Patent GB-1057044-A (GB)
Title: Improved release of curing agents from molecular sieves
IPC: C08L83/04
Filed: 1963-06-07
Abstract: A storable mixture which can be cured by heating comprises (a) a curable organic resin or elastomer; (b) a crystalline zeolite molecular sieve having a curing agent adsorbed therein; and (c) a release agent which is a substantially anhydrous hydroxy or carboxy compound and has a critical dimension not larger than the apparent pore size of the zeolite and which is adsorbable at, but not appreciably below, curing temperature.  Zeolites A, D, L, R, S, T, X and Y are specified; suitable release agents are substantially anhydrous monohydric and polyhydric alcohols, phenols, organic acids, glycol ethers, ketones and alkanolamines; and the following combinations of the remaining constituents are mentioned:  Epoxy resins based on 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 - epoxypentoxy) 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 - hexane, 1,2,5,6 - diepoxyhexane, 1,2,3,4 - tetra(2 - hydroxy - 3,4 - epoxybutoxy) butane, polyglycidyl esters formed by reacting an epihalohydrin with a salt of a polybasic acid, glycidyl polyethers of polyhydric phenols (polyhydric phenol reacted with 3-6 mols. per hydroxy group of epihalohydrin in alkaline medium and polyhydric phenol (e.g. bis(4-hydroxyphenyl) - dimethylmethane) with 1-2 mols. per hydroxy group of epichlorhydrin with an alkaline catalyst. Curing agents for epoxy resins: polyamines e.g. diethylenetriamine, triethylene tetramine, m-phenylenediamine, ethylenediamine and triethanolamine, N : N - dimethylethanolamine, benzyldimethylamine and trimethylamine.  (See also Examples 1-5 below.)  Unsaturated polyester resins e.g. formed by combining the reaction product of alkylene glycols and maleic acid with styrene: curing agents are t-butylhydroperoxide, di-t-butyl peroxide, and dicumyl peroxide. Dimethacrylate esters of a glycol e.g. polyethylene glycol, mixed with polyvinyl chloride: curing agents are peroxides.  Polysiloxane resins can be cured with amines such as diethanolamine. Polysiloxane-epoxy resins can be cured with the above-mentioned epoxy resin curing agents.  Phenolite resins can be cured with ammonia and formaldehyde or hexamethylene tetramine.  Rubber formulations may in general be cured with sulphur, a peroxide e.g. dicumyl peroxide or a polyamine e.g. triethylenetetramine: in particular neoprene rubbers (elastomers based on 2-chlorobutadiene-1:3) of sulphur-modified or non-sulphur-modified type may be cured with pyracatechol, resorcinol, ethyl catechol, ethyl resorcinol, salicylic acid and p-hydroxy benzoic acid, butyl rubbers (copolymers of isoolefin e.g. i-butylene or ethyl methylethylene with minor proportion of a C4- 14 multiolefinic unsaturate e.g. isoprene or butadiene) may be cured with HCl, HBr, HI, halogen substituted organic acids, 1:4-dichlorobutene, 2-chloropropene, 2-bromopropene, benzoyl chloride, and a :a :a :trichorotoluene, Buna (Registered Trade Mark) rubbers (75% butadiene, and styrene) may be cured with thiurams, arylamines, alkylarylamines, thioureas, piperidine, diethylamine and di-n-butylamine.  Natural rubbers, polyacrylates, polyisoprene, polybutadiene, ethylene propylene rubber, butadiene acrylonitrile copolymers, butadiene acrylic ester copolymers and silicone rubber are also mentioned.  The storable mixtures are obtained by mixing or blending the three components and curing is effected when desired by heating e.g. to 75-175 DEG  C., for rubber formulations 135-200 DEG C.  In the examples the following compositions are described, component (b) being in each case loaded on zeolite X: (1) (a) diglycidyl ether of bisphenol A; (b) diethylene triamine (C) glycerol, 1:3-propylene glycol, 1:4-butane diol, castor oil (non-effective as release agent), 2:3-butanediol, various polyethylene glycols, dipropylene glycol, polypropylene glycol, hexylene glycol or 1:5-pentanediol; (2) (a) diglycidyl ether of bisphenol A; (b) metaphenylene diamine and (c) glycerol; (3) (a) diglycidyl ether of bisphenol A, (b) diethylenetriamine, (c) hexylene glycol and in addition liquid coal tar was present; (4) for use on a glass tape a composition comprising (a) diglycidyl ether of bisphenol A (b) diethylene triamine, (c) 1:5-pentanediol and in addition acetone which was flashed off after application of the composition to the tape by dipping; and (5) (a) diglycidyl ether of bisphenol A and hexahydrophthalic anhydride, (b) dimethylethanolamine, and (c) propylene glycol, hexylene glycol or polyethylene glycol.  Reference has been directed by the Comptroller to Specification 884,074.ALSO:A storable mixture which can be cured by heating comprises (a) a curable organic resin or elastomer, (b) a crystalline zeolite molecular sieve having a curing agent absorbed therein and (c) a release agent whch is a substantially anhydrous hydroxy or carboxy compound, and has a critical dimension not larger than the apparent pore size of the zeolite and which is adsorbable at, but not appreciably below, curing temperature.  Various resins and elastomers are specified (see Division C3), together with zeolites A, D, L, R, S, T, X and Y and chabazite, erionite, faujacite, analeite, clinoptilolite and mordenite.  Specified curing agents are polyamines, organic peroxides, ammonia and formaldehyde, sulphur, dihydroxy benzenes, hydrohalic acids, halogen-substituted organic acids, unsaturated organic halides, acyl halides, alkyl benzenes, thiurams, thioureas and piperidine. Specified release agents are substantially anhydrous monohydric and polyhydric alcohols, phenols, organic acids, glycol ethers, enolising ketones and alkanolamines. The curing agent may be adsorbed on to the zeolite by placing the zeolite in a vacuum desicator with the curing agent in a separate container whereby the vapour is contacted with the zeolite; solid curing agent may be mixed with the zeolite; or the zeolite may be mixed with a solution of the curing agent or the curing agent in liquid form. The amount adsorbed is usually 0.001 - 25% by weight. The other components may be mixed conventionally with the loaded sieve. Curing of the resin or elastomer may be effected by heating to 75 - 200 DEG C.  Reference has been directed by the Comptroller to Specification 884,074.