Patent GB-915621-A (GB)
Title: New vinyl-substituted heterocyclic compounds and polymers derived therefrom
IPC: C08F24/00
Filed: 1958-12-17
Abstract: New compounds, which may be used in coating compositions, contain 2-6 vinyl cycloacetal radicals having the structural formula <FORM:0915621/III/1> in which <FORM:0915621/III/2> represents carbon atoms in the ring, a being an integer having a value of at least 3, and all but one of the valencies of the carbon atoms being satisfied by hydrogen, or an alkyl, aryl, alkaryl, chloroalkyl, fluoroalkyl, alkoxyalkyl, chloroalkoxyalkyl, fluoroalkoxyalkyl, cyanoalkoxyalkyl, cyanoalkyl or alkenyl group, the remaining valence connecting the cyclic radical to at least one other such radical through an interposed polyvalent connecting radical, and R is hydrogen, fluorine or chlorine or an alkyl, cyano, acyloxy, chloroalkyl, fluoralkyl, cyanoalkyl, alkoxy or carbalkoxy radical.  The interposed polyvalent radical contains in the chain of atoms directly connecting the cyclic radicals at least 2 different atoms, at least one of which is carbon. The preferred connecting groups are ester groups.  The compounds can be used as coating compositions, if desired, with the addition of solvents or pigments.  Driers, for example, the naphthenate, linoleate, resinate, tallate, octoate and other salts of metals such as cobalt, lead, iron, manganese, zinc, calcium, nickel or copper may be added to the coating compositions.  The drying of the film may be speeded by heating, e.g. at 100 DEG -150 DEG F. or higher. They become substantially insoluble in solvents for the original material when 0,05% of cobalt (in the form of a 10% solution of cobalt octoate) is mixed with it and the resultant mixture is flowed on steel test panels standing in air at 68 DEG -80 DEG F.  Examples are given of the preparation of coating compositions for wood and metal panels by mixing (a) titanium dioxide, an extender, linseed oil and an itaconic diester of 5 5-hydroxymethyl-5-methyl-2-vinyl-1,3-dioxane and (b) titanium dioxide, toluene, cobalt octoate and a sebacic acid diester of 5-hydroxymethyl-5-methyl-2-vinyl-1,3-dioxane or an o-phthalic acid diester of 4-hydroxypropyl-2-vinyl-1,3-dioxepane or a mixture of these.  (Examples LXX and LXXI).  Coating compositions containing the new compounds may be used on structural steel, structures and articles made of wood, metal, ceramics, glass, fabrics, fibres, plaster, concrete, asbestos and wire.  It is usually desirable when treating wood to apply a priming coat of different composition.  The coating compositions can also be used as primers or undercoats.ALSO:The invention comprises new compounds containing 2-6 vinyl cycloacetal radicals having the structural formula <FORM:0915621/IV(a)/1> in which <FORM:0915621/IV(a)/2> represents carbon atoms in the ring, a being at least 3, and all but one of the valencies of the carbon atoms being satisfied by hydrogen, or an alkyl, aryl, alkaryl, chloroalkyl, fluoroalkyl, alkoxyalkyl, chloroalkoxyalkyl, fluoroalkoxyalkyl, cyanoalkoxyalkyl, cyanoalkyl or alkenyl group, the remaining valence connecting the cyclic radical to at least one other such radical through an interposed polyvalent connecting radical, and R is hydrogen, fluorine or chlorine or an alkyl, cyano, acyloxy, chloroalkyl, fluoroalkyl, cyanoalkyl, alkoxy or carbalkoxy radical.  The interposed polyvalent radical contains in the chain of atoms directly connecting the cyclic radicals at least 2 different atoms, at least one of which is carbon.  The preferred connecting groups are ester or ether groups.  Among the connecting groups specified are some containing silicon.  For example, (a) a mixed dioxanyl-ethyl silicate ester is obtained by reacting 2-vinyl-4-ethyl-5-propyl-5-methylol-1,3-dioxane with tetraethyl silicate in toluene (Example XXXVIII) and (b) a bis-dioxanyl ether is prepared by reacting the sodium salt of 2-vinyl-5-methylol-1,3-dioxane with sym-dichloro-tetramethyldisiloxane in toluene (Example XXXIX). The new poly-vinylcycloacetal compounds may be used in air-drying coating compositions, both the cyclic acetal and vinyl groups disappearing as drying proceeds.  Solvents and pigments may be added if required. The coating compositions may also contain known film-formers, e.g. glyceride oils, oil-modified alkyd resins, oleoresinous varnishes, synthetic resins such as alkylated urea-aldehyde resins, alkylated melamine aldehyde resins, polyepoxypolyhydroxy resins, phenol-aldehyde resins, polymers and copolymers of vinyl and vinylidene compounds; elastomers such as neoprene, styrene-butadiene rubbers and isobutylene-isoprene rubbers; cellulose esters such as cellulose acetate and acetate-butyrate; polyurethanes and silicones. There may also be added metallic driers, e.g. the naphthenates, linoleates, resinates, tallates and octoates of cobalt, lead, iron, manganese, zinc, calcium, nickel and copper.  The drying may be hastened by heating, e.g. to 100 DEG -150 DEG F.  The new vinyl cycloacetal compounds may be homopolymerized or copolymerized with other ethylenically unsaturated monomers.  Examples are given of the preparation of (a) a black baking enamel by mixing carbon black, a coconut oil modified alkyl resin in toluene, a solution of butylated ureaformaldehyde resin in butanol, cobalt octoate and a diester obtained from dimethyl adipate and 4-hydroxypropyl-2-vinyl-1,3-dioxepane; (b) a clear varnish is prepared by dissolving ester gum in the diphthalate ester of 4-hydroxypropyl-2-vinyl-1,3-dioxepane under a blanket of carbon dioxide, diluting the mixture with mineral spirits and adding cobalt octoate (Example LXXIII); and polymers by treating the sebacic acid diester of 5-hydroxymethyl-5-methyl-2-vinyl-1,3-dioxane with styrene monomer or methyl methacrylate monomer in the presence of azobisisobutyronitrile (Examples LXXIV and LXXV).  Other monomers which may be used to form polymers with the new compounds are acrylic, methacrylic and maleic acids and their esters, butadiene, acrylonitrile, vinyl chloride, vinylidine chloride and vinyl acetate. The polymerization may be carried out in bulk or in aqueous or organic media preferably in the presence of an organic peroxide, per-salts or an azo compound.  The polymers are useful in coatings and in moulding and casting resins.ALSO:The invention comprises compounds containing 2-6 vinyl acetal radicals having the structural formula <FORM:0915621/IV (b)/1> in which <FORM:0915621/IV (b)/2> represents carbon atoms in the ring, a  being an integer having a value of at least 3, and all but one of the valencies of said carbon atoms being satisfied by hydrogen, or an alkyl, aryl, alkaryl, chloroalkyl, fluoralkyl, alkoxyalkyl, chloroalkoxyalkyl, fluoroalkoxyalkyl, cyanoalkoxyalkyl, cyanoalkyl or alkenyl group, the remaining valence connecting the cyclic radical to at least one other such radical through an interposed polyvalent connecting radical, which contains in the chain of atoms directly connecting the cyclic radicals at least two different atoms, at least one of which is carbon; and R is hydrogen, fluorine, chlorine, or an alkyl, cyano, acyloxy, chloroalkyl, fluoroalkyl, cyanoalkyl, alkoxy or carbalkoxy radical.  Examples of suitable polyvalent connecting radicals are, <FORM:0915621/IV (b)/3> -(OCH2CH2)-1-5 and -CH2-(OCH2CH2)1-5.  In addition to compounds containing vinyl cyclic acetal radicals and connecting radicals as illustrated above the invention includes compounds containing bivalent intermediate or bridging radicals between the cyclic acetal rings and the polyvalent connecting radicals e.g. compounds having the connecting radical -CH2-OOC-C6H4-COO-CH2.  The group <FORM:0915621/IV (b)/4> may be introduced into an intermediate by reacting acrolein or the appropriate a -substituted acrolein with a polyhydroxy compound as follows:-  <FORM:0915621/IV (b)/5> Alternatively an intermediate product may be prepared as follows:-  <FORM:0915621/IV (b)/6> is prepared by condensing 2,3-dichlorpropionaldehyde and trimethylolpropane and is dehydrochlorinated to give the group <FORM:0915621/IV (b)/7> The preferred class of new products is esters and these may be prepared by preparing a hydroxyalkyl 2-vinyl-1,3-cyclic acetal as above and reacting it with a C1-C6 alkyl ester or the acid chloride of the desired polycarboxylic acid, or reacting an acetoxyalkyl-2-vinyl-1-1,3-cyclic acetal with the desired polycarboxylic acid or a C1-C6 ester thereof, and eliminating acetic acid or alkyl acetate.  Alternatively a haloalkyl-2-vinyl-1,3-cyclic acetal may be reacted with a salt of the desired polybasic acid.  The preferred method of preparing the esters is by condensing substantially equimolar proportions of acrolein and a triol, e.g. trimethylolpropane, under mild acid conditions in a solvent forming a binary azeotrope with water, at a temperature below 130 DEG C. to give a hydroxyalkyl-2-vinyl-1,3-cyclic acetal and to esterify this by treatment with an alkyl ester of the desired acid, preferably under basic ester interchange conditions and in the presence of a solvent which forms a binary azeotrope with the alcohol by-product.  It is particularly preferred to carry out the esterification in the presence of an alkyl orthotitanate. Suitable starting materials are (a) for cyclic acetals containing 6 atoms in the cyclic acetal ring (i.e. a = 3): trimethylolmethane, trimethylolethane, trimethylolpropane, trimethylolbutane, methyl 3,5-dihydroxy hexanoate, 1-phenyl-2-hydroxymethyl-1,3-propanediol and ethyl 4-(11,31-dihydroxypropyl)cyclohexane carboxylate; (b) for cyclic acetals containing 7 atoms in the cyclic acetal ring; (i.e. a = 4): 1,4,7-heptanetriol, ethyl 8,11-dihydroxy stearate and 3-carbethoxy-2,5-hexanediol; (c) for cyclic acetals containing 8 atoms in the cyclic acetal ring (a = 5): 4-hydroxymethyl-1,7-heptanediol, 2-carbethoxymethyl-1,5-pentanediol and ethyl-3,7-dihydroxy octanoate; and (d) for cyclic acetals containing 9 atoms in the cyclic acetal ring (a = 6): 3-carbethoxy-1,6-hexanediol.  Suitable dicarboxylic