Patent GB-815103-A (GB)
Title: Aromatic acid amides of aminoalkyl vinyl ethers and their polymers
IPC: C08F16/28
Filed: 1955-12-07
Abstract: Monomeric compounds of formula <FORM:0815103/IV (a)/1> wherein A is a straight- or branch-chained alkylene group having 2 to 18 carbon atoms of which at least two in a chain separate the adjoining nitrogen and ether oxygen atoms, R is hydrogen, phenyl, tolyl, benzyl, cyclohexyl or an alkyl group having 1 to 18 carbon atoms and R1 is phenyl, tolyl or xylyl which may be substituted by halogen atoms or hydroxy or nitro groups (see Group IV (b)), may with the exception of those compounds wherein R1 is hydroxy or nitro substituted, be converted into polymers or copolymers in the presence of suitable catalysts. Specified catalysts are azodiisobutyronitrile, azodiisobutyramide, dimethyl or diethyl or dibutyl azodiisobutyrate, azobis (a  : a -dimethylvaleronitrile), azobis (a -methylbutyronitrile), azobis (a -methylvaleronitrile) and dimethyl azobis-methylvalerate.  The polymerization may be effected in bulk, in solution, or in emulsion systems.  Specified solvents are methanol, ethanol, isopropanol, butanol, dimethylformamide, dimethylacetamide benzene, toluene and xylene.  When the polymerization is effected in an aqueous emulsion, suitable emulsifying agents are the alkylaryl polyethoxyethanols.  The polymerization is best carried out in an inert atmosphere such as nitrogen gas.  Specified monomers which may be copolymerized with the compounds of formula (I) are the vinyl halides, 1 : 1-difluoro- or -dichloro-ethylene, isobutylene, 1 : 3-butadiene, styrene, 2-fluoro- or - chloro - 1 : 3 - butadiene, 2 : 3 - dichloro - 1 : 3-butadiene, methyl or ethyl or butyl or methoxymethyl or chloroethyl or betadiethylaminoethyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl formate or acetate or chloroacetate or butyrate or laurate, acrolein, methacrolein, methyl vinyl ketone, N-vinyl-phthalimide or -succinimide, vinyl ethyl ether, 2-carbamidoethyl, or -aminoethyl or -formamidoethyl vinyl ether, vinylpyridines, N-vinyl caprolactam, tetrafluoroethylene, diethyl fumarate, dimethyl maleate and N - vinyl - N : N1 - ethyleneurea. The monomers may be reacted with up to 100 mols. of an alkylene oxide.  The monomers of formula (I) wherein R is hydrogen and those wherein R1 is hydroxy-substituted are capable of reacting with aldehydes such as formaldehyde and acetaldehyde or acids such as phthalic and maleic acids and thus may be employed as modifying components in aminoplasts, e.g. urea - formaldehyde, melamine - formaldehyde and mixed melamine-urea-formaldehyde condensates, in alkyd resins, e.g. in glycerolphthalates, and in styrene-maleic anhydride copolymers.  The polymers and copolymers of the monomers of formula (I) may also be used as modifying components in aminoplast, alkyd, epoxide and phenol-aldehyde resins.  Polymers having a hydrogen atom on the amido nitrogen may be cross-linked by condensation with difunctional acids and aldehydes.  Hydrophobic polymers may be reacted with an alkylene oxide to impart hydrophilic characteristics.  The water-soluble polymers may be used in paints such as those based on emulsions of polyvinyl acetate or polyacrylates.  The monomers of formula (I) may be copolymerized in small proportions, e.g. up to 10 per cent with monomers lacking an amide group, e.g. methyl methacrylate to render the copolymer reactive and thus suitable as a modifier in aminoplasts, alkyd resins and epoxy resins.  In examples: (1) 2-benzamidoethyl vinyl ether or 2 : 2-dimethyl - 2 - (o - chlorobenzamido) - ethyl vinyl ether is bulk polymerized using dimethylazoisobutyrate as catalyst; (2) 2-benzamidoethyl vinyl ether and methyl methacrylate are copolymerized in dimethylformamide solution using dimethylazoisobutyrate as catalyst; (3) N - methyl - 2 - benzamidoethyl vinyl ether and acrylonitrile are copolymerized as in (2), the resultant solution being spun through a spinnerette into an aqueous solution of dimethylformamide to form fibres; (4) 2 : 2-dimethyl - 2 - (o - chlorobenzamido) ethyl vinyl ether and vinyl chloride are copolymerized in aqueous emulsion in the presence of sodium lauryl sulphate and dimethylazoisobutyrate.ALSO:The invention comprises compounds of formula CH2 = CHOANRCOR1 (I) where A is a straight- or branched-chain alkylene group having 2-18 carbon atoms of which at least two in a chain separate the adjoining nitrogen and ether oxygen atoms; R is hydrogen, phenyl, tolyl, benzyl, cyclohexyl, or an alkyl group having 1-18 carbon atoms; and R1 is phenyl, tolyl, xylyl or such groups in which the benzene ring is substituted with halogen (especially chlorine) atoms, nitro or hydroxyl groups.  The compounds of formula (I) may be prepared by reacting a vinyl aminoalkyl ether of formula CH2 = CHOANHR (II) with an ester or chloride of an aromatic acid of formula R1COOH, wherein A, R and R1 are as defined above.  The monomers of formula (I) other than those in which R1 is hydroxy- or nitro-substituted may be polymerized to give homopolymers and copolymers (see Group IV (a)).  Specified amines of formula (II) are <FORM:0815103/IV (b)/1> and <FORM:0815103/IV (b)/2> (in the above formul  C16H33 = n-hexadecyl and C6H11 = cyclohexyl).  Specified acids of formula (III) are benzoic, p-benzobenzoic, o- or p-chlorobenzoic, 2 : 4-dichlorobenzoic, o- or p-nitrobenzoic, o- or m- or p-hydroxybenzoic, 3 : 4- or 2 : 3- or 2 : 4- or 3 : 5- or 2 : 6-dihydroxybenzoic, vanillic, gallic, o- or m- or p-toluic and 2 : 3- or 3 : 4- or 2 : 6- or 2 : 4- or 2 : 5-xylic acids. Compounds of formula (I) wherein R = hydrogen or and/or R1 is hydroxy-substituted may be reacted further, for example with alkylene oxides such as ethylene, propylene or trimethylene oxide to increase the hydrophilic character of the molecule and these compounds may be used as surface-active agents or softeners.  The hydrophobic monomers may be used as water-proofing agents.  In examples: (1) 2-aminoethyl vinyl ether in a mixture of toluene, water and potassium carbonate is reacted with benzoyl chloride to give 2-benzamidoethyl vinyl ether; (2) the following compounds are reacted together as in (1) to give compounds of formula (I): benzoyl chloride and 5-aminopentyl vinyl ether or N-phenyl- or benzyl- or methyl-2-aminoethyl vinylether o-toluic acid chloride and 2-aminoethyl vinyl ether, 2 : 3-xylic acid chloride and 2-aminoethyl vinyl ether, p-nitrobenzoyl chloride and 2-aminoethyl vinyl ether or N-methyl- or phenyl- or cyclohexyl-2-aminoethyl vinyl ether, o-chlorobenzoyl chloride and 2 : 2-dimethyl-2-aminoethyl vinyl ether or 2 - amino - 1 - hexadecylethyl vinyl ether; (3) the products obtained by reacting salycylic or gallic or 3 : 5-dihydroxybenzoic acid chloride with 2-aminoethyl vinyl ether are reacted further with ethylene oxide in the presence of sodium ethoxide.ALSO:Insecticidal bactericidal and fungicidal compositions comprise as active ingredient compounds of formula CH2=CHOANRCOR1, wherein A is a straight- or branch-chained alkylene group having 2-18 carbon atoms of which at least two in a chain separate the adjoining nitrogen and ether oxygen atoms, R is hydrogen, phenyl, tolyl benzyl, cyclohexyl or an alkyl group having 1 to 18 carbon atoms and R1 is phenyl, tolyl or xylyl which may be substituted by halogen atoms or hydroxy or nitro groups (see Group IV (b)).  An example specified that 2 : 2 - dimethyl - 2 - (o - chlorobenzamido) ethyl vinyl ether may be dissolved indeodorised kerosene or Stoddard solvent and used as a fly or moth spray.