Patent GB-841159-A (GB)
Title: Improvements to or relating to vulcanizable compositions
Inventor: BURKE OLIVER W JR
IPC: C08F291/06
Filed: 1956-11-07
Abstract: A vulcanizable composition comprises a vulcanizable unsaturated polymer and a cyanalkylamine, with a filler, the cyanoalkylamine being replaceable by its saponification product, the carboxyalkylamine.  The other usual additives can also be present, such as accelerators, activators, antioxidants and softeners.  It is preferred that the polymer or the filler (or both) contains a carbonyl and/or a carboxyl group capable of reacting with the cyanoalkylamine.  The polymer may be natural rubber, a polymerized diene such as polychloroprene or neoprene, or a diene-vinyl copolymer, e.g. of butadiene with styrene (with or without methacrylic acid) or acrylonitrile.  The filler may be inorganic or may be an organic polymer with or without the polar groups mentioned above.  Suitable inorganic fillers are carbon black, silica, clay, diatomaceous earth, metal oxides (e.g. titanium), metal silicates (e.g. calcium) and metal carbonates. The organic filler can be a copolymer of divinylbenzene with styrene or vinyltoluene, with an additional polar monomer if desired, e.g. acrolein, methacrolein, methacrylic acid, methyl-isopropenyl ketone or methacrylic acid.  The last-named terpolymer may be grafted with a butadiene-vinylpyridine copolymer and with a resorcinol-formaldehyde resin.  Other suitable polar copolymers are those of styrene and maleic anhydride, of methacrylic acid and maleic anhydride, and the terpolymer of styrene, triacrylyl-hexahydrotriazine and methacrylic acid.  The filler may also be polyacrylic acid, polymethacrylic acid, pectic acid or lignin.  Other specified ingredients of the compositions are zinc oxide, stearic acid, butylideneaniline (and its condensation product with butyraldehyde), diphenylguanidine, di-otolylguanidine, phenyl-b -naphthylamine, polytrimethyldihydroquinoline, copper diethyl-dithiocarbamate, tetraethyl thiuram disulphide, mercaptobenzthiazole, benzthiazolyl disulphide, N - cyclohexyl - benzthiazolesulphenamide, petroleum oil, and a condensation product from ethyl chloride, formaldehyde and ammonia.  The cyanoalkylamine may be an a - or b -cyanoalkyl derivative of ammonia, a monoamine or a polyamine, and there may be more than one cyanoalkyl group attached to the same and/or different nitrogen atom.  The molecule may contain substituents such as hydroxy, ether, aryl, cycloalkyl or heterocyclic groups, and the amine may be cyclic as morpholine.  Many suitable cyanoalkylamines are specified.  Resinous products are stated to be obtained by heating poly-cyanoalkyl-polyamines with metal oxides or salts above 100 DEG  C.  In examples the following are heated with zinc oxide and stearic acid (equivalent to zinc stearate): allylamino-propionitrile, and the reaction products from lactonitrile and hexamethylenediamine, diethylenetriamine, tetraethylenepentamine and mixed polyethylene polyamines.  In a further example, lactonitrile, mixed polyamines, zinc oxide, tall oil, stearic acid and a petroleum fraction are heated together, the last three ingredients being examples of plasticizers that can be used.  Other suitable metallic compounds are the oxides of cadmium, calcium, magnesium, lead and tin, and the naphthenates of cobalt and manganese.  Specifications 799,043 and 820,930 are referred to.ALSO:Cyano-alkylamines and N-substituted derivatives thereof are made by reacting aldehyde cyanhydrins, ketone cyanhydrins or a ,b -unsaturated nitriles with ammonia or mono- or poly-amines. One, two or three a -cyanoalkyl or b -cyanoalkyl groups may thus be introduced on to the nitrogen atom.  When the products contain more than one amino group they react on heating with metallic oxides (e.g. Zn, Cd, Ca, Mg, Pb, Sn) or salts thereof (especially Zn stearate and Co or Mn naphthenate) to give waxy or resinous materials.  Specified cyano compounds for use as starting materials are glycollonitrile, lactonitrile, acetone - cyanhydrin, acetophenone - cyanhydrin, methyl - isopropenyl - ketone - cyanhydrin, acrylonitrile and methacrylonitrile. Specified amines for reaction therewith are isopropylamine, t-butylamine, t-octylamine and higher t-alkylamines, allylamine, ethanolamine, diethylamine, di - isopropylamine, b  - isopropylamino-propionitrile, a - and b -imino-bis-propionitrile, aniline, cyclohexylamine, rosinamine, morpholine, N - (3 - aminopropyl) - morpholine, furfurylamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, imino - bis - 3 - propylamine, ethylene - bisoxypropylamine, hexamethylenediamine, benzidine, N-octylbenzidine, m- and p-phenylenediamines and N : N - di - s - butyl - p - phenylenediamine.  Carboxyalkylamines are made by saponification of the cyanoalkylamines, e.g. of the product from lactonitrile and tetraethylenepentamine.