Alkoxylation Liquid

Unilaneth PPG-12-PEG-65 [Universal Preserv-A-Chem http //www.upichem.com], VIgllan AWS [Fanning http //www.fanncorp.com] PPG-40-PEG-60 lanolin oil Synonyms POE (60) POP (40) lanolin oil POP (40) POE (60) lanolin oil Classification Alkoxylated liquid lanolin Definition Polyoxypropylene, polyoxyethylene deriv. of lanolin oil... 

Ether carboxylates are used not only in powdered detergents but in liquid laundry detergents for their hard water stability, lime soap dispersibility, and electrolyte stability they improve the suspension stability and rheology of the electrolyte builder [130,131]. Formulations based particularly on lauryl ether carboxylate + 4.5 EO combined with fatty acid salt and other anionic surfactants are described [132], sometimes in combination with quaternary compounds as softeners [133,163]. Ether carboxylates show improved cleaning properties as suds-controlling agents in formulations with ethoxylated alkylphenol or fatty alcohol, alkyl phosphate esters or alkoxylate phosphate esters, and water-soluble builders [134]. 

If primary alcohols with a straight chain of 10-20 carbon atoms are initially alkoxylated by a mixture of ethylene and propylene oxides followed by phosphorylation, a pour point depression to 8°C will occur, whereas phosphate esters derived from nonylphenol are liquid at temperatures as low as 2°C. Phosphoric acid esters on the base of linear primary alcohols (Cn-Cl5) generally solidify below 24°C [50] (Table 2). 

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. 

Extensive data concerning the influence of the polar groups on the activation energies for abstraction reactions were obtained by analyzing the experimental data on reactions involving alkoxyl and peroxyl radicals in the liquid phase. These data are discussed in Chapters 7-9. 

The situation with 7V-acyloxy-/V-alkoxyureas and carbamates is similar although infrared data were mostly determined by liquid film or condensed phase (KBr/nujol mull).52,131 However, the limited data for V-acyloxy-TV-alkoxyureas (Table 2, entries 69-72) give amide carbonyl frequencies ca. 1730 cm-1 that are raised by some 37-40 cm-1 by acyloxylation. Values for carbamates (Table 2, entries 73-77) are higher (mostly 1780 cm-1) but are raised to a lesser extent (10-20 cm-1) relative to their parent carbamates. Clearly, carbonyl vibrational frequencies will be influenced strongly by the adjacent amino or alkoxyl group in both analogues. 

The liquid phase alkoxylation of limonene (3) with C4-C4 alcohols to 1-methyl-4-[a-alkoxy-isopropyl]-l-cyclohexene (5) was carried out both in batch and continuous fixed-bed reactor at 60 °C on various acidic catalysts (Scheme 3.1) [16]. The best yields were obtained in batch (85%) or continuous reactor (81%) using a /1-type zeolite with Si02/Al203 = 25. 

Alkoxy)diborons, alkyne additions, 10, 727-728 Alkoxy-hydro carbonylation, in ionic liquids, 1, 863 Alkoxy ketones, asymmetric hydrogenation, 10, 47 Alkoxylation... 

In order for such glycosides to be utilized for polyurethane formation, further chemical modification is required to reduce hydrogen-bonding interactions. Chain extension, often by alkoxylation at elevated temperature and under pressure, is used to obtain suitable liquid polyols. Otey (if), for example, has modified EGG in this manner in a bulk alkoxylation to yield polyols that could then be used to form polyurethane foams. 

This synthesis is applicable to many aromatic compounds, including alkoxyl or N,N dimethylamino derivatives of benzene and naphthalene, naphthols, indole, and certain reactive hydrocarbons, namely, anthra-cene, 1,2-benzanthracene, 3,4-benzpyrene, ° and pyrene. The high-melting polynuclear hydrocarbons react best in the presence of a solvent, such as o-dichlorobenzene. For example, a solution of anthracene, methyl formanilide, and phosphorus oxychloride in o-dichlorobenzene is heated 1 hour at 90-95° then an aqueous solution of sodium acetate is added, and the solvent and N-methylaniline are removed by steam distillation. The solid residue is readily purified to yield 9-anthraldehyde (84%). With liquid or low-melting compounds a solvent is not required. 

Hence, under the experimental conditions of the 185 nm liquid phase photolysis the alkoxyl radicals practically do not react with other radicals. 

The decomposition of peroxides (RO-OR) and azo compounds (R-N=N-R) to form radicals is favoured by an increase in entropy. One peroxide molecule decomposes to give two alkoxyl (RO ) radicals, whereas an azoalkane will form three species two carbon-centred radicals (R ) and nitrogen gas. The formation of the gas is particularly favourable because of the greater freedom of motion in gases (than in liquids or solids), resulting in an increase in disorder. 

Koester, Behler, Neuss, Schmid, Eisner Cognis Hand dishwashing liquid comprising an alkoxylated carboxylic acid ester Contains an alkoxylated carboxylic acid ester... 

The solubility of alkylene oxides in the reaction mass is another important parameter, because the reaction takes place in the liquid phase and the gaseous monomer is transferred from the gas phase to the liquid phase. Because all the propoxylation and ethoxylation reactions are strongly diffusion dependent, the surface of the gas-liquid interface is a very important parameter for the mass transfer from the gas to liquid, and the real consumption of alkylene oxides depends strongly on this parameter. Between the alkoxylation of fatty alcohols and the alkoxylation of glycerol, there are many similarities if we use the Santacesaria kinetic model. Thus if RXH are considered to be the hydroxyl groups of the starter, the reaction rate of alkylene oxides addition is ... 

Aminic polyols are low molecular weight adducts of propylene oxide (PO) [and/or ethylene oxide (EO)] made from aliphatic or aromatic polyamines such as ethylenediamine (EDA), diethylene triamine (DETA) [1, 2], ortho-toluene diamine (o-TDA) [3, 4] or diphenylmethanediamine (MDA) [2, 5, 6]. Because these starters are liquid at room temperature (EDA, DETA) or low melting point solids (o-TDA, MDA), they are alkoxylated in the absence of solvents. 

Bisphenol A is a compound with a melting point of around 157 °C, which is higher than the normal alkoxylation temperatures (90-120 °C). Bisphenol A can be alkoxylated in a liquid reaction medium such as an inert solvent (toluene, xylene) or in a reactive liquid reaction medium such as PO or in the final polyether polyol [28, 30]. 

A second method is to suspend the solid bisphenol A in liquid PO, in the presence of the tertiary amine used as catalyst (molar ratio 1 mol of bisphenol per 1.5-2 mols of PO). After 1.5-2 hours of mixing at 90-100 °C, the alkoxylation is continued by adding 6-8 mols of EO. Finally, the resulting diol is degassed under vacuum and is used in PU fabrication... 

A third process of solid bisphenol A alkoxylation is to use a suspension of solid bisphenol A in final polyether polyol (40-60% bisphenol A and 60-40% liquid polyether diol). This suspension, in the presence of a tertiary amine as catalyst, is ethoxylated at 80-95 °C, with 8-9 mols of EO/mol of bisphenol A. At the end of the reaction, all the solid bisphenol A was totally transformed into liquid polyether diols [30]. The resulting polyether diols are used successfully for production of urethane-isocyanuric foams with very good physico-mechanical properties and intrinsic fire resistance. 

The alkoxylation of lignin is possible in a solvent (dimethylformamide, N-methylpyrrolidone or in liquid PO [20]). A process using a lignin-glycerol mixture (3 1) in a polyether polyol based on lignin was developed [20]. The catalysts of this reaction are KOH, but a tertiary amine, such as dimethylaminoethanol is preferred. By alkoxylation with a PO-EO mixture (e.g., 18-25% ethylene oxide EO) a totally liquid dark-brown lignin-based polyether polyol with a viscosity in the range 4,700-8,000 mPa-s at 25 °C, with an hydroxyl number... 

It is very interesting that in the alkoxylation (with PO or EO) of a flexible or semiflexible PU foam, the PU crosslinked polymer is transformed into a liquid product. 

We see in these examples that great effect can be created by substitutions on the two ends of the mesogenic cores. The consequence includes not only the formability of liquid crystal phases and transition temperatures, but also the types of the liquid crystalline phase. It is well known that substitution on the end with longer linear alkyls and alkoxyls favor the formation of smectic phases. One example for this remark has been given in Table 3.3. In the design of liquid crystal polymers, especially in the cases of side-group type and molecular shish-kebabs, the concept of end-substitution has been fully utilized. 

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