Patent GB-665191-A (GB)
Title: Improvements in or relating to the preparation of resinous materials and polymerizable compositions for producing the same
IPC: C08F16/28
Filed: 1947-08-14
Abstract: Resinous material is prepared by polymerizing a triazine derivative having the formula <FORM:0665191/IV (a)/1> wherein A represents (a) a monovalent saturated aliphatic, aromatic or nuclearly halogenated aromatic hydrocarbon radical, or (b) a radical represented by the formula -NRR1, wherein R and R1 are hydrogen, monovalent saturated aliphatic hydrocarbon radicals or monovalent aromatic or nuclearly halogenated aromatic hydrocarbon radicals, or (c) a radical represented by -OR11, where R11 has the same meaning as R and R1, R111 representing a monovalent radical which is the residue of a primary, ethylenically unsaturated monohydric alcohol containing from 3 to 10 carbon atoms, and n is 1, 2 or 3.  Examples of such compounds are triallyl cyanurate, 2-amino-4,6-dialloxy - 1,3,5 - triazine, 2 - alloxy - 4,6-diamino - 1,3,5 - triazine, 2 - butylamino - 4,6-dimethalloxy - 1,3,5 - triazine, tricrotyl cyanurate, trimethallyl cyanurate and diallyl methallyl cyanurate.  One or more other monomeric compounds having a CH2=C< group in the molecule and/or one or more unsaturated non-crystalline alkyd resins may be copolymerized with the triazine derivative.  Examples of copolymerizable monomers are styrene, mono- and di-chloro- and methyl-styrenes, vinyl naphthalene, vinyl cyclohexane, vinyl furane, vinyl dibenzofuran, divinyl benzene, ethyl vinyl ether, diallyl ether, methallyl ethyl ether, methyl vinyl ketone, divinyl ketone and methyl allyl ketone, methylene malonic esters, butadiene, chlorobutadiene, methyl acrylate and methacrylate, saturated alcohol esters of unsaturated aliphatic mono- and polycarboxylic acids and the allyl, methallyl, chloroallyl, crotyl, cinnamyl, vinyl, methvinyl, a -phenyl allyl or propargyl esters of saturated or unsaturated, aliphatic and aromatic, mono- and polybasic acids.  A long list of allyl compounds, including alcohol-amino esters and silicon compounds, is given. p  The alkyd resins may be prepared from any unsymmetrical glycol or other polyhydric alcohol, e.g. glycerol or pentaerythritol, and an unsaturated acid such as maleic, fumaric, itaconic, citraconic, mesaconic, aconitic and halogenated maleic acids.  The alkyd resins may be modified with one or more monohydric alcohols, monocarboxylic acids, saturated aliphatic polycarboxylic acids or aromatic polycarboxylic acids, of which many examples are given. Lower alkyl maleates may also be introduced.  The polymerization of the triazine derivatives is preferably effected in the presence of a catalyst such as benzoyl, phthalic, succinic, benzoyl acetic, lauric, stearic, oleic or coconut oil peroxides, tert. butyl hydroperoxide, ascaridole, cobalt linoleate and naphthenate, p-toluene sulphonic acid, aluminium chloride, stannic chloride and boron trifluoride.  The polymerizable mixture containing an alkyd resin may be thinned by heating with an esterification catalyst, e.g. p-toluene sulphonic acid, before polymerization, or may be bodied by heating alone before adding the catalyst and polymerizing.  Partial polymers of the triazine derivatives may be incorporated in the copolymerizable material to produce the required viscosity.  Inhibitors such as phenolic compounds, aromatic amines, sulphur compounds, benzaldehyde, ascorbic or isoascorbic acids may be used.  Examples describe polymerization in bulk and by refluxing in xylene and in water.  The polymerizable compositions may be used in moulding operations, as impregnants for fibrous materials, for laminating and coating, for castings and as adhesives.  Optional additives to the compositions include cellulose pulp, asbestos or glass fibres, cotton flock, cloth cuttings, wood flow, mica dust, sand, clay, diatomaceous earth, shellac, ester gum, cellulose esters or ethers, urea-aldehyde resins, amino-triazine-aldehyde resins, phenol-aldehyde resins, hydrocarbon-substituted polysiloxane resins, phenyl polysiloxane resins, conventional alkyd resins and natural or synthetic rubber.  Specifications 644,287 and 653,396 are referred to.ALSO:Triazine derivatives are prepared having the formula <FORM:0665191/IV (b)/1> wherein A represents (a) a monovalent saturated aliphatic, aromatic or nuclearly halogenated aromatic hydrocarbon radical, or (b) a radical, represented by the formula -NRR1, wherein R and R1 are hydrogen, monovalent saturated aliphatic hydrocarbon radicals or monovalent aromatic or nuclearly halogenated aromatic hydrocarbon radicals, or (c) a radical represented by -OR1, where R11 has the same meaning as R and R1, R111 representing a monovalent radical which is the residue of a primary, ethylenically unsaturated monohydric alcohol containing from 3 to 10 carbon atoms, and n is 1, 2 or 3.  Their preparation is effected by reacting, under alkaline conditions in the presence of an inorganic base, a compound of the formula <FORM:0665191/IV (b)/2> where X is chlorine or bromine, with the above defined alcohol. Reaction may be at normal or elevated temperature and pressure. Specified end products are triallyl cyanurate, 2 - amino - 4,6 - dialloxy - 1,3,5 - triazine, 2-alloxy - 4,6 - diamino - 1,3,5 - triazine, 2 - butyl-amino - 4,6 - dimethalloxy - 1,3,5 - triazine, tricrotyl cyanurate, trimethallyl cyanurate and diallyl methallyl cyanurate.  Specifications 644,287 and 653,396, [both in Group IV (a)], are referred to.