Patent GB-617273-A (GB)
Title: Vulcanization of rubber compositions
IPC: C08K5/23
Filed: 1946-06-17
Abstract: Synthetic rubbers are vulcanized by mixing them with a polyazo ester having the structural formula <FORM:0617273/IV(a)/1> in which R1 is a monovalent radical of the group consisting of hydrocarbon, oxahydrocarbon, thiahydrocarbon and the corresponding halogen and nitrosubstituted radicals, R is a multivalent radical of the group consisting of hydrocarbon, oxahydrocarbon and thiahydrocarbon, and the corresponding halogen-substituted and nitro radicals, and x is a whole number from 2 to 5 inclusive, and then subjecting them to slight heat, or allowing them to stand at air temperature.  R1 may be methyl, ethyl, hexyl, cetyl, melissyl, phenyl, naphthyl, benzyl, phenylethyl, naphthyl methyl, cyclohexyl, cyclopentyl, 2-methoxyethyl, 2-ethoxyethyl, 2-isopropoxy-n-propyl, methoxyphenyl, ethoxynaphthyl, and thiahydrocarbon radical such as (C2H5-S-C2H4-), 2-chloroethyl, 3 - bromopropyl, fluoromethyl, parachlorophenyl, meta-ethylphenyl, tolyl, xylyl, 2-nitro-phenoxymethyl and 2,4-dinitro-benzyl radicals.  Radical R may be ethylene, hexamethylene, decamethylene, 1,2 - propylene, (-C2H4-O-C2H4-), (-C2H4-O-C2H4-O-C2H4-), para phenylene, a -naphthylene, tolylene, toluylene, xylylene, diphenylene methane, 2,2-bis-(diphenylene) propane, glyceryl and pentaerythryl.  Specified esters are decamethylene - bis - (ethyl azodicarboxylate), diethylene - bis - (phenyl azodicarboxylate), glyceryl - tris - (benzyl azodicarboxylate), paraphenylene - bis - (cyclohexyl azodicarboxylate), thiodiethylene-bis-(gamma-chloro-propyl azodicarboxylate), para - xylylene - bis - (methoxyethyl azodicarboxylate), 2,2-(p,p1-dihydroxyphenyl) propane-bis-(p-nitro phenyl azodicarboxylate), hexamethylene glycol-bis-(ethyl azodicarboxylate), diethylene glycol-bis-(ethyl azodicarboxylate), decamethylene glycol-bis-(ethyl azodicarboxylate).  The synthetic rubbers include polymers of butadiene-1 : 3, isoprene, chloroprene, triolefine hydrocarbons and copolymers of these substances with styrene, acrylonitrile, vinyl acetate, alkyl acrylates, a -alkyl- and a  - halogen - acrylates, vinylidene chloride, isobutylene, alkyl fumarate and alkyl maleate.  The esters may be added to latices and solutions, the resulting mix being particularly suitable for coating cloth, paper and metal and as an adhesive for rubber.ALSO:Polyazo ester used for vulcanizing having the structural formula <FORM:0617273/IV(b)/1> in which R1 is a monovalent radical of the group consisting of hydrocarbon, oxyhydrocarbon, thiohydrocarbon and the corresponding halogen and nitro-substituted radicals, R is a multivalent radical of the group consisting of hydrocarbon, oxahydrocarbon, and thiahydrocarbon and the corresponding halogen-substituted and nitro radicals, and x is a whole number from 2 to 5 inclusive are prepared by reacting any hydroxy compound containing the desired multivalent radical with phosgene until at least a plurality of the hydroxyl radicals are substituted with chlorocarbonate radicals.  The resulting polychlorocarbonate is then condensed with an ester of hydrazine monocarboxylic acid in a solvent such as dioxane in the presence of a basic reagent such as triethylamine, pyridine, or the oxide, carbonate, or hydroxide of an alkali or alkali earth metal.  The polyhydrazo ester thus formed may be recrystallized from ethyl acetate and then oxidized preferably by concentrated nitric acid to the corresponding polyazo ester. Specified esters are decamethylene-bis-(ethylazodicarboxylate), diethylene - bis - (phenylazodicarboxylate), glyceryltris-(benzylazodicarboxylate), para-phenylenebis - (cyclohexylazodicarboxylate), thiodiethylene-bis-(gamma-chloropropylazodicarboxylate), para-xylylene-bis-(methoxyethylazodicarboxylate, 2,2-(p,p1-dihydroxyphenyl)-propane-bis-(p - nitrophenylazodicarboxylate), hexamethyleneglycol - bis - (ethylazodicarboxylate), diethyleneglycol - bis - (ethylazodicarboxylate), decamethyleneglycol - bis - (ethylazodicarboxylate).  It is stated that R1 may be cetyl, melissyl, phenylethyl, cyclopentyl, methoxyphenyl, C2H5-S-C2H4-, 3 - bromopropyl, fluoromethyl, tolyl or 2 : 4-dinitrobenzyl and R may be hexamethylene, propylene, naphthylene, diphenylene or C2H5-O-C2H4-.ALSO:Natural and synthetic rubbers are vulcanized by mixing them with a polyazo ester having the structural formula <FORM:0617273/V/1> in which R1 is a monovalent radical of the group consisting of hydrocarbon, oxahydrocarbon, thiohydrocarbon and the corresponding halogen and nitro substituted radicals, R is a multivalent radical of the group consisting of hydrocarbon, oxahydrocarbon and thiahydrocarbon and the corresponding halogen-substituted and nitro radicals and X is a whole number from 2 to 5 inclusive, and then subjecting them to slight heat, or allowing them to stand at air temperature.  R1 may be methyl, ethyl, hexyl, cetyl, melissyl, phenyl, naphthyl, benzyl, phenylethyl, naphthyl methyl, cychohexyl, cyclopentyl, 2-methoxyethyl, 2-ethoxyethyl, 2-isopropoxy-n-propyl, methoxyphenyl, ethoxynaphthyl, and thiohydrocarbon radical such as (C2 H5-S-C2 H4-), 2-chloro ethyl, 3-bromopropyl, fluoromethyl, para-chlorophenyl, meta-ethylphenyl, tolyl, xylyl, 2-nitro-phenoxymethyl and 2, 4 dinitro-benzyl radicals. Radical R may be ethylene, hexanethylene, decamethylene, 1, 2, propylene, (-C2H4-O-C2H4-), (C2H4-O-C2H4-O-C2H4-para -phenylene, a -naphthylene radical, tolylene, toluylene, xylylene, diphenylene methane, 2.2 bis (diphenylene) propane, glyceryl, and pentaerythryl. Specified esters are decamethylene-bis (ethyl azodicarboxylate), diethylene-bis (phenyl azodicarboxylate), glyceryl-tris (benzyl azodicarboxylate), paraphenylene-bis (cychlohexylazo dicarboxylate), thiodiethylene-bis (gamm-chloro-propylazo dicarboxylate), para-xylylene-bis (-methoxy-ethyl-azo dicarboxylate), 2, 2-(p,p1 dihydroxyphenyl) propane bis (p-nitro phenyl azo dicarboxylate), hexamethylene glycol bis (ethyl azo dicarboxylate), diethylene glycol bis (ethyl azo discarboxylate), decamethylene glycol bis (ethyl azo dicarboxylate).  The synthetic rubbers include polymers of butadiene 1:3, isoprene, chloroprene, triolefine hydrocarbons and copolymers of these substances with styrene, acrylonitrile, vinyl acetate, alkyl acrylates, a -alkyl- and halogen-acrylates, vinylidene chloride, isobutylene, alkyl fumarate and alkyl maleate.  The esters may be added to rubber latices and solutions the resulting mix being particularly suitable for coating cloth, paper, and metal and as an adhesive for rubber.