Patent GB-475131-A (GB)
Title: Esters of acids of the acrylic series and their applications
IPC: C07C69/54
Filed: 1936-05-15
Abstract: Esters are manufactured by reacting an a -substituted acrylic acid, its anhydride, halide or ester with an aminoalcohol or an alkaline-earth or alkali metal aminoalcoholate.  Preferably, an ester, e.g. a lower alkyl ester, of the acid is reacted with the aminoalcohol in the presence of an inert solvent, e.g. benzene, toluene or dioxane, preferably in the presence of a polymerization inhibitor, e.g. hydroquinone, p-phenylenediamine, pyrogallol, tannic acid, sulphur, selenium, cuprous chloride or benzidine, and an ester interchange catalyst, e.g. an alkali metal alcoholate such as sodium methylate or ethylate, sodium oxide or hydroxide, calcium oxide or litharge, or the halide of the acid is reacted with an alkali metal aminoalcoholate in the presence of a solvent. The aminoalcohols employed are amines containing at least one primary, secondary or tertiary alcoholic hydroxyl group, in which the nitrogen of the amino group, which may be primary, secondary or tertiary, may carry alkyl, aryl, aralkyl or cycloaliphatic groups, or may form part of a ring, the remainder of which may consist of carbon atoms with or without other atoms; e.g. b -diphenylaminoethanol, b -propylaminoethanol, b -diisopropylaminoethanol, b -di-n-propylaminoethanol, g -diethylaminopropanol, d -diethylaminobutanol, b -diisobutylaminoethanol, 2-phenylaminocyclohexanol, b -ethylaminoethanol, g -methylaminopropanol, b -cyclohexylaminoethanol, 2-aminocyclohexanol, the mono-, di- and triethanolamines, butanolamines, propanolamines and isobutanolamines, glucamine, methylglucamine, dimethylglucamine, laurylglucamine, 1 : 3-diaminopropanol, dimethylaminomethanol, b -thiomorpholine - N - ethanol, b  - hydroxy - b <1>-dialkylaminodiethyl ethers and analogous compounds from tri- and tetraethylene glycol, triethanolamine diesters, tert. butanolamine (made by reducing acetone cyanhydrin), aminotetra- and decahydronaphthols and the corresponding mono- and dialkyl derivatives, the glycol monoesters of aminoacids, the aminoalcohol esters of hydroxy acids, and the aminoalcohols produced by reacting camphene oxide, dipentene oxide, pinene oxide or bornylene oxide with ammonia or amines, e.g. borneolamine.  Suitable acids are methacrylic, a -phenylacrylic, a -butylacrylic, a -isopropylacrylic and a -ethylacrylic acids.  In examples: (1) b -dimethylaminoethanol and methyl methacrylate are heated in benzene in the presence of p-phenylenediamine and sodium methylate; (2) b -diethylaminoethanol is similarly reacted; the p-phenylenediamine may be replaced by benzidine; (3) b -dicyclohexylaminoethanol is reacted as in (1); (4) b -di-n-butylaminoethanol is similarly reacted; (5) b -morpholine-N-ethanol is similarly treated; (6) triethanolamine is reacted with sodium in dioxane, to form the monosodium alcoholate, which is stirred with methacrylyl chloride, with addition of hydroquinone, producing triethanolamine monomethacrylate; by employing sufficient sodium to form the di- or trisodium alcoholate, there may be obtained triethanolamine di- and trimethacrylates respectively; (7) 2-(diethylamino)-cyclohexanol is reacted with sodium in dioxane and the mixture is refluxed with methacrylyl chloride; (8) b -piperidinoethanol is reacted with methyl methacrylate as in (1).  Specification 426,062 is referred to.  The Specification as open to inspection under Sect. 91 comprises also the manufacture of the methacrylic esters by reacting acetone p cyanhydrin with the aminoalcohol in the presence of a dehydrating agent, e.g. sulphuric, phosphoric or chlorsulphonic acid.  The following additional starting materials are specified: b  - dilaurylaminoethanol, d  - dibutylaminobutanol, d -diisobutylaminobutanol, 2-(o-tolylamino) - cyclohexanol, d  - butylaminobutanol, d -isobutylaminobutanol, b -(methylcyclohexyl)-aminoethanol, the alkylcyclohexylaminoalcohols, e.g. b -ethylcyclohexylaminoethanol, "b -decahydroquinyl-N-ethanol," the vinylalkylaminoethanols, p-hydroxyphenylmorpholine, the aminophenols, e.g. o-, m- and p-aminophenol, the diethers of triethanolamine, e.g. the dimethyl ether, b -piperazine-N-ethanol, "b -(monoalkylpiperamine)-N-ethanols," N-alkyl-2-hydroxymorpholine, aminooctadecanol, the aminonaphthols, and "the primary, secondary or tertiary-3-aminoalcohols, such as 2-dimethyl propanol-1, made by reducing b -aminoaldehydes or ketones"; a -amylacrylic, a -hexylacrylic, a -(methylphenyl)-acrylic, a -hexahydrotolylacrylic and a -cyclohexylacrylic acids.  This subject-matter does not appear in the Specification as accepted.  b -Dicyclohexylaminoethanol is prepared by reacting dicyclohexylamine with ethylene chlorhydrin.  b -Di-n-butylaminoethanol is similarly prepared from dibutylamine.  b - Morpholine - N - ethanol is obtained by pyrolysis of triethanolamine hydrochloride.  2-(Diethylamino)-cyclohexanol is obtained by reacting cyclohexene oxide with diethylamine. Polymerization products are manufactured by the polymerization of the aminoalcohol esters of a -substituted acrylic acids. Polymerization of the esters takes place on standing, or may be effected by emulsifying the ester in a non-solvent medium with the aid of a dispersing agent, e.g. the potassium or sodium salt of an alkylnaphthalenesulphonic acid, the potassium or sodium salt of an acid sulphate of an alcohol obtained by hydrogenation of fatty oils, sodium or potassium oleate or resinate, and subjecting the emulsion to polymerizing conditions, with or without the aid of a polymerization catalyst.  Interpolymers may be made by mixing the esters with other polymerizable compounds, e.g. vinyl esters or ethers, styrene, butadienes, e.g. 2-chloro-1 : 3-butadiene, indene, acrylic or methacrylic acid esters, drying, semi-drying or non-drying oils or natural or synthetic resins, and subjecting the mixture to polymerizing conditions.  The aminoethyl methacrylate polymers may be used, especially in thin films, for improving the anchorage of moisture proofing and other lacquers to paper, cotton, rayon, thin transparent sheets of regenerated cellulose, glycol cellulose or low substituted methyl or ethyl cellulose. The free base polymers are suitable as adhesives, e.g. for joining wood to wood, as stabilizers for motor spirit, for chlorine-containing resins, e.g. vinyl chloride or chloracetate, or for chlorinated rubber, as fixatives for pigments, oils or waxes to paper, leather and cloth, as fixatives for acid dyes, and as ingredients of coating compositions, e.g. in conjunction with nitrocellulose, ethyl cellulose, fatty oils and polyhydric alcoholpolycarboxylic acid resins.  The free base interpolymers are suitable as adhesives, as dispersing agents for pigments, oils and waxes, the dispersions being useful for fixing these substances to fabrics, leather and paper), and as ingredients of water paints, alone or in combination with pigments, oils or waxes.  The polymers may be reacted with alkyl, aryl, aralkyl or alicyclic halides to produce quaternary salts, which are useful as dispersing agents for 2-chloro-1 : 3-butadiene, as emulsifying agents for pigments, oils and waxes, as adhesives, and as fixatives for pigments, oils and waxes to fabrics, leather and paper.  In examples: (1) to (8) the products of these examples (see above) are stated to polymerize spontaneously on standing; (9) a mixture of b -diethylaminoethyl methacrylate and methyl methacrylate is polymerized, in emulsion in water containing sodium lauryl sulphate, by heating with benzoyl peroxide; (10) the same substances are polymerized in solution in dioxane; (11) a mixture of b -dicyclohexylaminoethyl methacrylate and b -dimethylaminoethyl methacrylate is polymerized in hydrochloric acid solution by heating with benzoyl peroxide.  The Specification as open to inspection under Sect. 91 comprises also the manufacture of interpolymers of the aminoalcohol esters by ester interchange between an aminoalcohol and a polymeric ester, e.g. polymeric methyl methacrylate or acrylate. In an example, methyl methacrylate is polymerized by heating with benzoyl peroxide in benzene solution, and ester interchange is effected with diethylaminoethanol.  This subject-matter does not appear in the Specification as accepted.