Phosphonic poly

Yanagimachi, S., Kaneko, K., Takeoka, Y. and Rikukawa, M. 2003. Synthesis and eyaluation of phosphonated poly(4-phenoxybenzoy 1-1,4-phenylene) Synthetic Metals 135-136 69-70. 

This specifity is dependent on the acidity of the catalyst, and was studied using the heterogeneous catalysts sulfonated and phosphonated poly benzene, and the homogeneous catalysts paratoluenesulfonic acid and phosphoric acid. The differences between the sulfonic and phosphonic acid groups were greater than the differences between heterogeneous and homogeneous phase, in spite of a considerable difference in reaction temperature. It was thus shown that for a typical Class A reaction, the type of acidity is more important than the physical state of the catalyst. These acidic catalysts were extremely active, and had to be partially neutralized in order to obtain reasonable rates ans selective reactions. 

Phosphonated polymers have been proposed for fuel cells with the expectation of being thermally more stable and better retaining water than sulfonic groups [210, 211]. Phosphonated poly(phenylene oxide) [212], poly(4-phenoxy-benzoyl-l,4-phenylene) [213] and polysulfones [214, 215] have been reported. Phosphonated fluoromonomers were polymerized [164]. Characterization of phosphonated films in terms of their proton conductivity has been reported for some of the phosphonated polymers polyphosphazene [216], trifluoropolysty-rene [217], poly(4-phenoxybenzoyl-l,4-phenylene) [218]. Relatively low conductivity values were reported for most of the polymers prepared up to now. The values for polyphosphazene [216] and for perfluorocarbon polymers [219] were quite encouraging. Phosphonated poly(phenylene oxide) [211] was evaluated in fuel cell-tests. 

S. Yanagimachi, K. Kaneko, Y. Takeo-KA, M. Rikukawa, Synthesis and evaluation of phosphonated poly(4-pheno -benzoyl-l,4-phenylene). Synthetic Metals 135/136 (2003) 69 70. 

Poly(phosphate) Poly(phosphonate) Poly(phosphite) Figure 6.9 Polymers with Phosphate Linkages... 

Phosphonated poly(pentafluoro- styrene) 3.89 10-100 mS cm at 10 Pa partial water pressure between 97 and 180 °C 63... 

Fukuzaki et al. have prepared highly phosphonated poly(N-phenylaciyl-amide). The proton conductivity of a crosslinked membrane was 88 mS cm at 95% RH and 80 °C, and it reached 1.9 and 4.7x10 mS cm at 50 and 30% RH, respectively. Like with the polyaciylates, the hydrolytic stability of this material is questionable. 

Aromatic polymers with phosphonated sites directly linked to the main chain have also been prepared by direct polymerization (Scheme 13.2a-d). For example, phosphonated poly(l,3,4-oxadiazole)s have been prepared by direct polycondensation of l,4-dicarbo3y-2-phenyl-phosphonic acid and their dihydrazides in an ionic liquid using triphenyl phosphite as a reaction activator. " The membranes obtained from these polymers were thermally and chemically stable and possessed proton conductivities in the range between 4x10 " and 5x10 mS cm at 100% RH, which is three orders of magnitude lower than the state-of-the-art PFSA membrane Nation . 

Scheme 13.2 Selected phosphonated aromatic backbone polymers (a) phospho-nated pol5 aiylene ether),(b) phosphonated poly(phenyl sul-fone), (c) poly(m-phenylene-5-phosphonic acid), (d) PAES with a phosphonic acid group directly attached to the aromatic backbone, (e) methylenephosphonic acid functionalized PAES, (f) PAES with a phosphonated aUgrl chain, (g) PAES bearing a bis(phosphonic acid) on short alkyl chains, and (h) PAES with a pendant phenyl-CF2P03H2 group. ...

Figure 8. Conversion of the polymeric diethyl phosphonate, poly-(5), to the sodium salt poly-(5 ) under mild conditions.

Yanagimachi S, Kaneko K, Takeoka Y, Rikukawa M (2003) Synthesis and evaluation of phosphonated poly(4-phenoxybenzoyl-l, 4-phenylene). Synth Met 135 69-70... 

Partially fluorinated ionomer membranes Among this material class is the BAM3G membrane type composed of sulfonated or phosphonated poly(a,(5,(5-trifluorostyrene) and its copolymers [2-4] and the different types of grafted membranes based on partially fluorinated polymer foils, as developed by Scherer [5], Sundholm [6], and others. 

Poly-28 after acetolysis gave the corresponding poly (H-phosphonate) (poly-22) with characteristic P-H coupling. Its farther oxidation led to the polyphosphate 23. ... 

Hay and coworkers [76] reported on a catalyzed P - C coupling reaction to synthesize phosphonated poly(arylene ethers) (Scheme 17). 

Membranes were fabricated from phosphonated poly[(4-methylphenoxy)(4-bro-mophenoxy)phosphazene]s with an lEC between 1.17 and 1.43mmoI/g by solution... 

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