Phosphate Ester Polymers

Certain phosphate esters can be polymerised to give polymers on their own account (homopolymers), with the P atom either in the side chain (12.75) or in the main chain (12.76). Natural polymers of the latter type include the nucleic acids and the teichoic acids (Chapter 10.3). 

Some 5- and 6-membered ring phosphate esters can be polymerised as, for example, methyl ethylene phosphate (12.77). 

Tris allyl phosphate, (CH2=CH-CH20)3P0, will give rise to a clear hard cross-linked polymer, although polymerised allyl or vinyl phosphates (12.75) have not generally led to successful commercial products. Simple monoalkyl phosphates on heating (12.76) can be made to yield polyphosphate esters with molecular weights approaching a million. 

High polymers (mw 15,000) or relatively short-chain oligomers can be prepared by the reaction of POCI3 or aromatic derivatives ArPOCl2 with some dihydric phenols (12.78) [26]. 

Products of type (12.78), first obtained about 50 years ago ( phoryl resins ), have good flame resistance, high transparency and hardness, but they lack resistance to hydrolysis because of the P-O-C linkages which are present. Similar polymers based on phosphonates (12.79) are somewhat more stable, but satisfactory stability towards hydrolysis is more likely to be achieved with chains based on P-C linkages. 

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Synthetic oils have been classified by ASTM into synthetic hydrocarbons, organic esters, others, and blends. Synthetic oils may contain the following compounds diaLkylben2enes, poly(a-olefins) polyisobutylene, cycloaUphatics, dibasic acid esters, polyol esters, phosphate esters, siUcate esters, polyglycols, polyphenyl ethers, siUcones, chlorofluorocarbon polymers, and perfluoroalkyl polyethers. 

The development of monoalkyl phosphate as a low skin irritating anionic surfactant is accented in a review with 30 references on monoalkyl phosphate salts, including surface-active properties, cutaneous effects, and applications to paste and liquid-type skin cleansers, and also phosphorylation reactions from the viewpoint of industrial production [26]. Amine salts of acrylate ester polymers, which are physiologically acceptable and useful as surfactants, are prepared by transesterification of alkyl acrylate polymers with 4-morpholinethanol or the alkanolamines and fatty alcohols or alkoxylated alkylphenols, and neutralizing with carboxylic or phosphoric acid. The polymer salt was used as an emulsifying agent for oils and waxes [70]. Preparation of pharmaceutical liposomes with surfactants derived from phosphoric acid is described in [279]. Lipid bilayer vesicles comprise an anionic or zwitterionic surfactant which when dispersed in H20 at a temperature above the phase transition temperature is in a micellar phase and a second lipid which is a single-chain fatty acid, fatty acid ester, or fatty alcohol which is in an emulsion phase, and cholesterol or a derivative. 

Anionic Association Polymer. Another type of lost circulation agent is a combination of an organic phosphate ester and an aluminum compound, for example, aluminum isopropoxide. The action of this system as a fluid loss agent seems to be that the alkyl phosphate ester becomes crosslinked by the aluminum compound to form an anionic association polymer, which serves as the gelling agent [1488]. 

The thioester hypothesis can be summed up as follows the formation of thiols was possible, for example, in volcanic environments (either above ground or submarine). Carboxylic acids and their derivatives were either formed in abiotic syntheses or arrived on Earth from outer space. The carboxylic acids reacted under favourable conditions with thiols (i.e., Fe redox processes due to the sun s influence, at optimal temperatures and pH values) to give energy-rich thioesters, from which polymers were formed these in turn (in part) formed membranes. Some of the thioesters then reacted with inorganic phosphate (Pi) to give diphosphate (PPi). Transphosphorylations led to various phosphate esters. AMP and other nucleoside monophosphates reacted with diphosphate to give the nucleoside triphosphates, and thus the RNA world (de Duve, 1998). In contrast to Gilbert s RNA world, the de Duve model represents an RNA world which was either supported by the thioester world, or even only made possible by it. 

The flame retardant mechanism for phosphorus compounds varies with the phosphorus compound, the polymer and the combustion conditions (5). For example, some phosphorus compounds decompose to phosphoric acids and polyphosphates. A viscous surface glass forms and shields the polymer from the flame. If the phosphoric acid reacts with the polymer, e.g., to form a phosphate ester with subsequent decomposition, a dense surface char may form. These coatings serve as a physical barrier to heat transfer from the flame to the polymer and to diffusion of gases in other words, fuel (the polymer) is isolated from heat and oxygen. 

We previously reported that brominated aromatic phosphate esters are highly effective flame retardants for polymers containing oxygen such as polycarbonates and polyesters (9). Data were reported for use of this phosphate ester in polycarbonates, polyesters and blends. In some polymer systems, antimony oxide or sodium antimonate could be deleted. This paper is a continuation of that work and expands into polycarbonate alloys with polybutylene terephthalate (PBT), polyethylene terephthalate (PET) and acrylonitrile-butadiene-styrene (ABS). 

Results have generally been disappointing. It can be difficult to remove the TSA from the polymer, but a more fundamental problem concerns the efficiency of the catalysis observed. The most efficient systems catalyze the hydrolysis of carboxylate and reactive phosphate esters with Michaelis-Menten kinetics and accelerations (koAJKM)/kunoJ approaching 103,1661 but the prospects for useful catalysis of more complex reactions look unpromising. Apart from the usual difficulties the active sites produced are relatively inflexible, and the balance between substrate binding and product inhibition is particularly acute. 

The last work pertaining to the discovery of new catalysts is perhaps the most novel approach to be reported thus far. In one of the earliest approaches taken toward catalyst development, Menger et al. (61) attempted to find catalysts for phosphate ester hydrolysis. A series of eight functionalized carboxylic acids were attached to polyallylamine in various combinations. Each of these polymers were then treated with one of three metals, Mg2+, Zn2+, or Fe3+. The different members of each library were identified by the relative percentages of each carboxylic acid attached to the polyamine. For example, one polymer possessed 15% Oct, 15% Imi, 15% Phe, and 5% Fe3+. There is no attempt to identify the location of the various carboxylic acids in a given polymer. This approach is novel since each system consists of an ensemble of different ligands with the carboxylic acids positioned in various locations. Each polymer within a given ratio of carboxylic acids consists of a combinatorial library of potential catalysts. 

Epoxy phosphate esters, 10 383-384 Epoxy plasticizers, for PVC polymers, 25 674... 

Reduction of polymer flammability is of broad interest for applications ranging from plastics to textiles. For polyesters, given their inherent instability towards water at elevated temperatures, and the high temperatures of manufacture, many classes of flame-retardant (FR) agents, including most halogen-containing materials, are impractical. Phosphate esters, capable of incorporation into the polymer backbone, were pioneered by Hoechst AG, and continue to be the materials of choice [84, 85],... 

The early patent disclosures have claimed the application of a wide spectrum of gas-evolving ingredients and phosphorus-based organic molecules as flame retarding additives in the electrolytes. Pyrocarbonates and phosphate esters were typical examples of such compounds. The former have a strong tendency to release CO2, which hopefully could serve as both flame suppressant and SEI formation additive, while the latter represent the major candidates that have been well-known to the polymer material and fireproofing industries.The electrochemical properties of these flame retardants in lithium ion environments were not described in these disclosures, but a close correlation was established between the low flammability and low reactivity toward metallic lithium electrodes for some of these compounds. Further research published later confirmed that any reduction of flammability almost always leads to an improvement in thermal stability on a graphitic anode or metal oxide cathode. 

Nucleic acids are polymeric nucleotides in which phosphate esters link ribose or deoxyribose molecules through the C OH of one and the C OH of the other. In rna, the aglycone nitrogen bases are cytosine, adenine, guanine, and uracil. In dna, thymine replaces uracil. The rna polymer is like that of dna, except that a CH, replaces the OH group on C of the ribose ring. 

Some exploratory experiments have also been carried out with some phosphate esters. Rate constants for one of these, dinitrophenyl-phosphate, are listed in Table VII. With this substrate, surprisingly, the intrinsic primary amines of the polymer seem to be acting in a turnover pathway, that is, are phosphorylated and then dephosphorylated, but this mechanism needs to be better substantiated. In any event it, it is clear that the rates in the presence of polymer are accelerated more than 103-fold with dinitrophenylphosphate. Even larger accelerations have been observed with other phosphate esters. 

Sometimes, addition of plasticizer imparts flame retardant characteristics in addition to other properties. Phosphate esters such as tris(2-ethyl hexyl) phosphate (TOP), tricresyl phosphate (TCP), chlorinated paraffin hydrocarbons etc. impart excellent flame retardant characteristics to many polymers. 

Phosphate -ester cross-linked polyethylene glycol)s [60] are obtained from the condensation of glycols with POCl3. Partition of Li-trifluoro-methanesulfonate-LiCF3S03 between acetone solution and the polymer gel results in the formation of the electrolyte salt complexes [60],... 

Benzoylresorcinol based phosphate esters are obtained by reacting a benzoylresorcinol compound with a chlorophosphate, e.g., benzoylresorcinol with diphenyl chlorophosphate or phosphorus oxychloride. These esters can function both as flame retardants and UV stabilizers for PC/ABS and a series of other polymers (78). 

FADH2 (Section 15-6C). Polynucleotides are polymers of nucleosides linked through phosphate ester bonds. Polynucleotides also are called nucleic acids (RNA and DNA) and are the genetic material of cells, as will be discussed in Chapter 25. 

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