Cyclic phosphorus compounds polymerization

T0 prepare models of TA, the corresponding cyclic alkylene phosphoric acids cannot be directly polymerized because the presence of acidic protons of the phosphate group makes the ionic polymerization impossible. Thus, cyclic phosphorus compounds with blocked third functions have to be used. These are phosphates., phosphoramidates and phosphites. After polymerization the obtained polymer is converted by deblocking into the polyalkylene phosphate, e.g. polysalt or polyacid form. 

Table 3 Propagation rate constants and activation parameters in the polymerization of tricoordinated cyclic phosphorus compounds...

A common theme in the speculated polymerization reactions discussed in this section is that the polymers were generally uncharacterized or were composed of small cyclic oligomers. No evidence for high molecular weight polymers from low-coordinate phosphorus compounds was obtained. Of course, multiple bond formation, not polymerization, was the focus of these studies. 

AllcockHR (1972) Phosphorus-nitrogen compounds.Cyclic,linear,andhigh polymeric systems. Academic, New York, chap 16, p 357... 

The chemistry of boron-phosphorus compouuds has been reviewed. Numerous boron-phosphorus derivatives have been reported, but relatively few boron-arsenic or boron-antimony compounds have been described. Boron-phosphorus compounds are similar in many ways to boron nitrogen derivatives, but the teudeucy to share boudiug electrons in covalent tetrahedral compounds is much more evident with phosphorus thau with uitrogeu. lu fact, most boron phosphorus chemistry iuvolves tetrahedral borou. They are typically either phosphiue-boraue complexes, such as R3P BR j, or phosphinoboranes (R2PBR2) , cyclic or polymeric derivatives of the hypothetical H3P BH3. The chemistry of these compounds and that of boron phosphate and thiophosphate is described below. Boron phosphides are discussed in Section 2.6. 

Electrophilic Ring-Opening Polymerization of New Cyclic Trivalent Phosphorus Compounds... 

This paper describes the electrophilic ring-opening polymerization of seven new cyclic phosphorus(III) compounds, 1-7. The polymerization of five- and slx-membered deoxophostones, 1 and and of a benzoxaphosphole 2, produced poly (phosphine oxldejs 11, and via Arbuzov type reactions. The polymerization of f e and slx-" membered deoxothlolphostones, 4 and 5, gave poly(phosphine... 

Thus, we first discuss thermodynamics, paying attention to features that are important for polymer synthesis (e.g., dependence of equilibrium monomer concentration on polymerization variables) then we describe kinetics and thermodynamics of macrocyclization, trying to combine these two related problems, usually discussed separately. In particular we present the new theory of kinetic enhancement and kinetic reduction in macrocyclics. Thereafter, we describe the polymerization of several groups of monomers, namely cyclic ethers (oxiranes, oxetanes, oxolanes, acetals, and bicyclic compounds) lactones, cyclic sulfides, cyclic amines, lactams, cyclic iminoethers, siloxanes, and cyclic phosphorus-containing compounds, in this order. We attempted to treat the chapters uniformly we discuss practical methods of synthesis of the corresponding polymers (monomer syntheses and polymer properties are added), and conditions of reaching systems state and reasons of deviations. However, for various groups of monomers the quality of the available information differ so much, that this attempt of uniformity can not be fulfilled. 

Cationic polymerization of cyclic trivalent phosphorus compounds, initiated by alkyl halides, Lewis acids, Friedel-Crafts catalysts, and/or esters, was reported for various cyclic phosphites (34), " " phosphonites (35), " phosphoramidites (36), cyclic phos-phanols (37), " and cyclic phosphanethiols (38). °° Mel, PhCH2Br, and CF3S03Me were mainly used as initiators. The resulting polymers had molar mass not... 

There are only a few papers discussing the mechanism and kinetics of cationic polymerization of cyclic tricoordinated phosphorus compounds. 

Process for the Polymerization of Cyclic Polyphosphazenes Using a Catalyst Composition of Boron Trihalide and Oxygenated Phosphorus Compounds, U.S. 

Allcock, H. R. (1972). Phosphorus-Nitrogen Compounds. Academic Press, New York. A useful treatment of linear, cyclic, and polymeric phosphorus-nitrogen compounds. 

Our interest in such compounds stems mainly from the possibility that they might be useful precursors to new classes of phosphorus-containing polymers or cyclic oligomers. Functional linkages such as E = NSiMe3 or CR SiMe3 could serve as sites for condensation-polymerization reactions, leading to novel cyclic or polymeric sys terns, ... 

Lapienis, G. andS. Penczek, Cyclic Compounds Containing Phosphorus Atoms in the Ring, Chap. 13 in Ring-Opening Polymerization, Vol. 2, K. J. Ivin and T. Saegusa, eds., Elsevier, London, 1984. 

Hexachlorocyclotriphosphazene (3.19) is prepared on an industrial scale by the interaction of phosphorus pentachloride with ammonium chloride in an organic solvent such as chlorobenzene. This compound, after careful purification and protection from moisture, is heated in the molten state at temperatures between 210 and 250 °C to induce polymerization.15-18 The mechanism of this reaction is discussed in a later section. Here it is sufficient to note that the process can also be applied, with minor variations, to cyclic phosphazo-phosphazenes (3.22a, 3.23), to cyclic fluorophosphazenes (3.24,3.25), and to cyclic carbo- (3.26), thio- (3.27), and thionyl (3.28) -phosphazenes. 

Phosphorous is a five-valent element, and its natural oxide is P2O5, phosphorous pentoxide. It is a highly hygroscopic powder and readily reacts with water to form phosphoric acid (H3PO4). This acid when reacted with various aUcaline compounds forms phosphates. These and other modified compounds are linear or chain, cyclic or ring, and branch chain polymers. Because these compounds are polymeric, phosphates can provide a continuous structure and, hence, form good ceramics. The reader is referred to Topics in Phosphorus Chemistry by Westman [1] for details. Because of the variety of polymeric compounds formed by phosphorous, a systematic nomenclature is used in phosphate chemistry. 

Cationic polymerization of cyclic compounds containing trivalent phosphorus atom has also been reported. Monomers include cyclic phoshites (a) [223,224], phosphonites (b) [225-227], and deoxophosphones (c) [228] ... 

Thietane is a superior inhibitor of corrosion of iron in 10% hydrochloric acid and its effectiveness is said to be due to partial polymerization on the surface of the iron. Addition of chloride ion reduces the inhibition, possibly by inducing ringopening with the formation of sulfhydryl groups. The cyclic sulfide also has been considered as an odorant for natural gas and its absorption by organic soil and clay have been determined. Stabilization of methylchloroform and trichloroethylene by thietane, 2-methylthietane, 3-hydroxythietane, and two spirothietane derivatives has been claimed. Phosphorus and tin derivatives of 3,3-bis-hydroxy-methylthie-tane are reported to be light stabilizers for poly(vinyl chloride), and the dibutyl-tin derivative is a catalyst for the polymerization of aliphatic isocyanates. Mercury and zinc compounds derived from phenylmercury or phenylzinc hydroxide and 3-... 

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