Quatemized Amines

Advincula et al. used the same initiator type (DPE activated with u-BuIi) to perform LASIP from colloidal sihca [265] or clay [266, 267]. The spacer between the DPE unit and the surface active group (quatemized amine for clay and chlorodi-methylsilane for silica) was a long n-alkyl chain. In all cases, a relatively broad polydispersity for the prepared polystyrene bmsh (PDI = 1.2-2) was observed. 

Hossain, M. A. Kang, S. O. Powell, D. Bowman-James, K. A new class of amide/quatemized amine macrocycles and die chelate effect, Inorg. Chem. 2003, 42, 1397-1399. 

The Type I resin is a quatemized amine resin resulting from the reaction of trimethylamine with the chloromethylated copolymer. This functionalized resin has the most strongly basic functional group available and has the greatest affinity for weak acids. However, the efficiency of regenerating the resin to the hydroxide form is somewhat lower than Type II resins, particularly when the resin is exhausted with monovalent anions. 

The choice of the Hofmann elimination is somewhat more involved. This classic reaction, discovered by Hofmann (1851), shows that quatemized amines on treatment with base (or simply heated in solution if the anion is OH) will eliminate the smallest alkyl group (larger than methyl) that is sterically least hindered, as an olefin, leaving a tertiary amine (Eq. 8.10). 

Cationic polymers include homopolymers and cationic copolymers obtained by the polymerization of a vinylic monomer with a quaternary ammonium group or a quatemized amine with another soluble monomer in water such as acrylamide and methacrylamide. The most frequently used polymers are those derived from gum guar such as guar hydroxyl propyl triamonium chloride. They are sold under the trade names Jaguar C13S, C17, etc. [12-16]. 

Cationic PUs possessing phosphonate or quatemized amine groups were synthesized by Flemming et al. Better activity was shown by the qnatemized amine PUs which significantly reduced the number of adherent bacteria compared to control PUs. A reduction in bacterial adhesion was also found on the surface of the zwitterionic phosphonated PU but to a lesser extent... 

Other compounds containing nitrogen and used as antistatic agents are quaternary ammonium salts, quatemized amines, quatemized heterocycles ob-... 

Postpolymerization reactions, such as grafting, cross-linking, acid and base hydrolysis, quatemization, amination, and pegylation, represent attractive alternatives to using... 

In efforts to conduct SIP from clay surfaces, Xiaowu and co-workers recently synthesized two initiators for free radical SIP, both contain quatemized amine endgroups for cation exchange with montmorillonite particles. The initiator molecule design is as follow ... 

Fig. 2. Functional groups on modified polyacrylamides (a) formed by reaction with dimethylamine and formaldehyde (Mannich reaction) (b), quatemized Mannich amine (c), carboxylate formed by acid or base-cataly2ed hydrolysis or copolymerization with sodium acrylate and (d), hydroxamate formed by...

Primary and secondary amines are usually converted to tertiary amines using formaldehyde and hydrogen in the presence of a catalyst (eqs. 5 and 6). This process, known as reductive alkylation (222), is attractive commercially. The desired amines are produced in high yields and without significant by-product formation. Quatemization by reaction of an appropriate alkylating reagent then follows. 

In addition to the stmctuies in Tables 30—33, commeicial quatemaiy surfactants include a variety of modifications, prepared, eg, by quatemization of simple tertiary amines ... 

Tertiary Amine-Containing Copolymers. Copolymers based on DMAEMA (dimethylarninoethyl methacrylate) in either free amine form or quatemized with diethyl sulfate or methyl chloride have achieved commercial significance as fixatives in hair-styling formulations, especially in the weU-pubhcized "mousses" or as hair-conditioning shampoo additives. This success has occurred because the cationic charge affords substantive resins that strongly adhere to the hair (141). 

CaveU and Chapman made the interesting observation that a difference exists between the orbital involved in the quatemization of aromatic nitrogen heterocycles and aromatic amines, which appears not to have been considered by later workers. The lone pair which exists in an sp orbital of the aniline nitrogen must conjugate, as shown by so many properties, with the aromatic ring and on protonation or quatemization sp hybridization occurs with a presumed loss of mesomerism, whereas in pyridine the nitrogen atom remains sp hybridized in the base whether it is protonated or quaternized. Similarly, in a saturated compound, the nitrogen atom is sp hybridized in the base and salt forms. 

Chloropyrimidine is aminated with alcoholic ammonia at 130° while 4-chloro-2-methyl- and 4-chloro-6-methyl-pyrimidine yield the corresponding 4-amino derivatives at 100°. 4-Aminopyrimi-dine is not prepared from the chloro analog because of facile self-quatemization (see Section III, B, 2 for comments on factors involved) of the latter. 

A methyl quatemized erucyl amine [660] is useful for aqueous viscoelastic surfactant-based fracturing fluids in high-temperature and high-permeability formations. 

Glycidyl ether additives are obtained by esterification of alkoxylated primary fatty amines and additives of polyether-block polymers and glycidyl ethers with dicarboxylic acids [1025], They are used as demulsifiers to break up oil emulsions and, as quatemized products, they are suitable as corrosion inhibitors. 

Summary New lyophilic cationic silicone surfactants have been synthesized by direct quatemization of halogenated siloxanyl precursors or by transformation of these precursors into tertiary amines with a subsequent quatemization step. After transformation of the precursors into secondary amines, reaction with maleic anhydride and neutralization, new anionic products were obtained. 

Quatemization of Tertiary Amines and Nitrogen-Containing Heterocycles with N,N-Bis(siloxy)Enamines Ammonium salts [HON=CR,CHR"NEt3]+ X- were found for the first time as by-products in studies of double silylation of AN (465, 466). To optimize the reaction, efforts were made to reduce the... 

Pentamethylpiperidine (21) is an exceptionally strong base that does not undergo quatemization hence it is employed as acid acceptor during the quatemization of amines by alkyl halides. 

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