Patent GB-984453-A (GB)
Title: Esters and polymers obtained therefrom
IPC: C08G75/025
Filed: 1961-06-23
Abstract: The invention comprises acetylenic esters of formula (ZC ­ C.COO)mR(OH)n where n is 0, 1, 2 or 3, m is 1, 2, 3 or 4, the sum of n plus m is 2, 3 or 4, R is the residue of a polyhydric alcohol, a polyhydric phenol or a phenolic alcohol and having the formula R(OH)(m + n) which residue contains only carbon and hydrogen or carbon, hydrogen and halogen atoms, the total number of carbon atoms therein being from 2 to 18, and Z is a hydrogen atom, an alkyl group of 1 to 5 carbon atoms or an aryl group having from 6 to 10 carbon atoms.  The esters are prepared by reacting a polyhydric alcohol, polyhydric phenol or phenolic alcohol of formula R(OH)(m + n) with an acetylenic acid of formula ZC ­ C.COOH or with a halide or anhydride of such acid at a temperature below 120 DEG  C.  Esters where m and n are both one may be prepared by reacting an acetylenic acid with an alkylene oxide of formula <FORM:0984453/C2/1> where R1 and R11 are hydrogen atoms or alkyl groups of 1 to 5 carbon atoms. In examples dipropiolate of ethylene glycol is prepared from propiolic acid and ethylene glycol, 2-hydroxyethyl propiolate is prepared from propiolic acid and ethylene oxide, dipropiolate of 2,2-dimethyl - 1,3 - propane diol is prepared from propiolic acid and the diol, tripropiolate of 2-(hydroxymethyl) - 2 - methyl - 1,3 - propane diol is prepared from propiolic acid and the diol, dipropiolate of 4,41-isopropylidenedicyclohexanol is prepared from propiolyl chloride and the hydroxy compound, dipropiolate of 2-ethyl - 2 - butyl - 1,3 - propanediol is prepared from propiolic acid and the diol, dipropiolate of 2,2-bis(chloromethyl)-1,3-propanediol is prepared from propiolic acid and the diol, dipropiolate of 4,41-diphenol is prepared from propiolyl chloride and 4,41-diphenol, dipropiolate of 4,41-isopropylidenebisphenol is prepared from propiolyl chloride and the bisphenol, dipropiolate of paraxylene-a ,a 1-diol is prepared from propiolic acid and the diol, dipropiolate of tetramethyl-para-xylene-a ,a 1-diol is prepared from propiolic acid and the diol, mono-propiolate of 4-(21-hydroxyethyl) phenol, is prepared from propiolic acid and the phenol, bis(phenylpropiolate) of 2,2-dimethyl-1,3-propane diol is prepared from phenylpropiolic acid and the diol, mono-propiolate of 4-(21-hydroxyethoxy) phenol is prepared from propiolic acid and the phenol, dipropiolate of hydroquinone is prepared from propiolyl chloride and hydroquinone, dipropiolate of resorcinol is prepared from propiolyl chloride and resorcinol, dipropiolate of 2-butene-1,4-diol is prepared from propiolic acid and the diol, and tetrapropiolate of pentaerythritol is prepared from propiolic acid and pentaerythritol; diluents used in the examples are benzene and ether, and catalysts are sulphuric acid, tetraethylammonium bromide, phosphoric acid, sodium hydroxide and para-toluene sulphonic acid. Lists of esters and starting materials are given.ALSO:Polymers are obtained by reacting an acetylenic diester of formula <FORM:0984453/C3/1> where Z is a hydrogen atom, an alkyl group of 1 to 5 carbon atoms or an aryl group of 6 to 10 carbon atoms, and R is the residue of a dihydric compound containing 2 to 18 carbon atoms, with (a) a glycol, thioglycol or bis-thiol of formula <FORM:0984453/C3/2> where X is oxygen or sulphur and Y is divalent hydrocarbon or halohydrocarbon group of 2 to 18 carbon atoms or a chain containing 2 to 101 alkylene groups and 1 to 100 oxygen atoms, the alkylene groups containing 2 to 6 carbon atoms, or (b) a urea or thiourea of formula <FORM:0984453/C3/3> where X is oxygen or sulphur and R is an alkyl group of 1 to 5 carbon atoms; or (c) a cyclic bis-secondary amine of formula <FORM:0984453/C3/4> where D and D1 are alkylene or monoxyalkylene groups of 1 to 3 carbon atoms in the chain and a total of 1 to 7 carbon atoms or D1 is a carbonyl group, D and D1 together with the nitrogen atoms forming a 5- or 6-membered ring; or (d) an N, N1-dialkylated disulphonamide of formula <FORM:0984453/C3/5> where Y is an alkyl group of 1 to 5 carbon atoms and X is a divalent hydrocarbon group which may be interrupted by 1 or 2 oxygen atoms, is free from aliphatic unsaturation, contains 6 to 18 carbon atoms and is linked through carbon atoms of an aromatic nucleus to the sulphonamide sulphur atoms. The polymers are unsaturated and may be cross-linked by reaction with vinyl compounds. In examples, polymers are obtained by reacting the dipropiolate of 2,2-dimethyl-1,3-propane diol with ethylene glycol, 4,41-isopropylidene bis-(dichlorophenol), a polypropylene glycol, 4,41-isopropylidene bisphenol,2-imidazolidinone, 1,3-dimethylurea, 1,3 - dibutyl - 2 - thiourea, 4,41 - oxybis - (N - methylbenzenesulphonamide) N,N1 - dimethyl - 2,4 - toluenedisulphonamide, 2,2 - dimethyl - 1,3 - propanediol and para - xylene - a ,a 1 - diol; the polymer prepared from polypropylene glycol is further reacted with styrene, acrylonitrile and methyl methacrylate; the catalysts used are triethylene - diamine, N - methylmorpholine, azobisisobutyronitrile and piperazine hexahydrate; dioxane is used as a diluent.  Lists of starting materials are given.ALSO:Bactericidal and fungicidal compositions comprise acetylenic esters of formula (ZC­C.COO)mR(OH)n where n is 0, 1, 2 or 3, m is 1, 2, 3 or 4, the sum of n plus m is 2, 3 or 4, R is the residue of a polyhydric alcohol, a polyhydric phenol or a phenolic alcohol having the formula R(OH)m+n which residue contains only carbon and hydrogen or carbon, hydrogen and halogen atoms, the total number of carbon atoms, therein being from 2 to 18, and Z is a hydrogen atom, an alkyl group of 1 to 5 carbon atoms or an aryl group having from 6 to 10 carbon atoms.  The compositions may be emulsions containing from 0,0001 to 1,0% by weight of the ester, and the emulsifying agent may be alkali metal salts of alkylbenzene sulphonates, polyalkylene glycols or salts of alkylsulphosuccinates. The esters also may be incorporated with solid carriers, e.g. clay, talc, pumice or bentonite, or dissolved in liquefied normally gaseous media, e.g. fluorochloroethanes or methyl chloride for application as aerosols.