Patent GB-776503-A (GB)
Title: N-tert-alkylaminoalkyl esters
IPC: A01N37/12
Filed: 1955-07-18
Abstract: N-Tertiary-alkylaminoalkyl esters of the formula <FORM:0776503/IV(a)/1> and salts thereof with inorganic or fatty acids, wherein R1, R2 and R3 are alkyl groups having a total of not over 23 carbon atoms, Rx is hydrogen or a methyl group and n is 2 or 3, there being at least two carbon atoms between nitrogen and oxygen atoms, alone or admixed with one or more other monomers, are polymerized in bulk, in aqueous emulsion or suspension, or in aqueous or organic solution in the presence of a polymerization catalyst. The comonomer may be acrylic and methacrylic acid esters, e.g. methyl, allyl, butyl, octyl, dodecyl, cetyl, oleyl, lauryl-myristyl, methoxymethyl, vinyloxyethyl, dimethylaminoethyl, benzyl and tetrahydrofurfuryl acrylates; methyl, allyl, butyl, nonyl, dodecyl, stearyl, cetylstearyl, lauryl-myristyl, ethoxyethyl, vinyloxyethyl, dimethylaminoethyl and cyclohexyl methacrylates; ethylene diacrylate and ethylene dimethacrylate, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, N - alkylacrylamides, N - alkylmethacrylamides; dialkyl esters of itaconic, maleic and fumaric acids, e.g. didecyl fumarate and dimethyl, diethyl, dioctyl and dilauryl itaconates, vinyl and allyl esters, e.g. diallyl phthalate and vinyl acetate, butyrate and laurate; divinylbenzene, styrene, vinyltoluene, para-chlorostyrene, vinylpyridine and vinylpyrrolidine. In aqueous emulsion the emulsifier may be the sodium salt of octylphenoxytriethoxyethyl sulphate or an octylphenoxypolyethoxyethanol.  The specified organic solvent is toluene.  Exemplified alkylaminoalkyl ester monomers are N-tert.-octylaminoethyl acrylate, N-tert.-nonylaminoethylacrylate, N - tert. - butylaminoethyl acrylate, N - tert. - (C12-C15) alkylaminoethyl acrylate, N - tert. - octylaminopropyl acrylate, N - tert. - butylaminoethyl methacrylate, N - tert. - octylaminoethyl methacrylate, N - tert. - dodecylaminoethyl methacrylate, N - tert. - (C18-C24) alkylaminoethyl methacrylate and N - tert. - octylaminopropyl methacrylate.  Specified salt-forming acids are sulphuric, hydrochloric and phosphoric acids.  The polymerization catalyst may be azodiisobutyronitrile; azodiisobutyramide; azobis - (a  : g  - dimethylvalero - nitrile); azobis - (a  - methylbutyronitrile); dimethyl, diethyl and dibutylazodiisobutyrates; dimethyl, diethyl and dibutyl azobis-(methylvalerates); benzoyl, caproyl, methylethylketone and acetyl peroxides; cumene and tert.-butyl hydroperoxides; butyl perbenzoate; hydrogen peroxide; ammonium, sodium and potassium persulphates.  The inorganic peroxidic catalysts are preferably employed in a redox system in conjunction with sodium sulphite, bisulphite, metabisulphite, or hydrosulphite, with or without a metal activator.  The polymer and copolymer products are used as oil additives, anti-corrosion agents, soil agglomerating agents, anti-static agents and textile finishing agents.  The polymers and copolymers may be formed into films or first dissolved in cellulose acetate solution which is then formed into films.  Both types of films may be dyed with acid dyes such as Calcoid Alizarine Blue.ALSO:The invention comprises compounds of the formula: <FORM:0776503/IV(b)/1> and salts thereof with inorganic or fatty acids, wherein R1, R2 and R3 are alkyl groups having a total of not over 23 carbon atoms, Rx is hydrogen or a methyl group and n is 2 or 3, there being at least two carbon atoms between nitrogen and oxygen atoms.  Specified salt-forming acids are hydrochloric, sulphuric and phosphoric acids.  The compounds are prepared by heating an alcohol of the formula: <FORM:0776503/IV(b)/2> with an ester of the formula R0OOC.C(Rx) = CH2, wherein R0 is an alkyl group of not over four carbon atoms, in the presence of a transesterification catalyst and of a polymerization inhibitor, distilling off an alcohol R0OH, and recovering the residue. Exemplified catalysts are sodium, potassium, sodium methoxide, potassium butoxide, aluminium isopropoxide and tetraisopropyl titanate.  Exemplified polymerization inhibitors are di-b -naphthol, hydroquinone and para-hydroxydiphenylamine.  The examples describe the preparation of N-tert. -octylaminoethyl acrylate, N-tert.-nonylaminoethyl acrylate, N-tert.-butylaminoethyl acrylate, N-tert.-(C12-C15) alkylaminoethyl acrylate, N-tert.-octylaminopropyl acrylate, N-tert. -butylaminoethyl methacrylate, N-tert.-octylaminoethyl methacrylate, N-tert.-dodecylaminoethyl methacrylate, N-tert.-(C18-C24) alkylaminoethyl methacrylate and N-tert.-octylaminopropyl methacrylate.  The above esters undergo reaction with alcohols, amines, nitroalkanes, malonates, acetoacetates, cyanogen halides and propiolactone. Tertiary-alkylaminolkanols of the formula: <FORM:0776503/IV(b)/3> are prepared by reacting the appropriate tert. -alkylamine with one mol. of ethylene or propylene oxide.  The preparation of N-tert.-octylaminoethanol, N - tert. - (C12-C15) alkylaminoethanol, N - tert. - (C18-C24) alkylaminoethanol, N - tert. - butylaminoethanol, N - tert. - octadecylaminoethanol, 1 - N - tert. -octylamino - 2 - propanol and 1 - N - tert. -nonylamino-2-propanol.ALSO:An aqueous solution of the hydrochloride of b -tert-butylaminoethyl methacrylate is heated in presence of dimethyl azodiisobutyrate polymerization catalyst until the viscosity of the solution is such that it is just pourable; the product is a cationic polyelectrolyte for use in agglomerating soil.