2-Keto-diazacycloalkane-urethane oligomers and U-V light stabilized compositions

Claim 2

A class of compounds comprising an oligomer of a 2-keto-1,4-diazacycloalkane and a urethane said oligomer ("2K-U oligomer") having the structure ##STR11## wherein, m represents an integer in the range from 0 to 5, being the number of methylene groups forming a bridge of variable length between the ring N atoms, and some of which groups (a) together with the carbons to which they are bound, may form a cyclopentyl, cyclohexyl or cycloheptyl endo ring, or (b) be substituted; so that, when m is 0, the 2KDZC moiety is a piperazinone ring; when m is 1 the 2KDZC moiety is a 5-keto-1,4-diazacycloheptane ring; when m is 4 and cyclized with the other two contiguous C atoms to form an endo ring, the 2KDZC moiety is decahydroquinoxalinone; x represents an integer in the range from 2 to about 15; R is selected from the group consisting of alkylene having from 2 to about 12 carbon atoms, toluyl, diphenylmethyl, naphthyl, dimethyl-biphenyl, dimethoxy-biphenyl, methylcyclohexyl, dicyclohexylmethyl, xylyl, isophoronyl, and trimethylhexyl; R 1 , R 2 , R 3 and R 4 are independently selected from the group consisting of hydrogen, aryl, alkyl having from 1 to about 24 carbon atoms, cycloalkyl having from 5 to about 7 carbon atoms, aralkyl having from 7 to about 20 carbon atoms, cycloalkyl having from 2 to about 12 carbon atoms, ether having from 4 to about 18 carbon atoms, and hydroxyalkyl having from 1 to about 18 carbon atoms; R 1 and R 2 together, or R 3 and R 4 together, or each pair, may be cyclized forming a ring having from about 5 to about 8 carbon atoms; except that not more than one of R 1 , R 2 , R 3 or R 4 may be hydrogen, and no more than three of R 1 , R 2 , R 3 and R 4 may be cyclic; R 5 and R 7 are each polymethylene having from 2 to about 12 carbon atoms each of which polymethylene constitutes a connecting link distally connecting a 2-keto-diazacycloalkane moiety to a urethane group; and, R 6 is selected from the group consisting of polymethylene having from 2 to about 12 carbon atoms, xylenyl substituted or unsubstituted phenyl, which group is a connecting link distally connecting one 2-keto-1,4-diazacycloalkane moiety to another such moiety.

Claim 3

The compounds of claim 1 wherein m=0; x represents an integer in the range from about 2 to about 10; and, R 1 , R 2 , R 3 , and R 4 are independently selected from lower alkyl having from 1 to about 5 carbon atoms.

Claim 4

The compounds of claim 1 wherein m=1; x represents an integer in the range from 2 to about 10; and, R 1 , R 2 , R and R 4 are independently selected from lower alkyl having from 1 to about 5 carbon atoms.

Claim 5

The compounds of claim 1 wherein m=4 and cyclized with the other two C atoms of said bridge to form an endo ring so that each 2KDZC moiety is a polysubstituted decahydroquinoxalinone; x represents an integer in the range from 2 to about 10; and, R 1 , R 2 , R 3 and R 4 are independently selected from lower alkyl having from 1 to about 5 carbon atoms.

Claim 6

The compounds of claim 1 wherein R 5 and R 7 are each polymethylene having from 2 to about 5 carbon atoms.

Claim 7

The compounds poly[oxycarbonylimino-1,6-hexanediyliminocarbonyloxy-1,2-ethanediyl(2,2,6,6-tetramethyl-3-oxo-1,4-piperazinediyl)-1,2-ethanediyl(3,3,5,5-tetramethyl-2-oxo-1,4-piperazinediyl)-1,2-ethanediyl]; poly[oxycarbonylimino(6-methyl-1,3-phenylene)iminocarbonyloxy-1,2-ethanediyl(2,2,6,6-tetramethyl-3-oxo-1,4-piperazinediyl)-1,2-ethanediyl(3,3,5,5-tetramethyl-2-oxo-1,4-piperazinediyl)-1,2-ethanediyl]; poly[oxycarbonylimino-1,4-phenylenemethylene-1,4-phenyleneimino-carbonyloxy-1,2-ethanediyl(2,2,6,6-tetramethyl-3-oxo-1,4-piperazinediyl)-1,2-ethanediyl(3,3,5,5-tetramethyl-2-oxo-1,4-piperazinediyl)-1,2-ethanediyl]; poly[oxycarbonyliminomethylene(1,5,5-trimethyl-1,3-cyclohexanediyl)iminocarbonyloxy-1,2-ethanediyl(2,2,6,6-tetramethyl-3-oxo-1,4-piperazinediyl)-1,2-ethanediyl(3,3,5,5-tetramethyl-2-oxo-1,4-piperazinediyl)-1,2-ethanediyl]; and, poly[oxycarbonylimino-1,4-cyclohexanediylmethylene-1,4-cyclohexanediyliminocarbonyloxy-1,2-ethanediyl(2,2,6,6-tetramethyl-3-oxo-1,4-piperazinediyl)-1,2-ethanediyl(3,3,5,5-tetramethyl-2-oxo-1,4-piperazinediyl)-1,2-ethanediyl].

Claim 8

The compounds poly[oxycarbonylimino-1,6-hexanediyliminocarbonyloxy-1,2-ethanediyl(2,2,6,6-tetramethyl-3-oxo-1,4-piperazinediyl)-1,2-ethanediyl(3,3,5,5-tetramethyl-2-oxo-1,4-piperazinediyl)-1,2-ethanediyl]; poly[oxycarbonylimino(6-methyl-1,3-phenylene)iminocarbonyloxy-1,2-ethanediyl(2,2,6,6-tetramethyl-3-oxo-1,4-piperazinediyl)-1,2-ethanediyl(3,3,5,5-tetramethyl-2-oxo-1,4-piperazinediyl)-1,2-ethanediyl]; poly[oxycarbonylimino-1,4-phenylenemethylene-1,4-phenyleneimino-carbonyloxy-1,2-ethanediyl(2,2,6,6-tetramethyl-3-oxo-1,4-piperazinediyl)-1,2-ethanediyl(3,3,5,5-tetramethyl-2-oxo-1,4-piperazinediyl)-1,2-ethanediyl]; poly[oxycarbonyliminomethylene(1,5,5-trimethyl-1,3-cyclohexanediyl)iminocarbonyloxy-1,2-ethanediyl(2,2,6,6-tetramethyl-3-oxo-1,4-piperazinediyl)-1,2-ethanediyl(3,3,5,5-tetramethyl-2-oxo-1,4-piperazinediyl)-1,2-ethanediyl]; and, poly[oxycarbonylimino-1,4-cyclohexanediylmethylene-1,4-cyclohexanediyliminocarbonyloxy-1,2-ethanediyl(2,2,6,6-tetramethyl-3-oxo-1,4-piperazinediyl)-1,2-ethanediyl(3,3,5,5-tetramethyl-2-oxo-1,4-piperazinediyl)-1,2-ethanediyl].

Claim 9

A composition of matter resistant to degradation by ultraviolet light comprising an organic material subject to ultraviolet light degradation having dispersed therein from about 0.01 part to about 5 parts by weight of a stabilizer compound consisting essentially of a bis compound of a polysubstituted 2-keto-1,4-diazacycloalkane distally linked through the N 4 atoms thereof to a urethane moiety, per 100 parts of said organic material, said stabilizer compound being represented by the structural formula ##STR12## wherein, m represents an integer in the range from 0 to 5, being the number of methylene groups forming a bridge of variable length between the ring N atoms, and some of which groups (a) together with the carbons to which they are bound, may form a cyclopentyl, cyclohexyl or cycloheptyl endo ring, or (b) be substituted; so that, when m is 0, the 2KDZC moiety is a piperazinone ring; when m is 1 the 2KDZC moiety is a 5-keto-1,4-diazacycloheptane ring; when m is 4 and cyclized with the other two contiguous C atoms to form an endo ring, the 2KDZC moiety is decahydroquinoxalinone; x represents an integer in the range from 2 to about 15; R is selected from the group consisting of alkylene having from 2 to about 12 carbon atoms, toluyl, diphenylmethyl, naphthyl, dimethyl-biphenyl, dimethoxy-biphenyl, methylcyclohexyl, dicyclohexylmethyl, xylyl, isophoronyl, and trimethylhexyl; R 1 , R 2 , R 3 and R 4 are independently selected from the group consisting of hydrogen, aryl, alkyl having from 1 to about 24 carbon atoms, cycloalkyl having from 5 to about 7 carbon atoms, aralkyl having from 7 to about 20 carbon atoms, cyanoalkyl having from 2 to about 12 carbon atoms, ether having from 4 to about 18 carbon atoms, and hydroxyalkyl having from 1 to about 18 carbon atoms; R 1 and R 2 together, or R 3 and R 4 together, or each pair, may be cyclized forming a ring having from about 5 to about 8 carbon atoms; except that not more than one of R 1 , R 2 , R 3 or R 4 may be hydrogen, and no more than three of R 1 , R 2 , R 3 and R 4 may be cyclic; R 5 and R 7 are each polymethylene having from 2 to about 12 carbon atoms each of which polymethylene constitutes a connecting link distally connecting a 2-keto-diazacycloalkane moiety to a urethane group; and, R 6 is selected from the group consisting of polymethylene having from 2 to about 12 carbon atoms, xylenyl and substituted or unsubstituted phenyl, which group is a connecting link distally connecting one 2-keto-1,4-diazacycloalkane moiety to another such moiety.

Claim 10

A composition of matter resistant to degradation by ultraviolet light comprising an organic material subject to ultraviolet light degradation having dispersed therein from about 0.01 part to about 5 parts by weight of a stabilizer compound consisting essentially of a bis compound of a polysubstituted 2-keto-1,4-diazacycloalkane distally linked through the N 4 atoms thereof to a urethane moiety, per 100 parts of said organic material, said stabilizer compound being represented by the structural formula ##STR12## wherein, m represents an integer in the range from 0 to 5, being the number of methylene groups forming a bridge of variable length between the ring N atoms, and some of which groups (a) together with the carbons to which they are bound, may form a cyclopentyl, cyclohexyl or cycloheptyl endo ring, or (b) be substituted; so that, when m is 0, the 2KDZC moiety is a piperazinone ring; when m is 1 the 2KDZC moiety is a 5-keto-1,4-diazacycloheptane ring; when m is 4 and cyclized with the other two contiguous C atoms to form an endo ring, the 2KDZC moiety is decahydroquinoxalinone; x represents an integer in the range from 2 to about 15; R is selected from the group consisting of alkylene having from 2 to about 12 carbon atoms, toluyl, diphenylmethyl, naphthyl, dimethyl-biphenyl, dimethoxy-biphenyl, methylcyclohexyl, dicyclohexylmethyl, xylyl, isophoronyl, and trimethylhexyl; R 1 , R 2 , R 3 and R 4 are independently selected from the group consisting of hydrogen, aryl, alkyl having from 1 to about 24 carbon atoms, cycloalkyl having from 5 to about 7 carbon atoms, aralkyl having from 7 to about 20 carbon atoms, cyanoalkyl having from 2 to about 12 carbon atoms, ether having from 4 to about 18 carbon atoms, and hydroxyalkyl having from 1 to about 18 carbon atoms; R 1 and R 2 together, or R 3 and R 4 together, or each pair, may be cyclized forming a ring having from about 5 to about 8 carbon atoms; except that not more than one of R 1 , R 2 , R 3 or R 4 may be hydrogen, and no more than three of R 1 , R 2 , R 3 and R 4 may be cyclic; R 5 and R 7 are each polymethylene having from 2 to about 12 carbon atoms each of which polymethylene constitutes a connecting link distally connecting a 2-keto-diazacycloalkane moiety to a urethane group; and, R 6 is selected from the group consisting of polymethylene having from 2 to about 12 carbon atoms, xylenyl and substituted or unsubstituted phenyl, which group is a connecting link distally connecting one 2-keto-1,4-diazacycloalkane moiety to another such moiety.

Claim 11

The composition of claim 7 wherein said stabilizer compound has a structure wherein m=0; x represents an integer in the range from about 2 to about 10; and, R 1 , R 2 , R 3 , and R 4 are independently selected from lower alkyl having from 1 to about 5 carbon atoms.

Claim 12

The composition of claim 8 wherein said stabilizer compound is selected from the group consisting of poly[oxycarbonylimino-1,6-hexanediyliminocarbonyloxy-1,2-ethanediyl(2,2,6,6-tetramethyl-3-oxo-1,4-piperazinediyl)-1,2-ethanediyl(3,3,5,5-tetramethyl-2-oxo-1,4-piperazinediyl)-1,2-ethanediyl]; poly[oxycarbonylimino(6-methyl-1,3-phenylene)iminocarbonyloxy-1,2-ethanediyl(2,2,6,6-tetramethyl-3-oxo-1,4-piperazinediyl)-1,2-ethanediyl(3,3,5,5-tetramethyl-2-oxo-1,4-piperazinediyl)-1,2-ethanediyl]; poly[oxycarbonylimino-1,4-phenylenemethylene-1,4-phenyleneimino-carbonyloxy-1,2-ethanediyl(2,2,6,6-tetramethyl-3-oxo-1,4-piperazinediyl)-1,2-ethanediyl(3,3,5,5-tetramethyl-2-oxo-1,4-piperazinediyl)-1,2-ethanediyl]; poly[oxycarbonyliminomethylene(1,5,5-trimethyl-1,3-cyclohexanediyl)iminocarbonyloxy-1,2-ethanediyl(2,2,6,6-tetramethyl-3-oxo-1,4-piperazinediyl)-1,2-ethanediyl(3,3,5,5-tetramethyl-2-oxo-1,4-piperazinediyl)-1,2-ethanediyl]; and, poly[oxycarbonylimino-1,4-cyclohexanediylmethylene-1,4-cyclohexanediyliminocarbonyloxy-1,2-ethanediyl(2,2,6,6-tetramethyl-3-oxo-1,4-piperazinediyl)-1,2-ethanediyl(3,3,5,5-tetramethyl-2-oxo-1,4-piperazinediyl)-1,2-ethanediyl].