Oxyethylation

Transesterification reactions between the methyl propionate and various alcohols produce another family of stabili2ers. Stearyl alcohol yields octadecyl 3-(3,5-di-/ f2 -butyl-4-hydroxyphenyl)propionate (27) (16), pentaerythritol gives the tetrakis ester (28) (17), and trishy dr oxyethyl isocyanurate gives (29) (18). 

The stability of the copolymers may be enhanced by alkaline hydrolysis following polymerisation to remove oxymethyl end-groups and replace them with the more stable oxyethyl groups. 

Chemical Designations - Synonyms Ethoxylated dodecyl alcohol, Ethoxylated lauryl alcohol, Poly(oxyethyl)dodecyl ether, Poly(oxyethyl) lauryl ether, Tergitol Nonionic TMN Chemical Formula CijHu0(CH2CH20) CHi CH OH n=6-10 (average). 

Chemical Designations - Synonyms Ethoxylated pentadecyl alcohol, Poly(oxyethyl) pentadecyl ether, Terrgitol nonionic 45-S-lO Chemical Formula C]3H3i0(CH2CH20) CH2CH20H n=10 (average). Observable Characteristics - Physical State (as normally shipped) Liquid Color Colorless Odor Mild, pleasant. 

The polymeric latex obtained in a hydrophobic organic solvent is poorly dispersed in water because of the presence of an emulsifier with a low HLB value. For this reason, a wetting agent is added to water or emulsion prior to the dissolution. The wetting agent (a surface active substance with a high HLB value) facilitates the inversion of latex phases to produce a direct type emulsion. Usually, it belongs to oxyethylated alkylphenols, fatty alcohols, or fatty acids. 

Reactions of this type are quite popular and widely used to introduce hydrophilic and ionogenic groups into linear polymers as well as directly into polymer networks. These reactions include hydrolysis (PAAm, PAAc and their analogs from PAN, PVA from poly (vinyl acetate), oxyethylation and oxymethylation of starch and cellulose, sulfurization, and other reactions. These processes are of industrial importance, well studied and widely reviewed. 

A solution of 1.93 g (6.91 mmol) of methyl 4-nitrobenzyl diazomalonate in 100 mL of dry benzene is added dropwise over 1 h to a refluxing solution of 1.79 (4.48 mmol) of (4S,5R/S )-4-acetoxy-l-(2-benzoyl-oxyethyl)-5-phenylthio-2-pyrrolidinone in 100 mL of dry benzene in the presence of a catalytic amount of rhodium acetate. The mixture is stirred under reflux for an additional hour after which the solvent is removed. The residue is chromatographed (silica gel, benzene/ethyl acetate 8 2) to furnish an oil yield 2.32 g (85%). 

Whereas nonionic ethylene oxide adducts discolor badly on contact with sodium hydroxide, phosphate derivatives of these nonionics exhibit good color stability even under these conditions. But in the presence of strong acids poly-oxyethylated phosphate esters undergo hydrolysis to the base nonionic and phosphoric acid. However, the free surface-active acids by themselves show little tendency to hydrolyze. They have a pH value of 2 in aqueous solution. 

D-a-azidaphenylacetamido)-penicillanlc acid 1-ethoxycarbonyl-oxyethyl ester (1)... 

Oxyethylated Alkylphenol, Fatty Acid Amide, and Alkylphosphate Mixtures... 

A solution of a surfactant mixture in liquid paraffin, containing oil-soluble oxyethylated alkylphenol, having the formula with an Cg to C12 alkyl rest, the alkylphosphate of a higher fatty acid alcohol (RO)2PO — OH where R is Cio to C20, and a fatty acid amide of diethanolamine, are suitable for removing oils... 

Petroleum spillages can be removed from water surfaces more efficiently with the following detergent mixture [1692], which contains mainly oxyethyl-ate fatty Cio to C20 alcohols and additional oxyethylated fatty Cn to Cyj acids with an oxyethylene chain length of one to two units. It is used in the form of an aqueous 20% to 25% emulsion, which is sprayed onto a contaminated surface. 

Y. A. Balakirov, A. I. Chemorubashkin, G. A. Makeev, I. P. Korolev, and V. N. Glushchenko. Composition for treatment of stratum head zone—contains oxyethylated isononyl phenol, aqueous solution of hydrofluoric acid and aqueous solution of hydrochloric acid. Patent SU 1770555-A, 1992. 

P. E. Chaplanov, A. D. Chemikov, O. G. Mironov, G. N. Semanov, A. G. Svinukhov, A. G. Yaremenko, F. V. Linchevskij, N. A. Melnik, 1. A. Murashev, and I. S. Akhmetzhanov. Removing oils and petroleum products from water surfaces—using mixture of oxyethylated alkyl-phenol, alkyl-phosphate and fatty acid diethanolamine. Patent SU 1325816-A, 1992. 

V. Kh. Dulaev, N. M. Bondarets, N. A. Polukhina, V. I. Petresku, R. G. Galiev, P. P. Kapustin, and O. S. Matrosov. Composition for preparation of aerated plugging solution—contains Portland cement, oxyethylated monoalkylphenol(s) of propylene trimers, glycol mixture, air, water, etc. Patent SU 1745893-A, 1992. 

A. B. Sulejmanov, T. B. Geokchaev, and R. A. Dashdiev. Removal of petroleum spillages from water surface— using a detergent mixture containing oxyethylated fatty 10-20 C alcohols and additional oxy-ethylated fatty 11-17 C acids to improve properties. Patent SU 1803418-A, 1993. 

Surfactants. The use of surfactants is greatly restricted in formulating ophthalmic solutions. The order of surfactant toxicity is anionic > cationic >> nonionic. Several nonionic surfactants are used in relatively low concentrations to aid in dispersing steroids in suspensions and to achieve or to improve solution clarity. Those principally used are the sorbitan ether esters of oleic acid (Polysorbate or Tween 20 and 80), polymers of oxyethylated octyl phenol (Tyloxapol), and polyoxyl 40 stearate. The lowest concentration possible is used to perform the desired function. Their effect on preservative efficacy and their possible binding by macromolecules must be taken into account, as well as their effect on ocular irritation. The use of surfactants as cosolvents for an ophthalmic solution of chloramphenicol has been described [271]. This com-... 

Ion-ion tautomerism Functional groups with a mobile hydrogen atom present in the ammonium cation can result in one more type of tautomerism, as in the case of /3-oxyethyl(triethyl)ammonium 1,3,2,5-dioxaborataphosphorinane (128) (88IZV155). In this case the equilibrium between two ionic forms (acyclic and cyclic) has been observed [Eq. (94)]. 

Poly-3-chloro-2-hydroxypropylmethacryl-oxyethyl dimethylammonium Chloride 1.0-5.0 Polysciences, Warrington, PA... 

Magnetic susceptibihty measurements [256] on Cu VCo VZn/Al LDHs indicate that the Cmie-Weiss law is obeyed with a Weiss temperature close to zero, indicating the lack of magnetic interactions between paramagnetic ions and thus a random distribution in the lattice. It has been proposed, however, that the catalytic activity of Mg Al LDHs n = 2,3) containing interlayer carbonate anions in the oxyethylation of 1-dodecanol with ethylene oxide can be correlated with the distance between AP" cations in ordered lattices [250]. 

Synonyms DMEP 1,2-benzenedicarboxylic acid bis(2-methyoxy-ethyl)ester bis (meth-oxyethyl) phthalate dimethyl cellosolve phthalate... 

Sahoo et al. [123] have studied the micellar behavior of a series of poly-oxyethylated alkyl ethers (a see below) and some anionic surfactants such as... 

Polychlorinated Biphenyl (PCB) Polychloropolyphenyls Polyformaldehyde Pclyisobutylene Plastics Polyisobutylene Resins Polyisobutylene Waxes Polyhethylene Polyphenyl Isocyanate Polyoxpropylene Ether, PPG Poly(Oxyethyl) Dodecyl Ether Poly(Oxyethyl) Lauryl Ether... 

Poly(Oxyethyl) Myristyl Ether Poly(Oxyethyl) Pentadecyl Ether Poly(Oxyethyl) Tetradecyl Ether Poly(Oxyethyl) Tridecyl Ether Polyoxymethylene Polyoxymethylene Glycol Polyoxypropylene Glycol Polyoxypropylene Glycol Methyl Ether Polyphosphoric Acid Polypropylene Polypropylene Glycol Polypropylene Glycol Methyl Ether Potassium Chromate Potassium Chromate (VI)... 

In explosive properties and explosive power it is similar to dinitrodi-(/ -hydr-oxyethyl)-oxamide, described above. 

Cyclopentene is readily available as a byproduct in the ethylene production. Norbornene 2-ethylhexyl carboxylate is obtained by the Diels-Alder reaction of 2-ethylhexyl acrylate with cyclopenta-diene (5). Norbornene isobornyl carboxylate, norbornene phen-oxyethyl carboxylate, and other related monomers are synthesized according to the same route. Polymers obtained from these esters exhibit excellent properties in terms of controlling the crosslinking density, the associated product modulus, and the glass transition temperature (Tg), thus allowing tailoring the properties of elastomers, plastics and composites. Other suitable monomers are summarized in Table 1.1 and sketched in Figure 1.2. 

QIM of Schiiurmann for Oxyethylated Surfactants Schiiurmann [63] studied Kow and its relation to aquatic toxicity for polyoxyethylene compounds of the type shown in Figure 13.5.4. The contribution of the -CH2-CH2-O- group is not a constant but depends on the length of the oxyethylene chain. For the insertion of a -CH2-CH2-O- group, Schiiurmann reports a variation from — 0.10 for long-chain molecules to —0.19 for short-chain molecules. 

Schiiurmann, G., QSAR Analysis of the Acute Toxicity of Oxyethylated Surfactants. Chemosphere, 1990 21, 467-478. 

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