Patent GB-732711-A (GB)
Title: Resinous esters of alkenylphenol-aldehyde condensates
IPC: C08G8/32
Filed: 1952-08-08
Abstract: A resin is made by reacting a condensation product derived from an aldehyde and a phenol having an ethylenically unsaturated hydrocarbon chain containing 14-28 carbon atoms attached to its aromatic nucleus with a substance capable of forming ester groups with the phenolic hydroxy groups in the condensation product. The Specification contains a list of aldehydes and a list of anarcardic phenols having the formula (R.C6H3OH.X)n where R is a hydrocarbon radical of 14-28 carbon atoms containing one or more double bonds, n is 1 or more and X is hydrogen or a hydroxyl, aryloxy, alkoxy, alkenyl, alkyl, acyl, aryl, aralkyl, halogen, sulphydryl, carboxy, amino, alkamino, dialkamino, acetamino, methylol, cycloalkyl, carbalkoxy, alkenoxy, alkenecarboxy or thiocarboxy group.  Esterifying agents specified are aliphatic monocarboxylic acid anhydrides, acid chlorides and esters, alkenyl, aralkyl, cycloalkyl aryl and monocarboxylic acid anhydrides and acid chlorides; and polycarboxylic acid anhydrides and acid chlorides, which agents may contain one or more halogen, nitro, alkoxy, carbalkoxy or keto groups; also furoyl chloride, the pyridine acid chlorides, the thiophene acid chlorides, ketene, methyl ketene, alkyl or aryl mono- and poly-isocyanates, cyanuric chloride and phosgene.  The resinous esters dissolved in V.M. and P. naphtha, or in the case of the low condensates (dimers-tetramers) without a solvent, are coating compositions after the addition of manganese, lead or cobalt driers.  The flexibility of the dried coatings may be increased (a) by replacing part of the alkenyl phenol with a long chain alkyl phenol (e.g. hydrogenated cardanol or wax phenols) containing 14-30 carbon atoms in the alkyl chain; (b) by using a long-chain aldehyde for all or part of the aldehyde in the condensation reaction, or (c) by using a long hydrocarbon chain esterifying agent.  The hardness of these films may be increased (a) by replacing part of the alkenyl phenol with phenol or cresols; (b) by using a short chain esterifying agent, e.g. oxalyl chloride or phosgene; or (c) by using 1-2 moles of aldehyde per mol. of phenol in the condensation reaction along with increased reaction times and temperatures.  Skinning of the varnishes is prevented by adding 1 per cent or less of free phenols, e.g. "Guai-A-Phene".  The esters may be plasticized with blown or unblown drying or non-drying oils, e.g. soyabean, linseed, oiticica, perilla, sardine, tung, cottonseed or dehydrated castor oils.  They may be added to semi-drying oils and may be co-blown with semi-drying or drying oils (see Group III).  The esters may be used as plasticizers for natural and synthetic rubbers and phenol-formaldehyde resins and may be cross-vulcanized with natural or synthetic rubbers using sulphur or sulphur containing compounds.  They may be copolymerized with butadiene, styrene, chloroprene, acrylonitrile, isoprene, or any combination of these in presence of peroxide, peroxide-redox systems, or sodium to give internally-plasticized rubbers.  In examples: Cardanol is refluxed with formalin in presence of ammonia, the reaction mixture dehydrated under reduced pressure and the mixture heated to 120 DEG  C. for three hours.  The product is then dissolved in xylol and (1) reacted with acetic anhydride in presence of pyridine; (2) reacted with acetic anhydride in presence of metanol and potassium hydroxide; (3) reacted with benzoyl chloride in presence of dioxane, methanol and potassium hydroxide.  Specification 721,713 is referred to.ALSO:A resinous product made by esterifying a condensation product of an aldehyde and a phenol having an ethylenically unsaturated hydrocarbon chain containing 14-28 carbon atoms attached to its aromatic nucleus (especially an anarcardic phenol) [see Group IV (a)], may be added to semi-drying oils to decrease their gelation and drying times and increase their resistance to salt water, alkali, organic solvents and acids.  The resin may be co-blown with oxygen or air with drying or semi-drying oils to give oils with better drying properties. Specification 721,713 is referred to.