Patent GB-1115596-A (GB)
Title: Uv absorbent light stable compounds and compositions containing the same
IPC: C08L21/00
Filed: 1966-07-22
Abstract: Polymeric materials have incorporated therein U.V. absorbent compounds of the general formula <FORM:1115596/C3/1> in which X1, X11, X2 and X12 independently of each other represent the groups -COR1 or -CN, wherein R1 represents the groups <FORM:1115596/C3/2> wherein the substituents R2, R3 and R4 contain none of the atom groupings -O-C-O-, -N-C-O- -N-C-S-, -C=C-O- and -C=C-N- and hereby R2 and R3 each represent an optionally substituted alkyl, alkenyl, cycloalkyl, aralkyl, monooxaaralkyl or aryl group, R4 represents an alkylene, monooxaalkylene or monothiaalkylene group.  Y and Y1 each represent a bivalent radical of the formula -NHCO-, -NHSO2- or -NHCOO- which radical is attached to the ring A or B by the nitrogen atom, or Y and Y1 is -O-.  R5 and R15 each represent an optionally substituted aryl group or, when all X1 are only -COR1 groups, they also represent hydrogen or, when at least two of the X's are cyano groups, they also represent an optionally substituted alkyl or aralkyl group.  R6 represents an alkylene, mono- or dioxaalkylene, mono- or di-thia-alkylene, cycloalkylene, aralkylene, or mono-oxa-aralkylene group and, when Y or Y1 is a nitrogen-containing group, it also represents the phenylene group, whereby two or more hetero atoms present in or bound to R6 are separated from each other by at least 2 carbon atoms, and oxygen atoms bound to R6 and linking it to the benzene rings A and B are bound at saturated carbon atoms of R6, and  n represents 2 or, when Y is oxygen, also 1, and the benzene rings A and B can be substituted by chemically inert and non-colouring substituents.  An extensive list of polymers is given and examples refer to unsaturated polyester resin or methyl methacrylate polymerization being effected in the presence of the U.V. compound, and to polyvinyl chloride, polyethylene, polypropylene, polystyrene, polyurea, polyurethane, polyester amide including polymers of lactams and E-caprolactam, phenol-, urea-, and melamine formaldehyde, epoxides, acetyl cellulose compositions containing the U.V. absorbent compounds.ALSO:The invention comprises U.V. absorbing compounds of the general formula <FORM:1115596/C2/1> wherein X1, X11, X2 and X21 independently of each other represent the groups -COR1 or -CN, wherein R1 represents the groups <FORM:1115596/C2/2> wherein the substituents R2, R3 and R4 contain none of the atom groupings -O-C-O, -N-C-O, -N-C-S, -C = C-O and -C = C-N- and whereby R2 and R3 each represent an optionally substituted alkyl, alkenyl, cyclo-alkyl, aralkyl, mono-oxo-aralkyl or aryl group, R4 represents an alkylene, mono-oxa-alkylene or monothia-alkylene group, Y and Y1 each represent a bivalent radical of the formula -NHCO-, -NHSO2-or-NHCOO- which radical is attached to the ring A or B by the nitrogen atom, or Y and Y1 is -O-, R5 and R51 each represent an optionally substituted aryl group or, when all X's are only -COR1 groups, they also each represent hydrogen or, when at least two of the X's are cyano groups, they also represent an optionally substituted alkyl or aralkyl group, R6 represents an alkylene, mono- or di-oxa-alkylene, mono- or di-thia-alkylene, cycloalkylene, aralkylene, or mono-oxa-aralkylene group and, when Y or Y1 is a nitrogen-containing group, it also represents the phenylene group, whereby two or more hetero atoms present in or bound to R6 are separated from each other by at least 2 carbon atoms, and oxygen atoms bound to R6 and linking it to the benzene rings A and B are bound at saturated carbon atoms of R6, and n represents 2 or, when Y is oxygen, also 1, and the benzene rings.  A and B can be substituted by chemically inert and non-colouring substituents. The compounds may be prepared: A by condensation of 1 mol of dicarbonyl compound of Formula II with 2 mols of identical or different malonic acid derivatives of Formulae III and IIIa <FORM:1115596/C2/3> <FORM:1115596/C2/4> under the known conditions for Knoevenagel condensation.  In some cases, particularly if R5 or R51 is not hydrogen, an improvement is attained by converting the carbonyl compounds into the activated forms such as into the corresponding bis-dichlorides or bis-imines, and then reacting with the malonic acid derivatives.  B.  By reaction of 2 mols. of identical or different compounds of Formulae IV and IVa wherein Y1 and Y11 represent the hydroxyl or amino group, with 1 mol of a bifunctional alkylating or acylating agent of Formula V Z-R6-Z (V) wherein Z, when Y1 or Y11 is HO-, represents halogen, preferably the chlorine, bromine or iodine atoms or the radical of a strong oxygen-acid, preferably the radical of a sulphur-oxygen-acid, e.g. the radical -OSO3, -OSO2-low-alkyl or -OSO2-aryl and, when Y1 or Y11 are H2N-, Z represents the group -COZ1, -SO2Z1 or -OCOZ1, wherein Z1 is halogen, preferably the chlorine atom.  Suitable alkylating agents of Formula V are bis-esters of diols of the formula HO-R6-OH which are derived from a hydrohalic acid or a strong oxygen acid.  Suitable acylating agents are dicarboxylic acid halides. Method B can only be used for the synthesis of compounds in which n = 2.  The dicarbonyl compounds of Formula II are obtained either by the usual aldehyde or ketone synthesis or, when n = 2, also by etherification or acylation of 1 mol of each of the corresponding carbonyl compounds of Formula VI and VIa by means of the bifunctional alkylating or acylating agents of Formula V.  These carbonyl compounds of Formula VI or VIa can also first be condensed with the malonic acid derivatives of Formulae III and IIIa as described above for method A, to form the methylene malonic acid derivatives of Formulae IV and IVa which can be further reacted according to method B.  Many compounds are exemplified.  In one example malonic acid dioctadecyl ester produced by reacting malonic acid and stearyl alcohol is reacted with p-hydroxy benzaldehyde to produce p - (2,2 - dicarbo - octadecyloxy - ethenyl)-phenol which is reacted with dibromobutane to produce 1,4 - bis - [4 - (2,2 - dicarbo - octa - decyloxy-ethenyl)-phenoxy]-butane.ALSO:Wood veneer is treated with a lacquer which retards the natural yellowings of the wood, the lacquer comprising cellulose acetate polybutylacrylate, or nitro &c. and a UV absorbent compound, e.g. p-bis-[4-(2,2-dicarboethoxyethenyl)-phenoxy]-methyl]-benzene, 1, 2 - bis-[4-(1-phenyl-2-cyano- 2 -carbomethoxy - ethenyl)-phenoxy]-ethane, p, p\sv-bis (1-phenyl - -2-cyano-2-carboethoxy-ethenyl) diphenyl oxide.