Patent GB-885839-A (GB)
Title: Monoepoxidation of diunsaturated esters of acrylic and methacrylic acids
IPC: D06M15/273
Filed: 1958-03-31
Abstract: Polymerization or copolymerization of epoxy esters of the formula <FORM:0885839/IV (a)/1> where R1 is hydrogen or a methyl radical, and R2 is an alkylene group containing up to nine carbon atoms with not less than two carbon atoms between the oxygen atom and the epoxy group, alone or with one or more other compounds containing a CH2 = C< group, can be effected in bulk, solution or in emulsion, at a temperature from about 0 DEG  to 100 DEG  C., preferably 40 DEG  to 80 DEG  C., in the presence of free-radical catalysts such as a , a 1-bis-azoisobutyronitrile, benzoyl peroxide, and stearoyl peroxide, in amounts from 0,01 to 5% based on the polymerizable compound. Examples of copolymerizable materials are alkyl esters of methacrylic and acrylic acids, the alkyl group of which is straight or branched and contains from 1 to 8 carbon atoms, such as methyl, ethyl, isopropyl, n-butyl, n-octyl and 2-ethylhexyl. Preferred epoxy esters are 10,11-epoxyundecyl acrylate and methacrylate.  Copolymers of these esters with the above alkyl esters are useful in coating compositions, paper treating, and shrink-proofing and felt-proofing textiles.  Aqueous dispersions of a copolymer of a mixture containing 5 to 40% of 10, 11-epoxyundecyl acrylate or methacrylate, and at least one alkyl ester of acrylic or methacrylic acid whose alkyl group contains not more than 8 carbon atoms, may be used to reduce the tendency of wool towards shrinkage.  In an example butyl acrylate, 10, 11-epoxyundecyl methacrylate, water and an aqueous solution of tert-octylphenoxypolyethoxyethanol are mixed and cooled to 15 DEG C., then ammonium persulphate and sodium hydrosulphite are added and the mixture is agitated for 20 minutes.  The dispersion is used for shrink-proofing wool.ALSO:The invention comprises 10,11-epoxyundecyl acrylate and methacrylate and the preparation of epoxy esters by selectively epoxidizing the o -located ethylenic bond in the alkenyl moiety of an ester of the formula <FORM:0885839/IV (b)/1> wherein R1 is hydrogen or a methyl group and R2 is an alkylene radical containing up to nine carbon atoms, and not less than two carbon atoms separating the adjacent oxygen atom and the unsaturated carbon atom, which method comprises bringing together said ester and at least one mole of an epoxidizing peracid per mole of ester and reacting said ester and peracid until monoepoxidation is substantially complete, the reaction being carried out at a temperature in the range from about 30 DEG C. to about 60 DEG C. preferably 40 DEG C. to 50 DEG C., and in the presence of a basic agent, namely a compound which when mixed with water imparts an alkaline pH thereto.  Preferably the peracid is used in an amount not exceeding 1.5 moles per mole of ester, and is added gradually, in a continuous or portionwise fashion, during the reaction.  Peracids specified are perbenzoic, monoperphthalic and peracetic acids in chloroform, ether and acetic acid, respectively.  Suitable basic agents are hydroxides, acetates, carbonates and bicarbonates of sodium and potassium.  The reaction may be effected in the presence of a polymerization inhibitor, such as p-hydroxydiphenylamine, N, N - diphenylphenylene - diamine, 2, 5 - di - tert -butylhydroquinone, di-b -naphthol, 2,21-bis -(p-hydroxyphenyl) propane and N,N1-di-2-(1,4 -naphthoquinonyl)-p-phenylenediamine.  The starting materials are made by acid-catalyzed esterification of unsaturated alcohols with glacial acrylic or methacrylic acid in an inert solvent with a polymerization inhibitor, or by basecatalyzed transesterification of the a ,o -unsaturated alcohols with an ester of acrylic or methacrylic acid in the presence of a polymerization inhibitor.  The olefinic alcohols may also be reacted with the appropriate acid chloride or anhydride.  Suitable starting materials are specified.  Examples describe the preparation of 4-pentenyl methacrylate and acrylate, 4,5-epoxypentyl methacrylate and acrylate, 3,4-epoxybutyl methacrylate and acrylate, 5,6-epoxyhexyl methacrylate and acrylate, 10,11-epoxyundecyl methacrylate and acrylate.  An example also describes the preparation of 5-hexen-1-ol by treatment of the Grignard reagent from 4-pentenyl bromide with gaseous formaldehyde.ALSO:A method for reducing the tendency of wool to shrink comprises impregnating the wool with an aqueous dispersion of a copolymer of 10,11-epoxyundecyl methacrylate or acrylate and at least one alkyl ester of acrylic or methacrylic acid in which the alkyl group contains up to eight carbon atoms, and then drying and heating the wool.  In an example, pieces of flannel are impregnated with an aqueous dispersion of a copolymer of butyl acrylate and 10,11-epoxyundecyl methacrylate, applied at 3.5% solids, followed by heating for ten minutes at 300 DEG F. in the presence of an acidic catalyst.  The treated flannel shows zero shrinkage in a standard laundering test which produces 39% shrinkage on the untreated flannel.  The butyl acrylate may be substituted by ethyl acrylate, octyl acrylate, butyl methacrylate, or propyl acrylate.