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
References
Allcock HR (2003) Chemistry and applications of polyphosphazenes. John Wiley & Sons, Hoboken
Liebig J (1834) A Compound of Phosphorus with Nitrogen (Supplement). Ann Chem Pharm 11:139
Rose H (1834) A Compound of Phosphorus with Nitrogen. Ann Chem Pharm 11:129
Stokes HN (1897) On the Chloronitrides of Phosphorus (II). Amer Chem J 19:782
Allcock HR, Kugel RL (1965) Synthesis of High Polymeric Alkoxy- and Aryloxyphosphonitriles. J Am Chem Soc 87:4216–4217
Allcock HR, Kugel RL, Valan KJ (1966) High Molecular Weight Poly[alkoxy- and aryloxyphosphazenes]. Inorg Chem 5:1709–1715
Allcock HR, Kugel RL (1966) High Molecular Weight Poly(diamino-phosphazenes). Inorg Chem 5:1716–1718
Allcock HR, Lampe FW, Mark JE (2003) Contemporary polymer chemistry, 3rd edn. Prentice-Hall, Englewood Cliffs
Odian G (2004) Principles of polymerization, 4th edn. John Wiley & Sons, Hoboken
Flindt EP, Rose H (1977) Trivalent-pentavalente Phosphosverbindi-dungen/Phosphazene. IV. Z Anorg Allg Chem 428:204
Wisian-Neilson P, Neilson RH (1980) Poly(dimethylphosphazene), (Me2)PN)n. J Am Chem Soc 102:2848
Neilson RH, Wisian-Neilson P (1988) Poly(alkyl/aryl phosphazenes). Chem Rev 88:54
Wisian-Neilson P, Jung J-H, Potluri SK (2006) Cyclic and Polymeric Alky/Aryl Phosphazenes in Modern Aspects of Main Group Chemistry. ACS symp. series 917, Washington, DC, pp 335–346
Montague RA, Matyjaszewski K (1990) Synthesis of Poly[bis(trifluoroethoxy)-phosphazene] Under Mild Conditions Using a Fluoride Initiator. J Am Chem Soc 112:6721
Matyjaszewski K, Moore MM, White ML (1993) Synthesis of Polyphosphazene Block Copolymers Bearing Alkoxyethoxy and Trifluoroethoxy Groups 26:6741–6748
(a) Honeyman CH, Manners I, Morrissey CT, Allcock HR (1995) Ambient Temperature Synthesis of Poly(dichlorophosphazene) with Molecular Weight Control. J Am Chem Soc 117:7035–7036. (b) Allcock HR, Reeves SD, Nelson JM, Crane CA, Manners I (1997) Polyphosphazene Block Copolymers via the Living Cationic, Ambient Temperature Polymerization of Phosphoranimines. Macromolecules 30:2213–2215
De Jaeger R, Potin P (2004) Ch.2. In: Gleria M, De Jaeger R (eds) Synthesis and characterization of poly(organophosphazenes). Nova Publishers, New York
Allcock HR (2004) Ch. 3. In Gleria M, De Jaeger R (eds) Synthesis and characterization of poly(organophosphazenes). Nova Publishers, New York
Allcock HR, Morozowich NL (2012) Bioerodible Polyphosphazenes and their Medical Potential. RSC Polym Chem 3:578–590
Allcock HR, Fuller TJ (1980) Phosphazene High Polymers with Steroidal Side Groups. Macromolecules 13:1338–1345
Allcock HR, Greigger PP, Gardner JE, Schmutz JL (1979) Water Soluble Polyphosphazenes as Carrier Molecules for Iron(III) and Iron(II) Porphyrins. J Am Chem Soc 101:606–611
Allcock HR, Scopelianos AG, O’Brien JP, Bernheim MY (1981) Synthesis and Structure of Carborane-Substituted Cyclic and Polymeric Phosphazenes. J Am Chem Soc 103:350–357
Modzelewski T, Allcock HR (2014) An Unusual Polymer Architecture for the Generation of Elastomeric Properties in Fluorinated Polyphosphazenes. Macromolecules 47:6776–6782
Modzelewski T, Wilts E, Allcock HR (2015) Elastomeric Polyphosphazenes with Phenoxy-cyclotriphosphazene Side Groups. Macromolecules 48:7543–7549
Li Z, Chen C, Tian Z, Modzelewski T, Allcock HR (2016) Polyphosphazenes with Cyclotetraphosphazene Side Groups: Synthesis and Elastomeric Properties. J Inorg Organomet Mater Polym 26:667–674
Modzelewski T, Wonderling NM, Allcock HR (2015) Polyphosphazene Elastomers Containing Interdigitated Oligo-p-phenyleneoxy Side Groups: Synthesis, Mechanical Properties and X-ray Scattering Studies. Macromolecules 48:4882–4890
Tong C, Tian Z, Chen C, Li Z, Modzelewski T, Allcock HR (2016) Synthesis and Characterization of Trifluoroethoxy Polyphosphazenes Containing POSS Side Groups. Macromolecules 49:1313–1320
Li Z, Allcock HR (2015) Polyphosphazenes with Immobilized Dyes as Potential Color Filter Materials. Appl Mater Interface 1:13518–13523
Weikel AL, Lee D, Krogman NR, Allcock HR (2010) Phase Changes of Poly(alkoxyphosphazene) and their Behavior in the Presence of Oligoisobutylene. J Polym Eng Sci 92A:114–125
Tian Z, Liu X, Manseri A, Ameduri B, Allcock HR (2013) Limits to Expanding the PN-F Series of Polyphosphazene Elastomers. Polym Eng Sci 54:1827–1832
Singler RE, Schneider NS, Hagnauer GL (1975) Polyphosphazenes: Synthesis-Properties-Applications. Polym Eng Sci 51:321–338
Allcock HR, Mang MN, Dembek AA, Wynne KJ (1989) Poly(aryloxyphosphazenes) with Phenylphenoxy and Related Bulky Side Groups. Synthesis, Thermal Transition Behavior and Optical Properties. Macromolecules 22:4179–4190
Reed CA, Taylor GP, Guigley KS, Kully KS, Bernheim KA, Coleman MM, Allcock HR (2000) Polyurethane/Poly[bis(carboxylato-phenoxy)phosphazene] Blends and their Potential as Flame Retardant Materials. J Polym Sci Eng 40:465–472
Chen C, Liu X, Tian Z, Allcock HR (2012) 2,2,2-Trichloroethoxy-Substituted Polyphosphazenes: Synthesis, Characterization, and Properties. Macromolecules 45:9085–9091
Weikel AL, Owens SG, Fushimi T, Allcock HR (2012) Synthesis and Characterization of Methionine- and Cysteine-Substituted Phosphazenes. Macromolecules 4:5205–5210
Weikel AL, Lee D, Krogman NR, Allcock HR (2010) Phase Changes of Poly(alkoxyphosphazenes) and Their Behavior in the Presence of Oligoisobutylene. J Polym Sci Eng 92A:114–125
Nichol JL, Hotham IT, Allcock HR (2014) Ethoxyphosphazene Polymers and their Hydrolytic Behavior. Polym Degrad Stab 109:92–96
Tian Z, Hess A, Fellin CR, Nulwala H, Allcock HR (2015) Phosphazene High Polymers and Models with Cyclic Aliphatic Side Structure-Property Relationships. Macromolecules 48:4301–4311
Kojima M, Magill J (1985) Phase Transitions in Polyphosphazene Films: Poly[bis(trifluoroethoxy)phosphazene]. Macromol Chem Phys 186:649–663
Rose SH, Cable J (1969) U.S. Govt Research Report, AD 693,28
Schneider NS, Desper CR, Singler RE (1976) The Thermal Transition Behavior of Polyorganophosphazenes. J Appl Polym Sci 20:3087–3103
Allcock HR, Kim C (1990) Liquid Crystalline Phosphazenes Bearing Biphenyl Mesogenic Groups. Macromolecules 23:3881–3887
Blonsky PM, Shriver DF, Austin PE, Allcock HR (1984) Polyphosphazene Solid Electrolytes. J Am Chem Soc 106:6854–6855
Allcock HR, Austin PE, Neenan TX, Sisko JT, Blonsky PM, Shriver DF (1986) Polyphosphazenes with Etheric Side Groups: Prospective Biomedical and Solid Electrolyte Polymers. Macromolecules 19:1508–1512
Allcock HR, Kwon S, Riding GH, Fitzpatrick RJ, Bennett JL (1988) Hydrophilic Polyphosphazenes as Hydrogels: Radiation Crosslinking and Hydrogel Characteristics of Poly[bis(methoxyethoxyethoxy)phosphazene]. Biomaterials 19:509–513
Greigger PP, Allcock HR (1979) A Spirocyclophosphazene with Iron-Phosphorus Bonds and a P-Fe-Fe Three-Membered Ring. J Am Chem Soc 101:2492
Allcock HR, Manners I, Mang MN, Parvez M (1990) Transition Metal Derivatives of Phosphinophosphazenes: X-Ray Crystal Structures of N3P3Cl4PhPh2, N3P3Cl4PhPPh4,Cr(Co)5 and N3P3Cl4PhPPh2.Ru3(CO)11. Inorg Chem 29:522–529
Manners I, Riding GH, Dodge JA, Allcock HR (1989) Role of Ring Strain and Steric Hindrance in a New Method for the Synthesis of Macrocyclic and High Polymeric Phosphazenes. J Am Chem Soc 111:3067–3069
Diefenbach U, Cannon AM, Stromberg BE, Olmeijer DL, Allcock HR (2000) Synthesis and Metal Coordination of Thioether-Containing Cyclo- and Poly(organophosphazenes). J Appl Polym Sci 78:650–661
Liu X, Breon J, Chen C, Allcock HR (2012) Substituent Exchange Reactions of Linear Oligomeric Aryloxy Phosphazenes with 2,2,2-Trifluoroethoxide. Inorg Chem 51(21):11910–11916
Liu X, Breon JP, Chen C, Allcock HR (2012) Substituent Exchange Reactions of Trimeric and Tetrameric Arylocyclophosphazenes with Sodium 2,2,2-Trifluoroethoxide. Roy Soc Chem Dalton Trans 41:2100–2109
Allcock HR, Steely L, Kim S, Kang B (2007) Plasma Surface Functionalization of Poly[bis(2,2,2-trifluoroethoxy)phosphazene] Films and Nanofibers. Langmuir 23:8103–8107
Tian Z, Chen C, Allcock HR (2014) Ethoxyphosphazene Polymers and their Hydrolytic Behavior. Macromolecules 47:1065–1072
Gleria M, De Jaeger R (eds) (2003) Applicative aspects of poly(organophosphazenes). Nova Publishers, New York
Chhour P, Gallo N, Cheheltani R, Williams D, Al-Zaki A, Paik T, Nichol JL, Tian Z, Naha PC, Allcock HR, Murray CB, Sourkas TA, Cormode DP (2014) Nano-Disco Balls: Control over Surface versus Core Loading of Active Nanocrystals into Polymer Nanoparticles. ACS Nano 8(9):9143–9153
Liu X, Tian Z, Chen C, Allcock HR (2013) UV-Cleavable Unimolecular Micelles: Synthesis and Characterization Toward Photocontrolled Drug Release Carriers. Polym Chem 4:1114–1125
Liu X, Zhang H, Tian Z, Sen A, Allcock HR (2012) Preparation of Quaternized Organic-Inorganic Hybrid Brush Polyphosphazene-co-poly-[2-(dimethylamino)ethylmethacrylate] Electrospun Fibers and their Antibacterial Properties. Polym Chem 3:2082–2091
Tian Z, Zhang Y, Chen C, Guiltinan MJ, Allcock HR (2013) Biodegradable Polyphosphazenes Containing Antibiotics: Synthesis, Characterization, and Hydrolytic Release Behavior. Polymer 4:1826–1835
Allcock HR, Kwon S (1989) An Ionically-Crosslinkable Polyphosphazene: Poly[di(carboxylatophenoxy)phosphazene] and its Hydrogels and Membranes. Macromolecules 22:75–79
Peach MS, James R, Toti US, Deng M, Morozowich NL, Allcock HR, Laurencin CT, Kumbar SG (2012) Polyphosphazene Functionalized Polyester Fiber Matrices for Tendon Tissue Engineering: In Vitro Evaluations of Human Mesenchymal Stem Cells. Biomed Mater 7:1–13
Nichol JL, Morozowich NL, Allcock HR (2013) Biodegradable Alanine and Phenylalanine Alkyl Ester Polyphosphazenes as Potential Ligament and Tendon Tissue Scaffolds. RSC Polym Chem 4:600–606
Peach MS, Kumbar SG, James R, Toti US, Balasubramaniam D, Deng M, Ulery B, Maxxocca AD, McCarthy MB, Morozowich NL, Allcock HR, Laurencin CT (2012) Design and Optimization of Polyphosphazenes Functionalized Fiber Matrices for Soft Tissue Regeneration. J Biomed Nanotechnol 8:107–124
Deng M, Kumbar SG, Nair LS, Weikel AL, Allcock HR, Laurencin CT (2011) Biomimetic Structures: Biological Implications of Dipeptide-substituted Polyphosphazene-Polyester Blend Nanofiber Matrices for Load-Bearing Bone Regeneration. Adv Funct Mater 21:2641–2651
Deng M, Kumbar SG, Wan Y, Toti US, Allcock HR, Laurencin CT (2010) Polyphosphazene Polymers for Tissue Engineering: An Analysis of Materials Synthesis, Characterization, and Applications. Soft Matter 6:3119–3132
Gettleman L (2003) Ch. 2. In: Gleria M, De Jaeger R (eds) Applicative aspects of poly(organophosphazenes). Nova Publishers, New York
Celonova Bio-Sciences (2010) Peachtree, Georgia, promotional material (2017) U.S. Patent US7922764
Fei S-T, Lee S-HA, Pursel SM, Bashem J, Hess A, Grimes CA, Horn MW, Mallouk TE, Allcock HR (2011) Electrolyte Infiltration in Phosphazene-Based Dye-Sensitized Solar Cells. J Power Sources 196:5223–5230
Fei S-T, Allcock HR (2010) Methoxyethoxyethoxyphosphazenes as Ionic Fire Retardant Additives for Lithium Battery Systems. Power Sources 195(7):2082–2088
Fei S-T, Allcock HR (2009) Recent Progress with Ethyleneoxy Phosphazenes as Lithium Battery Electrolytes. Mater Res Soc Symp. 1127-T01-05
Steely LB, Li Q, Badding JV, Allcock HR (2008) Foam Formation with Fluorinated Polyphosphazenes by Liquid CO2 Processing. Polym Sci Eng 48:683–686
Mukunoki Y, Kubota T (1992) Fuji Photo Film, Japan, U.S. Patent 5,135,846
Fukuwatari N, Ueda E, Kurachi Y (1998) Konica Corp., Japan, U.S. Patent 5,840,471
Ishikawa W, Fukuwatari N. Konica Corp., Japan, European Patent Application
Reed CA, Taylor JP, Guigley KS, Kully KS, Bernheim KA, Coleman MM, Allcock HR (2000) Polyurethane/Poly[bis(carboxylato-phenoxy)phosphazene] Blends and their Potential as Flame Retardant Materials. Report to U.S. Federal Aviation Administration
Olshavsky M, Allcock HR (1997) Polyphosphazenes with High Refractive Indices: Optical Dispersion and Molar Reactivity. Macromolecules 30:4179–4183
Allcock HR, Bender JD, Chang Y, McKenzie M, Fone MM (2003) Controlled Refractive Index Polymers; Polyphosphazenes with Chlorinated- and Fluoroinated-Aryloxy and Alkoxy Side Groups. Chem Mater 15:473–477
Allcock HR, Chang Y, Stone DA (2006) Control of the Conjugation Length and Solubility in Electroluminescent Polymers. J Polym Sci 44:69–76
Stewart FF, Luther TA, Harrup MK, Orme CJ (2003) In: Gleria M, De Jaegar R (eds) Applicative aspects of poly(organophosphazenes). Nova Publishers, New York. Chapter 10
Venna SR, Spore A, Tian Z, Marti AM, Albenze EJ, Nulwala HB, Rosi NL, Luebke DR, Hopkinson DP, Allcock HR (2017) Polyphosphazene Polymer Development for Mixed Matrix Membranes Using SIFSIX-Cu-2i as Performance Enhancement Filler Particles. J Membr Sci 535:103–112
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2019 Springer Nature Singapore Pte Ltd.
About this chapter
Cite this chapter
Allcock, H.R. (2019). Polyphosphazenes as an Example of the Element-Blocks Approach to New Materials. In: Chujo, Y. (eds) New Polymeric Materials Based on Element-Blocks. Springer, Singapore. https://doi.org/10.1007/978-981-13-2889-3_10
Download citation
DOI: https://doi.org/10.1007/978-981-13-2889-3_10
Published:
Publisher Name: Springer, Singapore
Print ISBN: 978-981-13-2888-6
Online ISBN: 978-981-13-2889-3
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)