Patent GB-1029732-A (GB)
Title: Improved release of agents from adsorbate-containing molecular sieves
Filed: 1962-09-27
Abstract: A curable composition comprises an organic synthetic resinous material capable of being cured and a zeolitic molecular sieve having coadsorbed thereon a curing agent and a polar release agent for said curing agent which does not itself act as a curing agent, but releases the curing agent on heating.  The following compositions are specified:-  Neoprene rubber compositions (sulphur-modified and non-sulphur-modified) using as curing agent (accelerator) dihydroxybenzenes, alkyl substituted dihydroxybenzenes and hydroxy-substituted benzoic acids: Example 1 refers to the use of mercaptoimidazoline with water as release agent with a non-sulphur-modified neoprene to cure the neoprene at 250-300 DEG  F. Butyl rubber compositions (isobutylene or other C4- 7 isoolefin and a C4- 14 polyolefin) using as accelerator HCl, HBr, HI, halogen-substituted organic acids, unsaturated organic halides, acyl halides and chlorinated alkyl benzenes.  Buna rubber compositions (butadiene/styrene) using thiurams, arylamines, alkylarylamines, thioureas, piperidine and alkylamines.  Epoxy resin compositions-monomeric type: vinyl cyclohexane dioxide, epoxidized soybean oil, butadiene dioxide, 1:4-bis-(epoxypropoxy) benzene, 1:3-bis-(2:3-epoxypropoxy) cyclohexane, 4:4-bis-(2-hydroxy-3:4-epoxybutoxy) diphenyldimethyl methane, 1:3-bis-(4:5-epoxy-pentoxy) - 5 - chlorobenzene, 1:4 - bis - (3:4-epoxybutoxy) - 2 - chlorocyclohexane, 1:3, bis - (2 - hydroxy - 3:4 - epoxybutoxy) benzene-1:4-bis (2-hydroxy-4,5-epoxypentoxy benzene) 1,2,5,6 - diepoxy - 3 - hexene, 1,2,5,6 - diepoxyhexane, 1,2,3,4 - tetra - (2 - hydroxy - 3:4-epoxybutoxy)-butane, glycidyl polyethers of polyhydric phenols and polyglycidyl esters Curing (hardening) agents are compounds containing reactive hydrogen, e.g. alkylamines, substituted and binuclear aromatic amines, polyhtdric phenols, novolak resins and acid anhydrides, examples of these compounds being given.  Epoxy resins-polymeric type-glycidyl polyethers of polyhydric phenols, using the above hardening agents. Examples of epoxy resins (2) diglycidyl ether of bis-phenol A hardened with diethylene triamine-loaded Zeolite A using water as release agent, at 400 DEG  F. or (3) with ethylene diamine using methanol, at 160 DEG  F. or (5) with ethylene diamine using water at 100 DEG  C., loaded on chabazite or (7) with diethylene triamine using acetone or methylisobutyl ketone on sodium zeolite X at 300 DEG F.  Polyurethane compositions of di- or poly-isocyanates or -isothiocyanates and active hydrogen-containing compounds, e.g. polyols, polyesters, polyester amides, polyamides, N-methyl diethanolamine, ethylene glycol and diethylenetriamine, water and polyalkylene ether glycols using as catalysts tertiary amines, organic tin compounds: Example 6 refers to catalysing polyurethane formation by curing a blend of 1:2:6-hexanetriol, itself also adsorbed on a molecular sieve, with tolylene diisocyanate at 300-325 DEG  F. using HCl as release agent.  An Example (4) also refers to curing ethyl acrylate polymer at 330 DEG  F. with triethylene tetramine released by water.  As curing agents in connection with rubber formulations, dicumyl peroxide and triethylene tetramine are specified.  In addition, sulphur, thiazoles, N-methyldiethanolamine and piperidinium pentamethylene dithiocarbamate are mentioned as curing agents without reference to particular polymer compositions. A large number of release agent is specified (not in connection with other components) which are alcohols, glycols, ethers, amines, esters, aldehydes, ketones, organic acids, acid anhydrides, unsaturated hydrocarbons, mercaptans, halogenated hydrocarbons, and furan, thiophene, water, SO2, H2S and HCl.  Reference has been directed by the Comptroller to Specification 884,074.ALSO:A composition consisting of a zeolitic molecular sieve having coadsorbed thereon an organic peroxide, an organic amine having at least 3 carbon atoms, an aldehyde, a thiazole, a thiocarbonate or sulphur, together with a polar release agent may be employed to cure polymer compositions (see Division C3), the release agent serving to release the first adsorbed component at a lower temperature than would otherwise be necessary.  In addition to the first adsorbed components mentioned above, there are disclosed in relation to specific polymer compositions the following: dihydronybenzenes, alkyl substituted dihydronybenzenes, hydronybenzoic acids, HCE, HBR, HI, water, halogen substituted organic acids, unsaturated organic halides, acyl halides, chlorinated alkyl benzenes, thiurams, thioureas, polyhydric phenols and alcohols, glycol, novolak resins, acid anhydrides, polyesters, polyester amides, polyamides, polyalkylene ether glycols, organic tin compounds, examples of some of these classes of materials being given.  The following materials are mentioned as release agents: alcohols, glycols, ethers, amines, esters, aldehydes, ketones, organic acids, acid anhydrides, unsaturated hydrocarbons, mercaptans, halogenated hydrocarbons, furan, thiophene, water, SO2, H2S and HCl.  Reference has been directed by the Comptroller to Specification 884,074.