HINDERED PHENOLIC ANTIOXIDANTS AND DIAZACYCLOALKANE UV STABILIZERS IN POLYMERIC FILMS

Abstract: In a preferred embodiment, slit tape is made by extruding a polyolefin in the form of a sheet into a cooling water bath, slitting the sheet into ribbons after the sheet is withdrawn from the water bath, and stretching the ribbons as they are conveyed through an oven, the improvement residing in the addition to the polyolefin a combination of a hindered phenolic antioxidant and a 2-keto diazacycloalkane UV stabilizer in sufficient amount to reduce water carryover and improve processing stability of the polyolefin.

Description: HINDERED PHENOLIC ANTIOXIDANTS AND DIAZACYCLOALKANE UV STABILIZERS IN POLYMERIC FILMS BACKGROUND OF THE INVENTION Polymer resins are used to prepare slit film ribbons which are subsequently woven into fabrics useful for producing industrial bags and carpet backings. In making the slit film ribbons, a resin is ex ruded at a melt temperature of about 500°F in the form of a sheet downwardly into a cooling water bath maintained at about 100°F. The extruded sheet, which is about 30 inches wide and about 5 mils in thickness, is slit into narrow ribbons of about 50 to 500 mils in width by a series of razors. These ribbons or tapes are drawn or stretched in an oven at about 350°F to where they are about 2 mils thick. The drawing operation orients the molecules and imparts other changes to the film which provide a many-fold improvement in tensile strength thereof. A water carryover problem occurs when the polymeric film emerges from the water bath. As the film is drawn upwardly from the water bath, a constant wall of water forms on the film just above the surface of the water which slowly moves up the film as the film speed is increased. When a critical speed is reached, the wall of water can no longer move upward and it breaks. This happens when the wall of water is about one inch above the surface of the water and the result of it is a formation of water droplets which break off from the wall of water in increasing numbers as the ilm speed increases. These droplets cling to the film surface and if they are not removed, cause the ribbons to break in the drawing operation. Even when the ribbon does not break, water carryover can cause uneven film orientation, reduced tensile strength, and other undesirable properties. Mechanical means, such as air blowers and wipers, are used to help remove these droplets but are not entirely effective in severe cases. ORIGINAL OMPI The water carryover problem can be reduced or avoided by running the film at a reduced rate. This, however, is not a practical solution to the problem since it is desired to operate a commercial plant at a maximum speed. Another more practical way to reduce water carryover is to reduce amount of the offending additive in the composition. If amount of the hindered phenolic antiαxidant is reduced to a level at which water carryover is acceptable, it was found that processing stability is adversely affected. It is, therefore, desirable to circumvent this problem by the addition of a small amount of a co-stabilizer that contributes significantly to main¬ taining adequate processing stability without creating- an additional increment of water carryover. Processing stability, referred to in the preceding paragraph, is the ability to maintain the melt flow index through repeated processing cycles. Since melt flow index is related, to polymer viscosity, degradative reactions occurring during processing lead either to chain scissions or chain crossiin ing and cause the melt flow index to change. Processing stability is important not only during the initial product formation.but also for re¬ processing scrap and waste. Loss of ultraviolet s.tability and loss of other properties of polyolefin films has also been shown to be related to the presence of hydroperoxides formed, during processing steps. At bottom of column 9 of U.S. patent.4,190,571, it is disclosed that polymeric compositions containing 2- keto-l,4-diazacyclαalkanes can also include hindered, phenolic antioxidants in amounts ranging from 0.1 to 10 parts, preferably from 0.2 to 5 parts. This patent dis¬ closes a gamut of polymeric compositions including poly¬ ethylene and polypropylene, se 'bottom of col. S. Amount of the diazacycloal ane in the polymeric compositions disclosed by the patent is 0-01 to 5 parts, preferably 0.1 to 1.0 part per 100 parts of the polymer. U.S. patent BAD ORIGINAL , 4,207,228 makes similar disclosure ^ in cols. 4, 11 and 12 with respect to 2-keto-l,5-diazacyσloalkane≤. SUMMARY OF THE INVENTION This invention relates to a method for making slit tape with improved water carryover and processing stability from polymeric films containing 0.01 to 0.09 part of a hindered phenolic antioxidant and 0.005 to 0.5 part of a 2-keto diazacycloalkane. These amounts are based on 100 parts of polymeric material. The polyolefin is preferably polyethylene or polypropylene, the hindered phenolic antioxidant . is selected from t-butyl hindered phenolic antioxidants and the diazacycloalkane is selected from bis compounds of 2-keto-l,4-diazaσycloalkanes . DRAWINGS Figure 1 is a. graph indicating processing stability at 270°C of polypropylene film containing varying amounts of antioxidant A, tris (3,5-di-t-butyl-4- hydroxybenzyl) isocyanurate, and UV stabilizer 3, 1,1'- (1 ,2-ethanediyl)-bis-(3,3,5,5,7-pentamethyl) -1 ,4-di za- cycloheptane-2-one; Figure 2 is a graph indicating processing stability at 270°C of polypropylene film containing varying amounts of compound A, tris (3,5-di-t-butyl-4- hydroxybenzyl) isocyanurate, and UV stabilizer C, 1,1'- (1,2-ethanediyl)-bis (3 ,3 , 5 ,5-tetramethyl-2-piperazinone) ; Figure 3 is similar to Figure 1 except proces¬ sing stability is tested at 300°C; Figure 4 is similar to Figure 2 except proces¬ sing stability is tested at 300°C; Figure 5 is a plot: of tensile strength versus hours in a weatherometer for polypropylene film samples containing two different loadings of antioxidant A, tris (3,5-di-t-butyl-4—hydroxy enz l) isocyanurate Figure 6 is a plot of tensile strength versus hours in a weatherometer for polypropylene film samoles BAD ORIGINAL containing antioxidant A, tris (3,S» i-t-butyl-4-hy roxy- benzyl)isocyanurate, alone or in combination with UV s-tabiiizer C, 1,1 l -(1,2-ethanediyl)-bis (3,3,5,5-tetra- ethyl-2-piperazinone) . DETAILED DESCRIPTION OF THE INVENTION It has been unexpectedly discovered that water carryover problem and processing stability of polymeric films can be improved by incorporating in a polymeric resin a hindered phenolic antioxidant and a 2-ke-o diazacycloalkane ultraviolet light stabilizer. Amount of the hindered phenol can vary from 0.005 to 0.5 part, preferably 0.01 to 0.09 part, and -amount of 2-keto diaza¬ cycloalkane can vary from 0.001 to 1, preferably 0.005 to 0.5, part per 100 parts of the polymeric material. Polymeric materials referred to herein are organic materials which undergo thermal and oxidative degradation as evidenced by discoloration and/or e brittle- ent. These materials include homopolymers, copolymers and mixtures thereof. Specific examples of such polymeric materials are natural rubber-, synthetic rubbers, poly- epichlαrohyάrin polymers, polyurethanes, FVC resins, A3S resins, polystyrene, polyamides, polyacrylonitrile, poly- acrylates, polymethacrylates, polycarbonates, phenol formaldehyde resins, polyepoxides, polyethylene, poly- propylene, ethylene—propylene polymers, ethylene-propyiene- diene polymers, ethylene vinyl acetate polymers, and the like. Preferred, polymeric materials for the invention described herein are homopolymers of α-oiefin≤ such as polyethylene and polypropylene, and their copolymers; vinyl resins made by polymerizing vinyl halides or by copolymerizing vinyl halides with unsaturated polymerizabl monomers? polyurethanes such as those made from polyois an organic poiyisocyanates; polycarbonates; polyacetais; polyethylene oxide; polyacrylics; etc. Partic iarlv preferred polymeric materials are homopolymers and O PI copolymers of α-olefins, particularly ethylene and propylene, which can be extruded into films. Antioxidants are generally divided into phosphat sulfide, and hindered phenolic antioxidants. These 5 materials serve to stabilize polymers against oxidation and deterioration by light or heat. It is the last class of hindered phenolic antioxidants that is of interest herein. Specific examples of this class of antioxidants include di-n-octadecyl(3-t-butyl-4-hydroxy-5-methyl- 10 benzyl)malonate; 2,4,6-tri-t-butylphenol; 2,2'-methylene- bi≤ (6-t-butyl-4-methylρhenol) ; 2,6-di-t-butylhydroquinone; r 4,4 '-thiobis-(2-t-butyl-5-methylρhenol) ; octade-cyl-(3,5- dimethyl-4-hydroxybenzylthio)-acetate; 1,1,3-tris (3,5- dimethyl-4-hydroxyphenyl)-propane; 1,4-di (3,5-di-t-butyl- 15 4-hydroxybenzyl)-2,3,5,β-tetramethylbenzene; 2,4-bis-(n- octylthio)—β-(3,5-di-t-butyl-4-hydroxyaniline)-1,3,5- triazine; δ-(4-hydroxy-3-methylphenoxy) -2,4-bis-(n-octyl- thio)-1,3,5-triazine; octadecyl 3- (4-hydroxy-3,5-di-t- butylphenyl) propionate; pentaerythritol-tetrakis-[3- 20 (3,5-di-t-butyl-4-hydroxyphenyl) ropionate] ; di— -tetra- decyl 3,5-di-t-butyl-4-hyd ' roxybenzyl-phosphonate; (ethyl 330) ; tris(3,5-di-t-butyl-4-hydroxybenzyl) isocyanurat ; and the like. Preferred hindered phenolic antioxidants are 25 based on isocyanuric acid and are represented by the general formula 0=C =0 N t R 2 where R is a hydroxyphenylalkyleneyl radical having the formula BAD ORIGINAL where m is an integer of 1 to 4; r, is an aliphatic or cvcloaliphatic alkyl group containing 1 to 18 carbon atoms positioned, immediately adjacent to the hydroxyl group on the ring, and r_, r 3 and r d are individually selected from hydrogen atoms and aliphatic or cvcloaliphatic groups containing 1 to 18 carbon atoms; and R-, and R- ra indivi¬ dually selected from hydrogen atoms or they can be same as R, defined above. In a preferred embodiment, R, and R- are defined as the R group. Preferred compounds in this class, are tris (dialkylhydroxybenzyl)isocyanurates, more specifically, tris (3,5—di-t-aikyl-4-hydroxybenzyl)iso¬ cyanurates wherein the al2<yl groups contain 3 to 3 carbon atoms. Especially useful hindered phenols are the symmetrical tris-(3,5-di-t-alkyl-4-hydroxybenzyi)iso¬ cyanurates wherein the alkyl groups contain 4 to 8 carbon atoms. Specific examples of these compounds are tris (3,5- di-t-butyl-4-hydroxybenzyl) isocyanurate, tris(3-t-butyI-4- hydroxybenzyl)isocyanurate , tris (3-t-butyl-5-t-amyl-4— hydroxybenzyl) isocyanurate, tris (2,o-dimethyl-3-t-butyl-3- hydroxybenzyl)isocyanurate, and the like. U.S. patent 3,531,483, which * fully describes such hindered phenols and their preparation, is hereby incorporated by reference to complete disclosure of such hindered, phenols. Another class of preferred hindered phenols has alkylhydroxyphenyi substituents on an ester nucleus. This class is represented by the general formula I AD ORIGINAL * where p is an integer from 1 to 4; ,x is an integer from 1 to 8; R is hydrogen or a lower alkyl of 1 to 8 carbon atoms; R' is a lower alkyl of I to 8 carbon atoms; and R" is a tetravalent radical selected from aliphatic hydro- carbons having 1 to 30 carbon atoms, and aliphatic mono and dithioethers of 1 to 30 carbon atoms. In a preferred embodiment, X is a number of 1 to 4, R and R 1 are selected from alkyl groups of 3 to 6 carbon atoms which are branched on the alpha carbon, and R" is selected from tetravalent aliphatic hydrocarbons containing 1 to 20 carbon atoms- This class is examplified by n-octadecyl 3- (3,5-di-t-buty1-4-hydroxypheny1)propionate, pentaerythrito tetrakis- [3- (3,5-di-t-butyl-4-hydroxyphenyl)propionate] , n-dodeσyl 3 ,5-di-t-butyl-4-hydroxyphenylbenzoat , 2 ' - (2- octylthio) ethyl 3 , 5-di-t-b tyi-hydroxybenzoate, n-octa¬ decyl S- (3,5-di-t-butyl-4-hyd oxyphen 1) ropionate, and the like. These phenolic ester stabilizers, and their use and preparation, are disclosed in U.S. patents 3,330,359 and 3,441,575, which- are incorporated herein by reference for completeness of their disclosure. The 2-keto diazacycloalkanes are known ultraviole light stabilizers. Those useful in this invention include 2-keto-l,4-diazacycloalkanes (I and II) and 2-keto-l, 5- diazacycloalkanes (III) having the following structural formulas: R, ^ 1 (I) (II) ( II) where R, and R- are individually selected from hydrogen, alkyl groups of I to 12 carbon atoms, hydroxyalkyl groups of 1 to 12 carbon atoms , hydroxycycloalkyl and cycloalkvl groups of 5 to 14 carbon atoms, haloalkyl groups of 1 to 12 carbon atoms, cyanoalkyl groups of 2 to 12 carbon atoms, aminoalkyl and iminoalkyl groups of 1 to 12 carbon atoms, ether groups of 3 to 13 carbon atoms, hydroxyalkyl 5 ether and cyanoalkyl ether groups of 4 to 18 carbons, alkenyl and aralkenyl groups of 7 to 14 carbons, alkylene groups of 2 to 7 carbons, optionally containing a phos¬ phite, ester, or a hindered phenol group; and one or both of the hydrogen atoms on the ring carbon atoms can be 10 substituted with groups corresponding to the definition of R, and R-, above. In the context of the general disclosure of the 2-keto diazacycloalkanes, R-, and R_ are individually selected from hydrogen atoms and lower alkyl groups of 1 to 5 carbon atoms, and one or both of 15 the hydrogen atoms on the ring carbons can be substi¬ tuted by lower alkyl groups of 1 to 5 carbon atoms. Preferred 2-keto diazacycloalkanes are the bis compounds of 2-keto-l,4-diazacycloalkane having the following structural formula: where R * is an alkylene group of 1 to 8, preferably 2 to 4, carbon atoms? and each R group is individually selected from hydrogen and alkyl radicals of 1 to 8, preferably 1 to 4, carbon atoms. Especially preferred are the com— 25 pounds defined above wherein the R- groups at the βth position are both hydrogen. Specific examples in the preferred class of 2-keto-l,4-diazacycloalkanes include l,2-ethane-bis-(N * -3,3,5,5-tetramethyi-2-piperazinone) , 1,2-ethane-bis-( '-3,3,5,5,S-pentamethy1-2-piperazinone) , 30 and the like. These compounds, their preparation and use, are disclosed in U.S. patents 4,157,512 and 4,190,571 which are incorporated herein by ref rence for complete¬ ness of their disclosure. BAD ORIGINAt Processing stability of-a polymeric resin is determined by extruding and re-extruding the resin at a predetermined temperature for four or five passes. The melt flow index, which is described in ASTM method D1238, is determined on a sample of resin after each pass by determining a weighed amount of heated polymer which flows through an orifice in a fixed time interval at a constant pressure. Ideally, melt flow inde of a given compound should not change wi~h repeated passe through the extruder. In practice, however, the rate of change at a given temperature is dependent on the effec¬ tiveness of the processing stabilizer present in the resin. A higher melt flow index and lower viscosi-εy indicate resin degradation. To determine processing stability, aging, and water carryover, polypropylene resin formulations were prepared by blending a portion of polypropylene powder with or without antioxidants and/or ϋV stabilizers in a Waring blender to form a concentrate which was then mixed with the remaining polypropylene powder in a Henschel mixer for 3 minutes at 2000 rp . The powder blend was extruded in~o rods at 215°C using a 1-1/4 inch Brabender extruder with air cooling. The extrudate was water-cooled and pelletized. Stretched ribbons were prepared by extruding the compounds through a film .die to form a film, quenching the film in a water bath, slitting the film into a plurality of ribbons, and stretching the ribbons in a hot air oven at a draw ratio of 6:1. Pursuant to the melt index test described above, experiments were run to determine processing stability of stabilized polypropylene during extrusion. In -hese experiments, a batch of stabilized polypropylene resin was extruded and re-extruded for a total of five passes. A small sample was retained after each pass and its melt flow index, i.e., viscosity, was determined, as described previously. The greater the change in melt flow between two consecu-cive passes the greater the degradation that has taken place during the extrusion process. Melt flow values were plotted on the Y-axis with the corresponding extrusion pass number on the X-axis. The steeper the slope of a plot, which is indicated by the number on the 5 plot, the more unstable is the polypropylene resin toward repeated extrusion. Figures 1 and 2 summarize results of melt flow index tests obtained at an extrusion temperature of 270°C at 40 rp with a 1-1/4 inch screw for up to five passes. 10 The resin was polypropylene containing antioxidant A alone as well as increasing amounts of compounds B and C. Antioxidant A was tris(3,5-di-t-butyi-4-hydroxybenzyl) - isocyanurate, compound B was 1,1'-(1,2-ethanediyl) -bis- (3,3,5,5,7-pentamethyl)-l,4-diazacycloheptane-2-one, and 15 compound C was 1,1'-(1,2-ethanediyl) -bis (3,3,5,5-tetra- methyl-2-ρiρerazinone) . Compound A is a well known anti¬ oxidant and compounds 3 and C are well known ultraviolet light absorbers. Analysis of Fig. 1 shows that at a loading of * 200.05 phr of antioxidant A alone, melt flow index after four passes was 15.3 whereas with 0.05 phr of antioxidant and 0.02 phr of compound 3, melt index dropped to 13.0 which further dropped to 11.5 when compound 3 was increase to 0.05 phr. Another phenolic antioxidant tested for 25 processing stability was 3,5-di-t-butyl-4-hydroxyhydro- cinna ic acid triester with l,3,5-t is-(2-hydroxyethyl) -s- triazine—2 ,4,5(1H_, 3H, 5H_) -trione. This antioxidant had a better (lower) melt flow index than compound A. Fig. 2 shows a melt index of 15.4 for 0.05 phr 0 of antioxidant A in polypropylene after four passes at 270°C which index was reduced to 12.2 when 0.02 phr of compound C was added. Increasing amount of compound C to 0.05 phr resulted in melt index of 10.1, a reduction of about one-third. Performance of compounds 3 and C at the 5 extrusion temperature of 270°C has shown achievement of an acceptable level of processing stability. Perusal of Figs. 3 and 4, which show melt indices at extrusion | - t ' ,M AL temperature of 300°C, illustrates the better performance of compound B over compound C at the higher temperature of 300°C. Melt index of polypropylene resin containing 0.05 phr of antioxidant A and 0.10 phr compound 3 was 13.3 afte four passes whereas with 0.10 phr of compound C in place of compound B, the resin became degraded. To determine effect of the additives on aging of the polypropylene film, the ribbons were mounted on holders and exposed in an Atlas carbon arc weathero eter, Model X R. The ribbon samples were exposed to 102 minutes of light followed by 18 minutes of water spray per cycle. Black panel temperature was set at.145°F.. Tensile strength was measured at various intervals to determine the aging effect thereon. Figs. 5 and 6 are plots of tensile strength versus hours in a weatherometer of polypropylene film containing antioxidant A in one series and antioxidant A with compound C in the other. Fig. 5 shows that increas¬ ing amount of antioxidant A from 0.05 phr to 0.10 phr is beneficial beyond a certain period of time in the weather- ■ ometer with bene icial effect accelerating beyond about 100 hours. When the polypropylene film was prepared with 0.05 phr of antioxidant A and 0.02 phr of compound C, Fig. 6 shows that beyond about 120 hours in the weatherometer, tensile strength was vastly and unexpectedly benefited by inclusion of compound C. The water carryover tests were measured using test apparatus which included a 2-1/2 inch Johnson extruder operated at 120 rpm at head pressure of 1500 psi equipped with a downwardly mounted 10-inch film die, a water bath and a set of motor driven nip rolls mounted immediately above the bath which pull the film out of water and also provide means of varying the speed of the film. Water bath temperature was maintained at lOQ'-'F. Extruder was operated at a temperature of 500°F. This equipment is about 1/3 the size of typical production equipment and was found to be necessary to obtain meaningful water carrvover data. Smaller equipment does not appear to provide meaningful results. The distance between surface of the water in the bath and the lip of the film die was held constant at 3/4 of an inch. Criterion for measuring water carryover is the speed of the film at which the wall of water formed on the film just above the surface of the water breaks or begins to dissipate drops which stick to the moving film. Results of the water carryover tests on polypropylene film are given in Table I, below, where water carryover (WCO) is measured in feet per minute and amounts of additives are given in parts per 100 parts of the polymeric material. 99 JJ W -.!. -__ ._ " TABLE I 10 11 Compound A 0.10 0.05 0.05 Compound B 0.05 0.05 0.05 0.10 5 Compound C 0.05 0.05 0.05 0.10 Compound D 0.10 0.05 0.05 Compound E 0.10 0.05 0.05 Lϋ WCO 109 128 128 111 132 125 132 , 137 132 135 130 / The water carryover values given in Table I represent an average of about five tests. Com p ounds A, 3 and C have already been defined whereas com p ound D was pentaerythritol-tetrakis-[3-(3,5-di-t-butyl-4-hydroxy- phenyl)propionate] and compound E was octadecyl 3-(4- hydrσxy-3,5-di-t-butylphenyl) ropionate, the latter two being, of course, phenolic antioxidants. As is shown in Table I, sample 1 of polypropylene film containing 0.10 part of compound A, a phenolic anti- oxidant, had a water carryover of 109 feet per minute. When 0.05 part of compound A and 0.05 part of compound C, a 2-keto-l, -diazacycloalkane ϋV s-tabilizer, were used to make polypropylene sample 2, water carryover increased dramatically to 128 feet per second which was the same- for sample 3 wherein compound B, another 2-keto-l,4- diazacycloalkane, was substituted for compound C in the same amount of 0.05 part. An amount of 0.10 part of compound D in sample 4 of the polypropylene film gave water carryover of 111 ft/sec, which is within the experi- mental error of 109 ft/sec for sample 1 where 0.10 part of compound A was used. A combination of 0.05 par * t of compound D and 0.05 part of compound C resulted in a splendid water carryover of 132 ft/sec for sample 5 film which dropped to 125 ft/sec for sample 5 where compound C was replaced with an equivalent amount of compound 3. Film sample 7 contained 0.10 part of compound Ξ and had a very high water carryover of 132 ft/sec which was increased to an incredible 137 ft/sec by incorporating in film sample 8 0.05 part of compound E and 0.05 part of compound C. 3y substituting an equivalent amount of compound 3 for compound C, water carryover was reduced to 132 ft/sec for sample 9 compared to sample 8. Samples 10 and 11, which contained 0.10 part of compound C and 3, respectively, had respective water carryover of 135 ft/sec and 130 ft/sec It should be remembered that compounds 3 and C are UV stabilizers, and although they exhibit superb water carryover property, they do not provide the desired antioxidant protection of compound A, the presence of which is imperative for sundry applications. Other antioxidants are tested in connection wit different 2-keto-l,4-diazacycloalkanes and 2-keto-l,5- diazacycloalkanes with analogous results in terms of processing stability, aging and water carryover.

Claims: CLAIMS 1. Method of making slit tape comprising extruding a polymer composition in the form of sheet into a cooling water bath, slitting the sheet into ribbons after the sheet is withdrawn from the water bath, convey¬ ing the ribbons into an oven, and stretching the ribbons while they are in the oven to form slit tape, the polymer composition containing sufficient amounts of components A and 3 to reduce water carryover and improved processing stability, component A is selected from hindered phenolic compounds I and II, and mixtures thereof, wherein compound I has the following general formula: 0 R 2 where R is a radical having the formula where m is a number of 1 to 4; r, is an aliphatic or cycloaliphatic alkyl group containing 1 to 18 carbon atoms positioned immediately adjacent to the hydroxyl group on the ring, and r 2 , r^ and r^ are individually selected from hydrogen atoms and aliphatic or cycloaliphatic groups containing 1 to 18 carbon atoms; and R, and R are indivi¬ dually selected from hydrogen atoms or they can be indivi- dually defined as the R group, above; and compound II has the following general formula: * 4-p where p is a number from 1 to 4; x is a-number from 1 to 8; R is hydrogen or a lower alkyl of 1 to 8 carbon atoms; R' is a lower alkyl of 1 to 8 carbon atoms; and R" is a tetravalent radical selected from aliphatic hydrocarbons of 1 to 3 carbon atoms, aliphatic mono and dithioethers of 1 to 30 carbon atoms, and aliphatic mono and ciathers of 1 to 30 carbon atoms; and component 3 is. selected from 2-keto-l,4-diaza- cycloalkanes (I and II), 2-keto-l,5-diazacyσloalkanes (III and bis compounds thereof, having the following structural formulas: A ?1 R-, (I) (II) (III) where R, and R- are individually selected from hydrogen atoms, alkyl groups of 1 to 12 carbon atoms, hydroxyalkyl groups of 1 to 12 carbon atoms, hydroxycycloalkyl and cyσloalkyl groups of 5 to 14 carbon atoms, haloalkyl groups of 1 to 12 carbon atoms, cyanoalkyl groups of 2 to 12 carbon atoms, aminoalkyl and iminoalkyl groups of 1 to 12 carbon atoms, ether groups of 3 to 18 carbon atoms, hydroxyalkyl and cyanoalkyl ether groups of 4 to 18 carbon atoms, alkenyl and aralkenyl groups of 7 to 14 carbon atoms, and alkylene groups of 2 to 7 carbon atoms; and one or both of the hydrogens on the ring carbon atoms OMPI are substituted with groups corresponding to the definition of R, and 7 , above. 2. Method of claim 1 wherein in compound II of component. A, x is a number of 1 to 4, R and R' are indivi- 5 dually selected from alkyl groups of 3 to 6 carbon atoms which are branched on the alpha carbon, and R" is selected from aliphatic hydrocarbons containing 1 to 20 carbon atoms. 3. Method of claim 1 wherein amount of componen 0 A is 0.005 to 0.5 part and amount of component 3 is 0.001 to 1 part, per 100 parts of the polymer composition; and component B is selected from bis compounds of 2-keto-l,4- diazacycloalkanes having the following structural formula: where R' is selected from alkylene radicals of 1 to 8 carbon atoms and each R^ is individually selected from hydrogen atoms and alkyl radicals of 1 to 8 carbon atoms. 4. Method of claim 3 wherein compound I of component A is selected from tris (dialkylhydroxybenzyl)- 0 isocvanurates; compound II has x of 1 to 4, R and R' are individually selected from alkyl groups of 3 to 6 carbon atoms which are branched on the alpha carbon, and R" is selected from tetravalent. aliphatic hydrocarbons contain¬ ing 1 to 20 carbon atoms. 5 5. Method of claim 4 wherein component A is selected, f om tris (dialkylhydroxybenzyl) isocvanurates. 6. Method of claim 4 wherein component A is selected from tris(3,5-di-t-alky1-4-hydroxybenzyl) iso¬ cyanurates wherein the alkyl groups contain 3 to 8 carbon Q atoms. 7. Method of claim S wherein amount, of compon¬ ent A is 0.01 to 0.09- part and amount of component 3 is 0.005 to 0.5 part per 100 parts of_the polymeric material which is selected from homopolymers of alpha-olefins and their copolymers. 8. Method of claim 6 wherein the polymeric material is selected from polyethylene, polypropylene and copolymers thereof with copolymerizing monomers; vinyl resins; polyurethanes; polycarbonates; polyethylene oxide; and polyacrylics. 9. Method of claim 7 wherein the polymeric material is selected from polyethylene, polypropylene and copolymers thereof with σσpolymerizable monomers. 10. Method of claim 5 wherein the polymeric material is selected from polyethylene, polypropylene and copolymers with σopoly erizable monomers; amount of component A is 0.01 to 0.09 part and amount of component B is 0.005 to 0.5, per 100 parts of the polymeric material; component A is selected from tris (3,5-di-t-alkyl-4-hydroxy- benzyl) isocyanurates wherein the alkyl groups contain 3 to 8 carbon atoms, octadeσy-1 3-(4-hydroxy-3,5-di-t-butyl- phenyl)propionate, pentaerythritol-tetrakis- [3- (3,5-di-t- butyl-4-hydroxyphenyl) ropionate] , n-dodecyl 3,5-di-t- butyl-4-hydroxyphenylbenzoate and 2-(2-oσtylthio) ethyl- 3,5-di-t-buty1-hyd oxybenzσate.

Inventors: KLETECKA GEORGE
Applicants: GOODRICH CO B F, KLETECKA GEORGE
Application year: 1981
Main classification: B29D7
IPC codes: B29C55, B29D7, C08J5, C08K5, C08L101