Organophosphazenes. 19. Copolymerization of 2-(α-ethoxyvinyl)pentafluorocyclotriphosphazene with styrene and methyl methacrylate

Abstract

Figure 3. Values of pm/pr when the statistical weight denoted by w is varied about its reference value w,. The assignment of w is shown for each curve.should generally be greater than one for monosubstituted vinyl polymers.Acknowledgment is made to the donors of the Petroleum Research Fund, administered by the American Chemical Society, for support of this research. References and Notes(1) Flory, P.

Homo- and Copolymerization of (Methacryloylethenedioxy) pentachlorocyclotriphosphazene

“…The molecular weights of the i/MMA copolymers decrease with increasing phosphazene in the feed. The same result has occurred in all the previous copolymerizations between vinylphosphazenes and organic monomcrs [3][4][5], and indicates that the phosphazene monomer is acting as a chain transfer or terminating agent. Consequently, reduced molecular weights from the poly(methacryloyl phosphazene) homopolymer may be expected.…”

“…These materials are in contrast to the well established poly(phosphazenes) in which the backbone is a linear phosphazene unit [2]. While our earlier investigations focused on copolymers of alkenylfluorocyclotriphosphazenes [3][4][5] and organic comonomers, recent investigations have focused derivatives of the more readily available hexachlorocyclotriphosphazene, N30PCI. The next step in our investigations is to develop cyclophosphazene monomers derived from (relatively) inexpensive starting materials and which can be copolymerizied with standard organic monomers thus allowing for incorporation of useful cyclophosphazene properities into traditional polymers.…”

Polymerization of vinyl derivatives of the main group elements

“…Mediation of the electron withdrawing effect of the phosphazene by modification of the olefin has been C3HT)R (R=CH(OH)C6H&H=CH2, CH(OC(0)C TABLE 6 Alfrey-Price Parameters for Vinylphosphazenes System (Phosphazene/Comonomer) Q (Phosphazene) e (Phosphazene) Reference N3P3F5C(CH3) =CH,/styrene 0.21 0.18 111 N3P3F5C(OC2H5) = CH,/styrene 0.18 -0.06 126 para-N3P3F5C6H4C(CH3) = CHJstyrene 0.72 0.72 117 mefa-N3P3F5C6H4C(CH3) = CHz/styrene 0.63 0.58 117 N3P3Cl50CsH4CsH4CH=CHz/styrene 2.0 -0.39 124 N3P3Cl50(CHz)zOC(O)C(CH3) =CH,/MMA 0.96 1.24 121 studied using 2-(a-ethoxyvinyl)pentafluorocyclotriphosphazene. The reactivity ratios and the Q and e values(Tables 4 and 6) obtained in the styrene and methyl methacrylate copolymerization of the ethoxyvinylphosphazene show that the electronic behavior of the olefin is closer to that of vinyl acetate than to that of a vinyl ether[126].…”

Thermal properties, adhesive strength, and optical transparency of cyclolinear poly(aryloxycyclotriphosphazenes)

“…All chlorines on the phosphorus atoms can be readily replaced with a wide variety of functional organic groups via nucleophilic substitution reaction, affording different organocyclotriphosphazenes and poly(organocyclotriphosphazenes) depending on the number of functional groups of the substituents 1–5. Phosphazene is a versatile compound, which has a wide range of industrial applications such as preparation of phosphazene‐based epoxy resin,6–8 inherent fire‐ and heat‐resistant polymers,9, 10 copolymers with organic backbones and cyclotriphosphazene as pendant units,11, 12 additives for improving thermal degradation and flame retardancy,13–15 precursor for curing agents,16 lubricants,17 photocurable,18 antioxidants,19 coatings,20 and adhesives 21. The phosphazene backbone is completely transparent from the mid‐UV to the near infrared region, this due to the unfavorable geometry of the PN bond present in the phosphazene polymer chain; therefore, no delocalization of the charges or π electron is allowed in these materials, their resonance forms being limited within the three P N P atomic system 22…”