COMBINATION OF PHENOLIC ANTIOXIDANT AND STABILISER FOR USE IN ORGANIC MATERIALS

Abstract: Organic materials such as polypropylene are stabilized with a mixture of (A) N,N′-bis[2-(3-[3,5-di-t-butyl-hydroxyphenyl]­ propionyloxy)ethyl]oxamide with one of the following stabilizers: (B₁) 2-hydroxy-4-n-octoxybenzophenone; (B₂) 2-(3,5-di-t-butyl-5-hydroxypheny)-5-chlorobenzo­ triazole; or (B₃) N-hydroxyethyl-2,2,6,6-tetramethylpiperidino suc­ cinic acid ester.

Description: COMBINATION OF PHENOLIC ANTlOXID ANT AND STABILIZER FOR USE IN ORGANIC MATERIAL This invention relates to a combination of antioxidant and stabilizer for organic materials. More particularly the invention relates to stabilizing compositions comprising a mixture of (A) the phenolic antioxidant N,Ntbis [2-(3- j3 ,5-di-t-butyl -4-hydroxyphenyll-propionyloxy)el:hylloxarnide¯ with one of the following stabilizers: (B1) 2-hydroxy-4-n-octoxybenzoph enone; (B2) 2- (2, 5-di-t-butyl-2-hydroxypheny i)-5- cMorobenzo- triazole; or (B3) N-hydroxyethyl-2 ,2, 6, 6-tetramethylpiperidino succin ic acid ester. The protection of organic materials, especially polymers, normally subject to deterioration over a period of time by exposure to such adverse influences as the weather (especially ul traviolet light), by the addition of various antioxidants and stabilizers has previously been known, but it has been desired to provide more satisfactory protection in an economical and convenient manner. Typical prior stabilization practices are illustrated in Canadian Serial No. 318,249, Hirsch et awl., Dec. 20, 1978; U. S. patents 2,154,723, Hirsch et al, May 15, 1979; 4,187,212; Zinka et al, Feb 5, 1980; and 4,104,248, Cantatore, Aug. 1, 1978. The present invention is based on the surprising discovery that a remarkably high level of protection is achieved by employing a combination of the phenolic antioxidant (A) described above with one of the stabilizers (B) described above, as the stabilizer system. The phenolic antioxidant (A) and the stabilizers (B) described above employed in the stabilizing mixtures of the invention are known materials. The ratio of phenolic antioxidant compound (A) to stabilizer compound (B) employed in the mixed stabilizer composition of invention may vary widely, for example from 1:9 to 9:1, preferably from 2:8 to 8;2, and more preferably from 4:6 to 6:4, by weight. To stabilize an organic material in accordance with the invention the material is mixed by any suitable conventional means, with the phenolic antioxidant compound (A) and one of the described stabilizer compounds (B), separately or together, in a stabilizingly effective amount. Remarkably small quantities of the mixed stabil- izer composition of the invention are effective, e.g., from 0 - 005% or less to 5% or more, preferably from 0.05 to r, more preferably from 01 to 0. 5%, based on the weight of the: material to be stabilized. The optimum amount id aiiy given case will depend on such variables as the degree of stabilization desired, the particular material being stabilized, etc. and is readily determinable with the aid of standard tests for evaluating stabilizers in various materials. If desired, the stabilizer composition of the invention can be employed in combination with other stabilizers, e. g. dilauryl or distearyl beta-thiodipropionate, antiozonants, thermal stabilizers, ultraviolet light absorbers and/or with coloring materials, dyes, pigments, metal chelating agents, etc. The organic materials which can be stabilized in accordance with this invention by admixing with phenolic antioxidant (A) and stabilizer (B) include polyolefins which can be homopolymers of unsubstituted olefinic hydrocarbons such as, e.g. ethylene, propylene, 1-butylene-, 1 ,3-butadiene and styrene, homopolb mers of substituted olefinic hydrocarbons such as, e.g.- vinyl halides such as vinyl chloride and esters such as acetate, vinyl alcohols, acrylonitrile and methacrylonitrile, or copolymers of two or more of such stubstituted and/or unsubstituted olefinic hydrocarbons. Also included are condensation polymers such as, e. g. polyalkylene oxides, polyurethanes, polycarbonates, polyesters such as polyethylene terephthalates and polyamides such as polyhexamethylene adipamide and polycaprolactam. Other organic materials which can be stabilized by this invention include lubricating oils, e.g. of the aliphatic ester type such as di(2-ethylhexyl)azelate and pentaerythritol tetracaprolate, animal and vegetable derived oils such as linseed oil, fat, tallow, lard, peanut oil, cod liver oil, castor oil, palm oil, corn oil and cottonseed oil, fatty acids such as soaps, and other hydrocarbon material such as gasoline, mineral oil, fuel oil, drying oil, cutting fluids and waxes. It is possible with the stabilizer mixture according to the invention to stabilize, for example, the following polyolefins: 1. polymers that are derived from singly unsaturated hydrocarbons, such as polyolefins, e.g. polyethylene of low and high density, which can optionally be crosslinked, poly propylene, polyisobutylene, polymethylbutene-1 and poly rnethylphentene-1; 2. mixtures of the homopolymars mentioned under 1, such as mixtures of polypropylene and polyethylene, poly propylehe and polybutene-1, polypropylene and polyisobu ethylene; ; 3. copolymers of the monomers on which the homopoly mers mentioned under 1 are based, such as ethylene/propylene copolymers, propylene/butene-1 copolymers, propylene/isobu tylene copolymers, ethylene/butene-1 copolymers, as well as terpolymers of ethylene and propylene with a diene, such as hexadiene, di-cyclopentadiene or ethylid enenorbornene. The following examples, in which all quantities are expressed by weight unless otherwise indicated, will serve to illustrate the practice of the invention in more detail. Example 1 This example illustrates the stabilization of polypropylene resin with a combination of phenolic antioxidant and stabilizer identified as follows in Table I: Phenolic antioxidant A: N,N '-bis 12- (3- (3, 5-di-t-butyl-4-hydroxyphenyl J propionyl oxy)ethyl)oxamide, "BPEO". Stabilizer B1: 2-hydroxy-4-n-octoxybenzophenone, "HOBP". The effectiveness of the stabilizer combinations is evaluated by observing changes in ultimate tensile strength upon prolonged exposure to simulated outdoor weathering conditions. Control stock containing no stabilizer (Run 1 in Table l), or the phenolic antioxidant component alone or stabilizer component alone (Runs 2 and 3 in Table I) are included for comparison with a stock of the invention containing both the phenolic antioxidant (A) and the stabilizer (B) (Run 4 in Table I). The stocks represented in Table I are prepared by dry mixing in a Hobart [trademark] mixer 100 parts of unstabilized powdered polypropylene (average molecular weight about 72,000; "Profax 6501" ltrademark]) with 0.1 part of the phenolic antioxidant A and 0.3 part of the stabilizer B1. The mixtures are extruded on a Davis Standard (trademark) extruder containing three screens (60/80/100 mesh) and a 3/4" bar die (length to diameter ratio 30:1). The extrusion is conducted with the following temperature profile: feed 1930; transition 1970, 2040; metering 2100, 2150; and die 2210C at 20 RPM. The extrudate is chopped and injection molded on an Ankerwerke (trademark) machine with rear, middle and front temperatures of 182"C, mold temperature at 52"C, into T-bars of dimensions 8·" long by 1/8" thick by ¸" wide. The T-bars are aged in an Atlas Sunshine Arc Weatherometer (trademark) model XW-W with conditions 63"C spray mist rate of 18 minutes every 2 hours. The samples are tested for tensile strength at break according to ASTM D638 Type I, dumbell specimens at a rate of 2" per minute. The results after 1200 hours exposure are shown in Table I. The data in Table I indicate the marked improvement in retained tentile strength using the antioxidant/stabilizer in the combination of this invention rather than alone. TAB I Aging of Stabilized Polypropylene Run No.: 1 2 3 4 Composition (parts) Polyethylene 100 100 100 100 BPEO - .1 - .1 HOBP - - .3 .3 Tensile Strength (psi) Aged 0 hrs 5590 5615 5600 5560 1200 hrs 3510 3500 4070 5370 Change -37.2 -37.7 -27.3 -3.4 Example 2 Polypropylene resin, Profax 6501 (Trademark), was dry blended with antioxidant (A) [BPEO; N,N'-bis[2-(3-[3,5-di-t-butyl4-hydroxyphenyl]propionyloxy)ethyl]oxamide] and/or stabilizer (B1) tHOBP; 2-hydroxy-4-n-oxtoxybenzophenone] at the amounts indicated in Table II and then mixed in a Brabender (Trademark) mixer for five minutes at 4000F (2040 C) and 25 RPM. A film was prepared by placing 7 g of compounded resin between ferro-type plates spaced apart by a 10 mil frame. The assembly was placed into a press, pre-heated for three minutes at 3700F (1880C), degassed several times and then kept for two minutes at 25,000 psi pressure. After quenching in cold water, the dried film was exposed in a Xenon weatherometer at 60-800C, 50% relative humidity and at maximum UV irradiation of 280-300 nm, for periods of exposure indicated in Table II. The carbonyl index (CI) of the exposed samples was determined by infrared spectroscopy in this manner: The optical density (OD) at 1720cm 1 (baseline tangential to the absorption minima at 1810 and 1580cm 1) measured and the following calculation carried out: CI (moles/1) = OD E.S Wherein E = Molar extinction coefficient (3,000 1/mol cm) S = Sample thickness, cm. TABLE II Run No.: 5 6 7 Blank Composition (parts) Polyethylene 100 100 100 100 Antioxidant A 0.1 - 0.05 Stabilizer B1 - 0.1 0.05 - RESULTS 1 2 3 Blank CI, Unaged 36 31 34 37 CI, Aged 202 Hours 55 50 50 344 Cl1 Aged 428 Hours 846 469 121 2000+ CI, Aged 600 Hours 1282 1321 937 (Off Scale) Carbonyl Index = reported number X 10 lt v. ill be apparent from the results shown in Table II that Run No. 7, which represents the invention and contained both (A) and (B1), provided a synergistic effect in the form of remarkably reduced CI, as compared to Run No. 5 containing (A) alone and Run No. 6 containing (B1) alone (all three runs containing the same total amount of protective material). Example 3 This example illustrates the synergistic effect obtained with combinations of the phenolic antioxidant A (BPEO) with stabilizer B2 "TB CB"; 2- (3, 5-di-t-butyl-2-hydroxyphenyl)-5-chlorobenzotiazole] or stabilizer B3 ["SATM"; Tinuvin (trademark) 622, belived to be N-hydroxyethyl-2 ,2,6, 6-tetramethylpiperidino succinic acid ester], as shown in Table lII. TABLE III Run No.: 8(3) 9 10 11 12 Blank (4) Composition (parts) Polypropylene 100 100 100 100 100 100 BPEO 0,1 - - 0.05 0.05 - TBCB(1) - 0.1 - 0.05 - - SATM - - 0.1 - 0.05 - - RESULTS CI, Unaged 36 37 63 31 52 37 CI, Aged 202 Hours 55 75 89 32 55 344 CI, Aged 428 Hours 846 615 618 82 306 2000+ CI, Aged 600 Hours 1282 639 1759 483 361 (Off Scale) CI = reported number X 10 5 Remarks (1)2-(3,5-di-t-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole. (2)Tinuvin (trademark) 622, believed to be N-hydroxyethyl-2,2,6,6 tetramethylpiperidino succinic acid ester. (3)same experiment as Table II Run 5. (4)Same blank as in Table II. The synergistic effect obtained with runs 11 and 12 of the invention is apparent in Table III.

Claims: CLAIMS: 1. A stabilizing composition characterised in that it comprises a mixture of (A) the phenolic antioxidant N,N'bis/2-(3-/3,5- di-t-butyl-4-hydroxyphenyl¯7propionyloxy)ethylS ethyl¯7oxamide with one of the following stabilizers: (B1)2-hydroxy-4-n-octoxybenzophenone, (B2) 2- (3 ,5-di-t-butyl-2-hydroxyphenyl-5-chloro- benzotriazole, or (B3) N-hydroxyethyl-2, 2,6 , 6-tetramethylpiperidino succinic acid ester. 2. A stabilizing composition according to claim 1 characterised in that it is a mixture of (A) and (B1). 3. A stabilizing composition according to claim 1 characterised in that it is a mixture of (A) and (B2). 4. A stabilizing composition according to claim 1 characterised in that it is a mixture of (A) and (B3). 5. A stabilized composition comprising an organic material normally subject to deterioration upon aging characterised in that the composition includes a stabilizing amount of a stabilizer composition as claimed in any of the preceeding claims. 6. A stabilized composition according to claim 5 characterised in that the said organic material is polypropylene. 7. A method of stabilizing an organic material normally subject to deterioration upon aging characterised in that the method comprises mixing said material with a stabilizingly effective amount of a stabilizer composition as claimed in any of claims 1 to 4. 8. A method according to claim 10 characterised in that the said organic material is polypropylene.

Inventors: PAOLINO, PAULA ANN
Applicants: UNIROYAL, INC.
Application year: 1981
Main classification: C08K5
IPC codes: C08K5