Bis(alkyleneoxybenzophenone) ultraviolet light absorbers

The present invention relates to novel bisbenzophenones and the use thereof as an ultraviolet light absorber. The presently claimed compounds are particularly useful, either alone or in combination with other additives, including other ultraviolet light absorbers, antioxidants and stabilizers, in stabilizing polymers and other materials from degradation by environmental forces such as actinic radiation (ultraviolet light), oxidation, moisture, atmospheric pollutants and combinations thereof.

What is claimed is:

1. A bisbenzophenone compound of the general formula I: ##STR13##

wherein

each X, Y, Z, X', Y' and Z' is independently selected from hydrogen, hydrocarbyl, functional hydrocarbyl, alkyl, aryl, aralkyl, alkaryl, alkoxyl, aroxyl, carboxyl, carboalkoxy, cyano, hydroxyl, halogen, or an S, N or P atom substituted for a carbon atom of the ring;

each R and R' is independently selected from hydrocarbylene or functional hydrocarbylene; and

L is selected from a carbonyl group, a dicarbonyl group or hydrocarbylene.

2. The compound of claim 1, wherein L is carbonyl, as described in Formula II: ##STR14##

3. The compound of claim 2, wherein X, Y, Z, X', Y' and Z' are hydrogen, and R and R' are (CH.sub.2).sub.2, as described in Formula III: ##STR15##

4. The compound of claim 1, wherein L is a branched methylene group, and T and T' are independently selected from hydrogen, hydrocarbyl and functional hydrocarbyl, as described in Formula V: ##STR16##

5. A process for the preparation of a benzophenone compound of claim 1, which comprises:

reacting a hydroxyhydrocarbyl functional benzophenone, described by the following structure: ##STR17##

wherein R is a hydroxyalkyl group containing from one to about 10 carbon atoms, and X, Y and Z are as described above, with a carbonyl compound, for a sufficient time and at a suitable temperature and pressure, optionally in the presence of a catalyst to form a compound of claim 1.

6. A process for the preparation of a benzophenone compound of claim 1 which comprises the following steps:

(i) reacting a hydroxyhydrocarbyl functional benzophenone, described by the following structure: ##STR18##

wherein R is a hydroxyalkyl group containing from one to about 10 carbon atoms, and X, Y and Z are as described above, with a carbonyl compound for a sufficient time and at a suitable temperature and pressure, optionally in the presence of a catalyst, to form a first reaction product; and

(ii) reacting the first reaction product with additional hydroxyhydrocarbyl functional benzophenone wherein the hydroxyalkyl group contains from 1 to about 10 carbon atoms to form a compound of claim 1.

7. The process of claim 5, wherein the hydroxyhydrocarbyl functional benzophenone is 2-hydroxy-4-hydroxyethoxy benzophenone, and the carbonyl compound is a dialkyl carbonate or dialkyl oxalate.

8. The process of claim 7, wherein each alkyl group of the carbonyl compound contains from one to about 4 carbon atoms.

9. The process of claim 8, wherein each alkyl group of the carbonyl compound is a methyl group.

10. The process of claim 5, wherein the catalyst is an inorganic acid, an organic acid, a Lewis acid or a base.

11. The process of claim 10, wherein the acid catalyst is RCO.sub.2 H, RSO.sub.3 H, RsO.sub.2 H, RSH, ROH, RPO.sub.3 H, RPO.sub.2 H, wherein R is a hydrocarbyl group, HCl, HBr, HI, HNO.sub.3, HNO.sub.2, H.sub.2 S, H.sub.2 SO.sub.4, H.sub.2 CO.sub.3, acetic acid, formic acid, propionic acid, butanoic acid, benzoic acid, phthalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, methanesulfonic acid, p-toluenesulfonic acid, aluminum halides, alkylaluminum halides, boron halides, dialkyl tin oxides and derivatives thereof, tin halides, titanium halides, lead halides, zinc halides, iron halides, gallium halides, arsenic halides, copper halides, cadmium halides, mercury halides, antimony halides and mixtures thereof.

12. The process of claim 10, wherein the Lewis acid catalyst is aluminum trichloride, aluminum tribromide, 1,3-diacetoxy-1,1,3,3-tetrabutyldistannoxane, trimethylaluminum, boron trifluoride, boron trichloride, zinc dichloride, titanium tetrachloride, titanium (IV) isopropoxide, tin dichloride, tin tetrachloride, a tetraalkoxytitanate or mixtures thereof.

13. The process of claim 10, wherein the base catalyst is an alkoxide compound, a hydroxide compound, an amide compound, a carbonate compound, a bicarbonate compound, an organic amine including triethylamine, 2,6-lutidine, DBU (1,8-diazobicyclo[5.4.0]undec-7-ene, or DBN (1,5-diazobicyclo[4.3.0]non-5-ene, a tertiary amine compound.

14. The process of claim 13, wherein the base catalyst is sodium methoxide.

15. The process of claim 5, wherein the catalyst is present in an amount between about 0.5 to about 30 molar percent based on the molar amount of benzophenone.

16. The process of claim 15, wherein the catalyst is present in an amount between about 0.5 to about 5 molar percent based on the molar amount of hydroxyhydrocarbyl functional benzophenone.

17. The process of claim 5, wherein the solvent is excess dialkyl carbonate, excess dialkyl oxalate, toluene, xylene, benzene, mesitylene, tetralin, naptha, hexane, heptane, cyclohexane, octane, an alcohol, a halogenated solvent including methylene chloride, chloroform, chlorobenzene, an ether including diethyl ether, diphenyl ether, dioxane and tetrahydrofuran, an amide including dimethylformamide, a sulfoxide including dimethyl sulfoxide, a ketone including 2-butanone and methyl butyl ketone and mixtures thereof.

18. The process of claim 5, wherein the reaction is carried out at a temperature of from about 25.degree. C. to about 250.degree. C.

19. The process of claim 5, wherein the reaction is carried out at a temperature of from about 75.degree. C. to about 150.degree. C.

20. A process for the preparation of a benzophenone compound of claim 1, which comprises:

reacting a hydroxyhydrocarbyl functional benzophenone, described by the following structure: ##STR19##

wherein R is a hydroxyalkyl group containing from one to about 10 carbon atoms, and X, Y and Z are as described above, with a halogenated compound selected from the group consisting of phosgene, diphosgene, triphosgene and oxalyl chloride for a sufficient time, and at a suitable temperature and pressure, optionally in the presence of a catalyst, to form a compound of claim 1.

21. The process of claim 20, which further comprises adding a stoichiometric amount of base based on the molar amount of hydroxyhydrocarbyl functional benzophenone.

22. The process of claim 20, wherein the base is selected from ammonia, a hydroxide compound, an amide compound, a carbonate compound, a bicarbonate compound, an organic amine including triethylamine, 2,6-lutidine, DBU (1,8-diazobicyclo[5.4.0.]undec-7-ene, or DBN (1,5-diazobicyclo[4.3.0]non-5-ene, a tertiary amine compound, and mixtures thereof.

23. The process of claim 20, wherein the solvent is selected from toluene, xylene, benzene, mesitylene, tetralin, naptha, hexane, heptane, cyclohexane, octane, an alcohol, a halogenated solvent including methylene chloride, chloroform, chlorobenzene, an ether including diethyl ether, diphenyl ether, dioxane and tetrahydrofuran, an amide including dimethylformamide, a sulfoxide including dimethyl sulfoxide, a ketone including 2-butanone and methyl butyl ketone and mixtures thereof.

24. The process of claim 20, wherein the reaction is carried out at a temperature of from about -100.degree. C. to about 175.degree. C.

25. The process of claim 20, wherein the reaction is carried out at a temperature of from about 0.degree. C. to about 100.degree. C.

26. A process for the preparation of a benzophenone compound of claim 2, which comprises:

reacting a hydroxy functional benzophenone, described by the following structure: ##STR20##

wherein R is hydrogen, and X, Y and Z are as described above, with a bis(2-haloalkyl)carbonate wherein the alkyl group of the bis(2-haloalkyl)carbonate contains from 1 to about 10 carbon atoms, for a sufficient time, and at a suitable temperature and pressure, optionally in the presence of a catalyst, to form a compound of claim 2.

27. The process of claim 26, wherein the hydroxy functional benzophenone is 2,4 dihydroxybenzophenone, and the bis(2-haloalkyl)carbonate is bis(2-haloethyl)carbonate.

28. The process of claim 26, wherein the base is selected from ammonia, a hydroxide compound, an amide compound, a carbonate compound, a bicarbonate compound, an organic amine including triethylamine, 2,6-lutidine, DBU (1,8-diazobicyclo[5.4.0]undec-7-ene, or DBN (1,5-diazobicyclo[4.3.0]non-5-ene, a tertiary amine compound, and mixtures thereof.

29. The process of claim 26, wherein the solvent is selected from toluene, xylene, benzene, mesitylene, tetralin, naptha, hexane, heptane, cyclohexane, octane, an alcohol, a halogenated solvent including methylene chloride, chloroform, chlorobenzene, an ether including diethyl ether, diphenyl ether, dioxane and tetrahydrofuran, an amide including dimethylformamide, a sulfoxide including dimethyl sulfoxide, a ketone including 2-butanone and methyl butyl ketone and mixtures thereof.

30. The process of claim 26, wherein the reaction is carried out at a temperature of from about 25.degree. C. to about 250.degree. C.

31. The process of claim 26, wherein the reaction is carried out at a temperature of from about 75.degree. C. to about 200.degree. C.

32. The process of claim 26, which further comprises adding a stoichiometric amount of base based on the molar amount of hydroxy functional benzophenone.

33. The process of claim 31, wherein the base is selected from potassium hydroxide and sodium hydroxide.

34. A process for the preparation of a benzophenone compound of claim 2, which comprises:

reacting a hydroxyhydrocarbyl functional benzophenone, described by the following structure: ##STR21##

wherein R is a hydroxyalkyl group containing from one to about 10 carbon atoms, and X, Y and Z are as described above, with a compound selected from carbon monoxide, carbon dioxide, urea and alkyl carbamate, for a sufficient time, and at a suitable temperature and pressure, optionally in the presence of a catalyst, to form a compound of claim 2.

35. The process of claim 34, wherein the alkyl carbonate contains an alkyl group containing from one to about 10 carbon atoms.

36. The process of claim 34, wherein the solvent is selected from toluene, xylene, benzene, mesitylene, tetralin, naptha, hexane, heptane, cyclohexane, octane, an alcohol, a halogenated solvent including methylene chloride, chloroform, chlorobenzene, an ether including diethyl ether, diphenyl ether, dioxane and tetrahydrofuran, an amide including dimethylformamide, a sulfoxide including dimethyl sulfoxide, a ketone including 2-butanone and methyl butyl ketone and mixtures thereof.

37. The process of claim 34, wherein the reaction is carried out at a temperature of from about 25.degree. C. to about 300.degree. C.

38. The process of claim 26, wherein the reaction is carried out at a temperature of from about 75.degree. C. to about 250.degree. C.

39. The process of claim 26, wherein the reaction is carried out at a pressure greater than one atmosphere.

40. A polymeric article comprising at least one polymeric material and a sufficient amount of a stabilizing composition to inhibit at least one of photo or thermal degradation, wherein the stabilizer composition comprises one or more compounds of general formula I: ##STR22##

wherein

each X, Y, Z, X', Y' and Z' is independently selected from hydrogen, hydrocarbyl, functional hydrocarbyl, alkyl, aryl, aralkyl, alkaryl, alkoxyl, aroxyl, carboxyl, carboalkoxy, cyano, hydroxyl, halogen, or an S, N or P atom substituted for a carbon atom of the ring;

each R and R' is independently selected from hydrocarbylene or functional hydrocarbylene; and

L is selected from a carbonyl group, a dicarbonyl group or hydrocarbylene.

41. A polymeric article of claim 40, wherein the stabilizer composition comprises one or more compounds of Formula III, wherein Formula III has the general formula: ##STR23##

42. The polymeric article of claim 40, wherein the amount of stabilizer composition is from about 0.01 to about 20 percent by weight of the polymeric material.

43. The polymeric article of claim 40, wherein the polymeric material is selected from the group consisting of polyolefins; polyesters; polyethers; polyketones; polyamides; natural and synthetic rubbers; polyurethanes; polystyrenes; high-impact polystyrenes; polyacrylates; polymethacrylates; polyacetals; polyacrylonitriles; polybutadienes; polystyrenes; ABS; SAN (styrene acrylonitrile); ASA (acrylate styrene acrylonitrile); cellulosic acetate butyrate; cellulosic polymers; polyimides; polyamideimides; polyetherimides; polyphenylsulfides; PPO; polysulfones; polyethersulfones; polyvinylchlorides; polycarbonates; polyketones; aliphatic polyketones; thermoplastic TPO's; aminoresin crosslinked polyacrylates and polyesters; polyisocyanate crosslinked polyesters and polyacrylates; phenol/formaldehyde, urea/formaldehyde, and melamine/formaldehyde resins; drying and non-drying alkyd resins; alkyd resins; polyester resins; acrylate resins cross-linked with melamine resins, urea resins, isocyanates, isocyanurates, carbamates, and epoxy resins; cross-linked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic and aromatic glycidyl compounds which are cross-linked with anhydrides or amines; polysiloxanes; Michael addition polymers of amines or blocked amines with activated unsaturated and methylene compounds, ketimines with activated unsaturated and methylene compounds, polyketimines in combination with unsaturated acrylic polyacetoacetate resins, and polyketimines in combination with unsaturated acrylic resins; radiation curable compositions; epoxymelamine resins; organic dyes; cosmetic products; cellulose-based paper formulations; photographic film paper; ink; and blends thereof.

44. The polymeric article of claim 40, wherein the stabilizer composition further comprises one or more hindered amine light stabilizers.

45. The polymeric article of claim 40, wherein the stabilizer composition further comprises one or more additional UV light absorbers selected from the group consisting of a benzotriazole, a triazine, a benzophenone, and mixtures thereof.

46. The polymeric article of claim 40, wherein the stabilizer composition further comprises at least one additional additive.

47. The polymeric article of claim 38, wherein the additive is selected from the group consisting of: antioxidants, ultraviolet light absorbers, ultraviolet light stabilizers, metal deactivators, phosphites, phosphonites, hydroxylamines, nitrones, thiosynergists, peroxide scavengers, polyamide stabilizers, nucleating agents, fillers, reinforcing agents, plasticizers, lubricants, emulsifiers, pigments, rheological additives, flameproofing agents, antistatic agents, blowing agents, benzofuranones and indolinones.

48. A multilayer polymeric article comprising a polymeric article having at least one surface and a thin film of polymer composition applied to the at least one surface that comprises a sufficient amount of at least one compound of general formula I to inhibit at least one of photo or thermal degradation, wherein formula I has the structure: ##STR24##

wherein

each X, Y, Z, X', Y' and Z' is independently selected from hydrogen, hydrocarbyl, functional hydrocarbyl, alkyl, aryl, aralkyl, alkaryl, alkoxyl, aroxyl, carboxyl, carboalkoxy, cyano, hydroxyl, halogen, or an S, N or P atom substituted for a carbon atom of the ring;

each R and R' is independently selected from hydrocarbylene or functional hydrocarbylene; and

L is selected from a carbonyl group, a dicarbonyl group or hydrocarbylene.

49. The multilayer polymeric article of claim 48, wherein the compound to inhibit at least one of photo or thermal degradation, is a compound of Formula III, wherein Formula III has the structure: ##STR25##

50. The multilayer polymeric article of claim 48, wherein the thin film is applied to each surface of the polymeric article.

51. The multilayer polymeric article of claim 48, wherein the amount of the compound is from about 0.1 to 20 percent by weight of the thin film.

52. The multilayer polymeric article of claim 48, wherein the thin film is from about 5 to 500 .mu.m in thickness.

53. The multilayer polymeric article of claim 48, wherein the article is prepared by a coextrusion process.

54. The multilayer polymeric article of claim 48, wherein the article comprises a compound of Formula III, wherein Formula III has the structure: ##STR26##

55. A coating comprising a sufficient amount of at least one compound of general formula I to inhibit at least one of photo or thermal degradation, wherein formula I has the structure: ##STR27##

wherein

each X, Y, Z, X', Y' and Z' is independently selected from hydrogen, hydrocarbyl, functional hydrocarbyl, alkyl aryl, aralkyl, alkaryl, alkoxyl, aroxyl, carboxyl, carboalkoxy, cyano, hydroxyl, halogen, or an S, N or P atom substituted for a carbon atom of the ring;

each R and R' is independently selected from hydrocarbylene or functional hydrocarbylene; and

L is selected from a carbonyl group, a dicarbonyl group or hydrocarbylene.

56. The coating of claim 55, wherein the compound to inhibit at least one of photo or thermal degradation is a compound of Formula III, wherein Formula III has the structure: ##STR28##

57. The coating of claim 55, wherein the amount of the at least one compound is from about 0.01 to 20 percent by weight of the coating.

58. A concentrate comprising a polymeric resin and from about 2.5 to about 25 percent of at least one compound of general formula I, wherein formula I has the structure: ##STR29##

wherein

each X, Y, Z, X', Y' and Z' is independently selected from hydrogen, hydrocarbyl, functional hydrocarbyl, alkyl, aryl, aralkyl, alkaryl, alkoxyl, aroxyl, carboxyl, carboalkoxy, cyano, hydroxyl, halogen, or an S, N or P atom substituted for a carbon atom of the ring;

each R and R' is independently selected from hydrocarbylene or functional hydrocarbylene; and

L is selected from a carbonyl group, a dicarbonyl group or hydrocarbylene.

59. The concentrate of claim 58, wherein the concentrate comprises the compound of Formula III, wherein Formula III has the structure: ##STR30##

60. A cosmetic composition comprising a sufficient amount of at least one compound of general formula I, wherein formula I has the structure: ##STR31##

wherein

each X, Y, Z, X', Y' and Z' is independently selected from hydrogen, hydrocarbyl, functional hydrocarbyl, alkyl, aryl, aralkyl, alkaryl, alkoxyl, aroxyl, carboxyl, carboalkoxy, cyano, hydroxyl, halogen, or an S, N or P atom substituted for a carbon atom of the ring;

each R and R' is independently selected from hydrocarbylene or functional hydrocarbylene; and

L is selected from a carbonyl group, a dicarbonyl group or hydrocarbylene.

61. The cosmetic composition of claim 60, wherein the composition comprises at least one compound of Formula III, wherein Formula III has the structure: ##STR32##

62. A method of stabilizing a material that is subject to at least one of photo or thermal degradation by incorporating into or onto the material an amount of one or more stabilizer compositions in an amount effective to stabilize the material against at least one of photo or thermal degradation, wherein the stabilizer composition comprises one or more compounds of general formula I, wherein formula I has the structure: ##STR33##

wherein

each X, Y, Z, X', Y' and Z' is independently selected from hydrogen, hydrocarbyl, functional hydrocarbyl, alkyl, aryl, aralkyl, alkaryl, alkoxyl, aroxyl, carboxyl, carboalkoxy, cyano, hydroxyl, halogen, or an S, N or P atom substituted for a carbon atom of the ring;

each R and R' is independently selected from hydrocarbylene or functional hydrocarbylene; and

L is selected from a carbonyl group, a dicarbonyl group or hydrocarbylene.

63. The method of claim 62, wherein the stabilizer composition comprises one or more compounds of Formula III, wherein Formula III has the structure: ##STR34##

64. The method of claim 62, wherein the stabilizer composition is incorporated in an amount of from about 0.01 to about 20 percent by weight of the material to be stabilized.

65. The method of claim 48, wherein the material to be stabilized is polymeric.

66. The method of claim 65, wherein the polymeric material is selected from the group consisting of polyolefins; polyesters; polyethers; polyketones; polyamides; natural and synthetic rubbers; polyurethanes; polystyrenes; high-impact polystyrenes; polyacrylates; polymethacrylates; polyacetals; polyacrylonitriles; polybutadienes; polystyrenes; ABS; SAN (styrene acrylonitrile); ASA (acrylate styrene acrylonitrile); cellulosic acetate butyrate; cellulosic polymers; polyimides; polyamideimides; polyetherimides; polyphenylsulfides; PPO; polysulfones; polyethersulfones; polyvinylchlorides; polycarbonates; polyketones; aliphatic polyketones; thermoplastic TPO's; aminoresin crosslinked polyacrylates and polyesters; polyisocyanate crosslinked polyesters and polyacrylates; phenol/formaldehyde, urea/formaldehyde, and melamine/formaldehyde resins; drying and non-drying alkyd resins; alkyd resins; polyester resins; acrylate resins cross-linked with melamine resins, urea resins, isocyanates, isocyanurates, carbamates, and epoxy resins; cross-linked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic and aromatic glycidyl compounds which are cross-linked with anhydrides or amines; polysiloxanes; Michael addition polymers of amines or blocked amines with activated unsaturated and methylene compounds, ketimines with activated unsaturated and methylene compounds, polyketimines in combination with unsaturated acrylic polyacetoacetate resins, and polyketimines in combination with unsaturated acrylic resins; radiation curable compositions; epoxymelamine resins; organic dyes; cosmetic products; cellulose-based paper formulations; photographic film paper; ink; and blends thereof.

67. The method of claim 62, wherein the material has one or more surfaces and the stabilizer composition is applied to at least one surface of the material.

68. The method of claim 67, wherein the stabilizer composition is part of a coating that is applied to the at least one surface of the material.

69. The method of claim 67, wherein the stabilizer composition is part of a capstock layer that is applied to the at least one surface of the material.

70. The method of claim 67, wherein the material is metallic, wood, ceramic, polymeric, or a fiber material.

71. The method of claim 62, further comprising forming the material into a fiber.

72. The method of claim 71, wherein the material is selected from the group consisting of silk, leather, wool, polyamide, polyurethane, cellulose-containing fibers, and blends thereof.

73. The method of claim 62, wherein the material is a photographic material.

74. The method of claim 62, wherein the material is a cosmetic composition.