STABILIZED TITANIUM DIOXIDE-PIGMENTED POLYOLEFIN COMPOSITIONS

Abstract: Polyolefin compositions which are pigmented with titanium dioxide are rendered actinic radiation stabilized by incorporating therein a C₁₂₋₂₀ alkyl ester of 3,5-di-tertabutyl-­ 4-hydroxybenzoic acid.

Description: STABILIZED TITANIUM DIOXIDE-PIGMENTED POLYOLEFIN COMPOSITIONS The present invention relates to the stabilization of titanium dioxide-pigmented polyolefin compositions against degradation caused by actinic radiation, particularly VV-radiation. More particularly, it relates to the use of C12-C20 alkyl esters of 3,5-di-tert.butyl-4-hydroxy- benzoic acid as light stabilizers for polypropylene, ethylenepropylene copolymer, and high-density polyethylene, containing a pigmenting amount of titanium dioxide. The invention particularly relates to the use of n-headecyl 3,5-di-tert.butyl-4-hydroxybenzoate as a light stabilizer for titanium dioxide-pigmented high-density polyethylene (EDPE). Pigmented polyolefins have wide use in diverse products. TiO2-pigmented HYPE, especially, finds wide use in camper tops, stadium seats, and food containers, particularly large storage containers for grain and the like. Presently used light stabilizers, such as certain 2 hydroxy- 4 -alkoxy benz ophenones and nickel-n-butyl amine complexes of 2,2'-thiobis(p-tert.octyl phenol), provide acceptable levels of protection against UV-degradation; however, there is a continuing need for improved light stabilizers, particularly for use in food containers. Tert.butylphenyl salicylate is believed to be the only compound acceptable for broad use in contact with food products; however, it is not a very effective light stabilizer. In accordance with the present invention, it has been discovered that higher alkyl esters, that is C12 to C20 alkyl esters, of 3,5-di-tert.butyl-4-hydroxybenzoic acid provide unexpectedly' high levels of protection against W-degradation when used in titanium dioxide-pigmented polyolefins. Moreover, n-hexadecyl 3 ,5-di-tert.butyl-4- hydroxybenzoate provides exceptional light stability in. titanium dioxide-pigmented high-density polyethylene. U. S. Patent 3,206,431 discloses the use of alkyl esters of 3,5-di-tert.butyl-4-hydroxybenzoic acid as light stabilizers for polyolefins in combination with a hindered phenol antiosidant. U. S. Patents 3,681,431 and 3,285,855 disclose the use of n-octadecyl 3,5-di-tert.butyl-4-hydroxybenzoate as an antioxidant for polyolefins. British Patent l,336,931 teaches the use of aryl esters of 3,5-di-tert.butyl-4-hydroxybenzoic acid as light stabilizers for polyolefins in combination with a benzcphenone and a percxide decomposer. U. S. Patent 3,502,613 teaches a synergistic combination of an aryl ester of 3,5-di-tert.butyl-4-hydroxybenzoic acid, a chlorobenzotriazole, a phenolic antioxiaant, and a thiodipropionate ester as a light stabilizer for polypropylene. Finally, Stretanski, in U. S. S. N. 951,230 now U. S. Patent No. discloses a light stabilizer composition for polyolefins comprising n-hexadecyl 3,5-di-tert.butyl-4-hy- droxybenzoate and a dialkyl pentaerythrityl diphosphite. None of. the aforementioned patents teach or suggest the high level of light stability provided to titanium dioxide-pigmented polyolefins by the incorporation therein of a C12 to C20 alkyl ester of 3,5-di-tert.butyl 4-hydroxybenzoic acid. Moreo er, there. is no suggestion that the incorporation of a higher alkyl ester of 3,5-di- tert.butyl-4-hydroxybenzoic acid into titanium dioxide- pigmented high-density polyethylene will provide unexpectedly high levels of light stability. The degree of light stability afforded by the esters of the present invention is unexpected, especially in TiO2-pigmented high-density polyethylene, because a similar degree of protection is not realized with aryl esters, for example, the 2,4-ditert.butylphenyl ester of 3,5-di-tert.butyl-4-hydroxybenzoic acid of the aforementioned British patent, nor with other commonly used light stabilizers, such as 2-hydroxy-4octyloxybenzophenone, 2- (2 '-hydroxy-3' '5 '-di-tert.butyl- phenyl) -4-chlorobenzotriazole, or the nickel-butylamine complex of 2,2'-thiobis(p-tert.octylphenol). The higher alkyl esters of 3,5-di-tert.butyl-4hydroxybenzoic acid are known compounds, prepared according to procedures described in U. S. Patent 3,681,431 for the preparation of n-octadecyl analog, except that other higher alcohols are used instead of n-octadecanol. The term "titanium dioxide-pigmented" means any polyolefin to which the present invention relates, such as polypropylene, ethylene-propylene copolymer, and high-density polyethylene, containing at least about 2% by weight of TiO2, although more may be used. Other pigments, of course, may be used in combination with TiO2 in such polymer compositions to provide a wide range of colors and shades. Commonly used pigments for such purposes include cadmium red, chrome yellow, and.molybdenum orange inorganic pigments, and diarylide yellow, Pigment Red 48, phthalo- cyanine.blue and green organic-pigments, and the like. The amount of such additional colorants used will vary widely and the invention is not limited to any amount. The amount of C12-C20 alkyl ester used will generally fall within the range of about 0.1-2 percent by weight, although about 0.2-1 percent is generally effective. Although the benefits of the invention are provided by the: use of the esters alone, additional benefits may be obtained by the use of a combination of the ester with a dialkyl pentaerythrityl diphosphite, as disclosed in the aforementioned Stretanski application, the disclosure of which is incorporated herein by reference. -- Other commonly used additives for polyolefins in general, and high-density polyethylene in particular, may be incorporated into the polymer, such as antioxidants, other light stabilizers, lubricants, and so forth. Example 1 Two commercial grades of high density polyethylene (I, Rigidex 002-55P, British Petroleum; and II, Rumiten 2745, Rlmianca) were compounded with the light stabilizers shown in the following table, with and without the additional presence of 2.5 percent titanium dioxide. The compounds were incorporated into the polymer at a temperature of l75-l850C and compression molded into films at 180-185 C. The films were exposed in a Xenotest 150 at 25 + 50C/60 + 108 relative humidity using.a rain cycle of 5 minutes rain, 25 minutes dry. The films were removed periodically and the carboxyl content determined. Failure is determined to occur at a change in carbonyl content of 0.058. Compounds tested were: A. n-hexadecyl 3 ,5-di-tert.butyl-4-hydroxy- benzoate B. 2-hydroxy-4-octyloxybenzophenone C. n-butylamine-nickel complex of 2,2' thiobis(p-t.octylphenol) D. 2- (2 '-hydroxy-31 .5'-di-tert.butylphenyl) - 4-chlorobenzotriazole Data are shown in the accompanying table. The data show that n-hexadecyl 3,5-di-tert.butylbenzoate (A) provides unexpectedly better light stability to tianium dioxide-pigmented high density polyethylene than other commonly used light stabilizer compounds. TABLE I Hours to #CO = 0.05% Stabilizer Percent Polymer I Polymer II Polymer I Polymer II Alone + 2.5% TiO2 Alone + 2.5% TiO2 None - 250 720 250 440 A 0.5 2900 5060 1390 4650 B 0.5 3150 960 870 860 C 0.5 3240 3850 1420 3470 D 0.5 1520 850 620 570

Claims: WHAT IS CLAIMED IS: 1. A composition stable toward degradation caused by actinic radiation comprising a polyolefin selected from the group consisting of polypropylene, ethylenepropylene copolymers, and high-density polyethylene, at least about 2 percent by weight of titanium dioxide, and an actinic. radiation stabilizing amount of a C12 to C20 alkyl ester of 3,5-di-tert.butyl-4-hydroxybenzoic acid. 2. The composition of Claim 1 wherein said polyolefin is high-density polyethylene. 3. The composition of Claim I wherein said polyolefin is a copolymer of ethylene and propylene. 4. The composition of Claim 2 whereinsaid ester is n-hexadecyl 3, 5-di-tert.butyl-4-hydroxybenzoate. 5. The composition of Claim 1 wherein said ester comprises from about 0.1 to 2 percent by weight of said composition. 6. The composition of Claim 1 wherein said composition additionally contains a dialkyl pentaerythrityl diphosphite. 7. The composition of Claim 1 wherein said composition additionally contains one or more inorganic or organic colored pigments. 8. A method of actinic radiation stabilizing a polyolefin selected from the group consisting of polypropylene, ethylene-propylene copolymers, and high-density polyethylene, containing at least 2 percent by weight of titanium dioxide, which comprises incorporating therein from about 0.1 to 2 percent by weight of a C12 to C20 alkyl ester of 3 ,5-di-tert.butyl-4-hydroxybenzoic acid. 9. The method of Claim 8 wherein said ester is n-hexadecyl 3 ,5-di-tert.butyl-4-hydroxybenzoate.

Inventors: LOFFELMAN, FRANK FRED, STRETANSKI, JOSEPH A.
Applicants: AMERICAN CYANAMID COMPANY
Application year: 1981
Main classification: C08K3
IPC codes: C08L23, C08L7, C08L101, C08L21, C08K5, C08K3