Ethoxylated tertiary amines

Ethoxylated tertiary amines can be produced by the reaction of primary or secondary amines with ethylene oxide. The water solubility of this amine increases with the increasing degree of ethoxylation (33). 

TOMAH AO-728 Special is a high foaming 50% active amine oxide. It is a very effective foam booster/stabilizer in liquid detergent formulations. It is an economical replacement for lauryl dimethyl amine oxide and many alkanolamldes. TOMAH AO-728 Special is manufactured from an ethoxylated tertiary amine. These amine oxides are generally considered to be milder to skin and eyes than amine oxides manufactured from methyl tertiary amines. 

The antistatic agents recommended for PO fibers are quaternary ammonium salts of fatty acids, alkano-lamines, alkanolamides, polyglycolesters, alkoxylated triglicerides, and ethoxylated tertiary amines (Table 2). The quaternary ammonium compounds and nonionic surfactants dominate this field because of their higher oil solubility and hygroscopicity. 

Ethoxylation and Propoxylation. Ethylene oxide [75-21-8] or propylene oxide [75-56-9] add readily to primary fatty amines to form bis(2-hydroxyethyl) or bis(2-hydroxypropyl) tertiary amines secondary amines also react with ethylene or propylene oxide to form 2-hydroxyalkyl tertiary amines (1,3,7,33—36). The initial addition is completed at approximately 170°C. Additional ethylene or propylene oxide can be added by using a basic catalyst, usually sodium or potassium hydroxide. 

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. 

A, air H, water W, waste Al, aliphatic amine AA, aromatic amine PAA, polyaromatic amine ABDAC, alkylbenzyldimethylammonium chloride AME, alkylamine ethoxylates T, tertiary amine PE, polyethylene PS/DVB, polystyrene/divinylbenzene PDMS, polydimethylsiloxane PA, polyacrylate PAB, polyacrilonitrilbutadiene. 

Ethylene oxide adds to the bis(2-hydroxyeth5i) tertiary amine in a random fashion where x y = n - -2. Ethoxylated amines, varying from strongly cationic to very wealdy cationic in character, are available containing up to 50 mol of ethjiene oxide/mol of amine. Ethyoxylated fatty amine quaternaries, cationic surfactants (both chloride from methyl chloride and acetate from acetic acid), are also available. 

Cationic surfactants can also be used as functional additives in traditional chain lubricant formulations, including biocides, stress-craze inhibitors and coupling agents. As mentioned above, the first use of alkylamines in chain lubricants was as an additive in a traditional, soap-based formulation to improve the stability of the system. Ethoxylated amines have also been employed as coupling agents in an alkaline diamine track lubricant, while tertiary amines have found utility as saponifying agents in traditional, soap-based chain formulations. 

Organic residual components are the most worrying because of their toxicity. Some of these compounds are formed as by-products. Volatile organic compounds are determined by headspace GC, GC-MS. Intermediate products, such as sultones and sulfones, from sulfonation of olefin and alkyl-benzene, respectively, can be detected by LC. Unreacted products, like ethylene oxide from the synthesis of ethoxylated nonionic and anionic surfactants, are studied by GC benzyl chloride from the quaternization of tertiary amines and aliphatic amines from amidation reaction are determined by LC (Figure 5). 

Retention was found to be related to the ethylene oxide (EO) content for primary alcohols of a particular alkyl chain (e.g., Cg-Ci2). The more hydrophilic (higher EO) surfactants were found to perform better as deposition agents than the more hydrophobic surfactants. Similarly, the size and shape of the hydrophobic moieties are important. Bulky, highly branched head groups, ethoxylated secondary alcohols, ethoxylated tertiary tallow amines with two ethoxylated tails, and sugars all appear to be efficient as deposition aids [37]. 

Rhodameen T-5 Tertiary amines ethoxylates of primary taUow amines... 

The ethoxylates of both mono- and diamines consist principally of tertiary amines, most of the primary nitrogen atoms adding on two ethylene oxide chains and the secondary nitrogen atoms of the diamines adding on one. Any surviving primary amine is the starting material, RNH2, and any secondary amine is either unreacted diamine or primary amine that has added on only one EO chain. Such chains are always short, mostly only one EO unit. The level of primary and secondary amines is low. 

Seven structural types of amphoterics and betaines are commonly known and used (Fig. 7). Structures B, CAPB, and HB are made by reacting sodium chloroacetate (SCA) with an appropriate substituted tertiary amine usually in water (Fig. 8). A mole of salt is produced, some of which precipitates out and is removed by filtration, with the rest remaining in solution. For B, a conunercially available alkydimethylamine is used, while for structure HB an ethoxylated alkylanune is the building block. For CAPB, an amidoamine is first prepared from dimethylaminopropylamine (DMAPA) and either a fatty acid or ester. 

Uses Intermediate for mfg. of alkyl sulfates and ethoxylates, alkyl halides, esters, alkyl amines, defoamers, aluminum rolling lubricants, tertiary amines, cosmetics, ethoxylates, halldes/mercaptans, polymerization stabilizers, sulfation Reguletery Not regulated for transport Canada DSL Australia Philippines China Korea Japan ENCS... 

Uses Intemiedlate for mfg. of alkyl sulfates and ethoxylates, alkyl halides, esters, alkyl amines, aluminum rolling lubricants, tertiary amines, cosmetics, ethoxylates, halldes/mercaptans, polymerization stabilizers, sulfation Properties Wh. waxy solid mild, soapy odor negligible sol. in water sp.gr. 0.811 (K C) vapor pressure < 1 mm Hg m.p. 56-WIC b.p. > 248.9 C flash pt. (PMCC) 172 C acid no. 0.5 max. iodine no. 2 max. sapon. no. 1 max. hyd. no. 200-215 Toxicology LD50 (oral, rat) > 20 g/kg may cause mild, transient eye irritation prolonged exposure may cause sL, transient skin Irritation Ing. may cause Gl Irritation TSCA listed... 

The property of f. to be local irritants of eyes and skin is reduced by ethoxylation. Manufacturing from RR is predominantly done via the fatty nitriles, which are made from fatty acids by reaction with ammonia. The nitriles are reduced by - hydrogenation (batch or continuous) into amines. The reaction conditions determine whether primary, secondary or tertiary amines result. Saturated f are formed when nitriles are hydrogenated at 80-140 °C and 1-4 MPa/lO O bar over Ni catalyst. Unsaturated f can be obtained with Raney Co or Cu-chromite as catalyst. Ammonia has to be present to suppress the formation of secondary amines. Saturated and unsaturated secondary amines are gained in yields of more than 90% if ammonia is vented from the reactor, the reaction temperature is 160-210 °C, and pressure is maintained at 5-10 MPa/50-100 bar. Trialkylamines are produced via the imine R-CH=NH and Schiff base R-CH=N-CH3 with Ni catalyst at 230 °C and 0.7 MPa/7 bar hydrogen pressure. Important amine types, which are the base for making dimethyl dialkyl ammonium compounds, are made by the following reaction ... 

The classical titration methods for determination of amines may be applied to ethoxylates. Primary amines are reacted with salicylaldehyde, allowing titration of secondary and tertiary amines, as the first break of the curve, then of the primary amines, to the second potentiometric break. In a second titration, primary and secondary amines are reacted with acetic anhydride, allowing selective titration of tertiary amines. 

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