Patent GB-899065-A (GB)
Title: New polymerisable vinyl-dioxolane compounds and their production
IPC: C07F7/02
Filed: 1958-09-01
Abstract: Coating compositions contain liquid compounds containing 2-6 cyclic radicals of the structural formula <FORM:0899065/III/1> in which R is hydrogen, fluorine, chlorine, alkyl, cyano, acyloxy, chloroalkyl, fluoroalkyl, cyanoalkyl, alkoxy or carbalkoxy; 3 of the 4 remaining valencies are satisfied by hydrogen, alkyl, aryl, alkaryl, chloroalkyl, fluoroalkyl, alkoxyalkyl, chloroalkoxyalkyl, fluoroalkoxyalkyl, cyanoalkoxyalkyl, cyanoalkyl or alkenyl; and the fourth valency connects the cyclic radical to at least one other such radical through an interposed polyvalent radical which contains, in the chain of atoms directly connecting said cyclic radicals, at least two different atoms, at least one of which is carbon.  Specified polyvalent radicals are -OOC(CH2)4COO-, -OOCCH2OCH2CCO-, -OOCCH2CH2SCH2CH2COO-, -OOCCH:CHCOO-, -OOCN:NCOO-, -OCH2O-, -OCH2CH2O-, <FORM:0899065/III/2> <FORM:0899065/III/3> <FORM:0899065/III/4> <FORM:0899065/III/5> <FORM:0899065/III/6> <FORM:0899065/III/7> <FORM:0899065/III/8> <FORM:0899065/III/9> <FORM:0899065/III/100> <FORM:0899065/III/111 <FORM:0899065/III/144> <FORM:0899065/III/155> <FORM:0899065/III/166> and <FORM:0899065/III/177> specific compounds in the examples contain other connecting radicals also.  The compounds may also contain bivalent bridging radicals between the dioxolane rings and the polyvalent connecting radical, such as -(CH2-)1-16, -CH2-(OCH2CH2-)1-5, <FORM:0899065/III/188> <FORM:0899065/III/199> <FORM:0899065/III/200> and <FORM:0899065/III/211> The preferred compounds are esters of hydroxyalkyl-2- substituted vinyl-dioxolanes, and many di- and polycarboxylic acids suitable for forming such esters are specified; other acidic compounds may also be used, such as cyanuric acid and also ortho-esters of acids of silicon, titanium, aluminium, boron and phosphorus; the ester linkages may also be urethane ester linkages.  Another type of polyester is that derived from a polyol and a monocarboxylic acid containing a dioxolane ring as defined above (see Group IV(b)).  The compositions can be unpigmented, with a solvent if desired, or pigmented with pigments such as metal oxides, sulphides, sulphates, silicates, chromates, iron blues, carbon black, organic colours and metal flake pigments. Other filmforming components may be present, such as vegetable oils, oil-modified alkyd resins, oleoresinous varnishes, synthetic resins, cellulose esters, polyurethanes and silicones.  Other ingredients may also be present, such as plasticizers, catalysts, hardeners, anti-skinning agents, surface-active agents and metallic driers.  The compositions may be applied, e.g. by brushing or spraying, to metal, wood, ceramics, glass, fibres, fabrics, plaster, concrete, asbestos and wire; wood is preferably primed with a different composition. The coatings may air-dry or be baked.ALSO:The invention comprises (a) liquid compounds containing 2-6 cyclic radicals of the structural formula <FORM:0899065/IV (a)/1> in which R is hydrogen, fluorine, chlorine, alkyl, cyano, acyloxy, chloroalkyl, fluoroalkyl, cyanoalkyl, alkoxy or carbalkoxy; 3 of the 4 remaining valencies are satisfied by hydrogen, alkyl, aryl, alkaryl, chloroalkyl, fluoroalkyl, alkoxyalkyl, chloroalkoxyalkyl, fluoroalkoxyalkyl, cyanoalkoxyalkyl, cyanoalkyl or alkenyl; and the fourth valency connects the cyclic radical to at least one other such radical through an interposed polyvalent radical which contains, in the chain of atoms directly connecting said cyclic radicals, at least two different atoms, at least one of which is carbon.  Specified polyvalent radicals are -OOC(CH2)4COO-, -OOCCH2OCH2COO-, -OOCCH2CH2SCH2CH2COO-, -OOCCH:CHCOO-, -OOCN:NCOO-, -OCH2O-, -OCH2CH2O-, -OCH2CH2OCH2CH2O-, <FORM:0899065/IV (a)/2> and <FORM:0899065/IV (a)/3> ; specific compounds in the examples contain other connecting radicals also.  The compounds may also contain bivalent bridging radicals between the dioxolane rings and the polyvalent connecting radical, such as -(CH2-)1-16, -CH2-(OCH2CH2-)1-5, <FORM:0899065/IV (a)/4> and <FORM:0899065/IV (a)/5> The preferred compounds are esters of hydroxyalkyl-2-substituted vinyldioxolanes, and many di- and polycarboxylic acids suitable for forming such esters are specified; other acidic compounds may also be used, such as cyanuric acid and also ortho-esters of acids of silicon, titanium, aluminium, boron and phosphorus; the ester linkages may also be urethane ester linkages. Another type of polyester is that derived from a polyol and a monocarboxylic acid containing a dioxolane ring as defined above (see also Group IV(b)).  Specific examples prepare (27) the ortho-silicate derived from 2-vinyl-4-phenyl-5-hydroxypropyl-1,3-dioxolane; (47) the disiloxane from symmetrical diglycidyl tetramethyl disiloxane and acrolein; and (48) the disiloxane from symmetrical tetramethyl diglycidyloxydisiloxane and acrolein.  The invention also comprises (b) homopolymers and copolymers of the above monomers.  The copolymers may be polymers inter se or with other ethylenically unsaturated monomers, such as acrylic, methacrylic and maleic acids and esters, styrene, butadiene, acrylonitrile, vinyl chloride, vinylidene chloride and vinyl acetate.  The invention also comprises (c) coating compositions containing the monomers of (a) above; said compositions may also contain cellulose esters such as the acetate and acetate butyrate; oil-modified alkyd resins, 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 such as vinyl chloride and acetate and vinylidene chloride, acrylic and methacrylic acids and esters, styrene and butadiene; elastomers such as neoprene, styrene-butadiene rubbers, acrylonitrile-butadiene rubbers, isobutylene-isoprene rubbers; polyurethanes and silicones.  Other additives may also be present, such as plasticizers, catalysts, hardeners, antiskinning agents, surface-active agents and metallic driers.ALSO:The invention comprises liquid compounds containing 2-6 cyclic radicals of the structural formula <FORM:0899065/IV (b)/1> In which R is hydrogen, fluorine, chlorine, alkyl, cyano, acyloxy, chloroalkyl, fluoroalkyl, cyanoalkyl, alkoxy or carbalkoxy; 3 of the 4 remaining valencies are satisfied by hydrogen, alkyl, aryl, alkaryl, chloroalky, fluoroalkyl, alkoxyalkyl, chloroalkoxyalkyl, fluoroalkoxyalkyl, cyanoalkoxyalkyl, cyanoalkyl or alkenyl; and the fourth valency connects the cyclic radical to at least one other such radical through an interposed polyvalent radical which contains, in the chain of atoms directly connecting said cyclic radicals, at least two different atoms, at least one of which is carbon.  Specified polyvalent radicals are <FORM:0899065/IV (b)/2> specific compounds in the examples contain other connecting radicals also.  The compounds may also contain bivalent bridging radicals between the dioxolane rings and the polyvalent connecting radical, such as <FORM:0899065/IV (b)/3> and <FORM:0899065/IV (b)/4> The preferred compounds are esters of hydroxyalkyl-2-substituted vinyl-dioxolanes, and many diandpolycarboxylic acids suitable for forming such esters are specified; other acidic compounds may also be used, such as cyanuric acid and also ortho-esters of acids of silicon, titanium, aluminium, boron and phosphorus; the ester linkages may also be urethane ester linkages.  Another type of polyester is that derived from a polyol and a monocarboxylic acid containing a dioxolane ring as defined above.  Ester-type compounds may be prepared by condensing acrolein or an alpha-substituted acrolein with a triol and reacting the resulting 4-hydroxyalkyl-2-vinyl-dioxolane with a C1-9 alkanolic ester of the desired polycarboxylic acid under ester-interchange conditions.  Esters may also be obtained by using the acid chloride of the polycarboxylic acid, or by reacting a 4-acetoxyalkyl-2-vinyl-dioxolane with polycarboxylic acid or its lower alkyl ester, or by reacting a 4-haloalkyl-2-vinyl-dioxolane with a salt of the desired polycarboxylic acid.  Examples illustrate the formation of esters and other compounds of the invention. Intermediates.  4-(41-Hydroxybutyl)-2-vinyl-1,3-dioxolane is prepared from acrolein and 1,2,6-hexanetriol. 2-Vinyl-4-(7-carbomethoxyheptyl)-5-1,3-dioxolane is prepared from acrolein and epoxidized methyl oleate. 2-Vinyl-4-heptyl-4-methyl-5-carbomethoxy-1,3-dioxolane is prepared from acrolein and beta-methyl-beta-heptyl-glycidic acid methyl ester. 2-(alpha-chlorovinyl)-4-(41-hydroxybutyl)-1,3-dioxolane is prepared by dehydrochlorinating the corresponding 2-(alpha,-beta-dichloroethyl) compound, obtained from 1,2,6-hexanetriol and 2,3-dichloropropionaldehyde. Alpha-fluoroacrolein is obtained by reacting pyruvic aldehyde tosylate with NaF.  Alpha-(cyanoethyl)-acrolein is obtained by cyanoethylation of beta-chloropropionaldehyde followed by dehydrochlorination.  The compounds of the invention can be polymerised (see Group IV (a)) and are of use for the preparation of coating materials (see Groups III and VIII).