3-phenyl-benzofuran-2-one derivatives containing phosphorus as stabilizers

Abstract

The invention relates to a composition comprising an organic material susceptible to oxidative, thermal or light-induced degradation and a compound of formula I-P, I-O or I-M ##STR00001##
Further embodiments are a compound of formula I-P, I-O or I-M, a process for protection of the organic material by the compound, the use of the compound for stabilizing the organic material, an additive composition comprising the compound, a process for manufacturing the compound and intermediates involved therein.

Claims

1. A composition, comprising: a) an organic material susceptible to oxidative, thermal or light-induced degradation, and b) a compound (101), (102), (103), (104), (105), (106), (107), (108) or (109): ##STR00041## ##STR00042## ##STR00043## ##STR00044##

2. The composition according to claim 1, wherein the organic material is a polymer, an oligohydroxy compound, a wax, a fat or a mineral oil.

3. The composition according to claim 2, wherein the organic material is a polymer, which is a polyolefin or a copolymer thereof, a polystyrene or a copolymer thereof, a polyurethane or a copolymer thereof, or a polyether, and which is obtained by a method comprising: polymerizing an epoxide, an oxetane or tetrahydrofuran, or a copolymer thereof, a polyester or a copolymer thereof, a polycarbonate or a copolymer thereof, a poly(vinyl chloride) or a copolymer thereof, a poly(vinylidene chloride) or a copolymer thereof, a polysulfone or a copolymer thereof, a polybutadiene or a copolymer thereof, a poly(vinyl acetate) or a copolymer thereof, a poly(vinyl alcohol) or a copolymer thereof, a poly(vinyl acetal) or a copolymer thereof, or a polyamide or a copolymer thereof.

4. The composition according to claim 1, wherein component b) is present in the composition in an amount of 0.0005% to 10% based on the weight of component a).

5. The composition according to claim 1, further comprising: as a component c), a first further additive.

6. The composition according to claim 5, which comprises as component c) a phenolic antioxidant, which is tetrakis-[?-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionyloxymethyl]methane or stearyl ?-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate.

7. The composition according to claim 5, which comprises as component c) a phosphite, which is tris-(2,4-di-tert-butylphenyl) phosphite.

8. The composition according to claim 5, wherein the first further additive comprises at least one selected from the group consisting of a phosphite or phosphorite different to component b), an acid scavenger, a phenolic antioxidant, and an aminic antioxidant.

9. The composition according to claim 8, wherein the further additive comprises a phenolic antioxidant, which is an ester of P-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid.

10. The composition according to claim 8, further comprising: as a component d), a second further additive, which is a phosphite or phosphorite different to component b), an acid scavenger, a phenolic antioxidant or an aminic antioxidant, with the proviso that component d) is a different substance than component c).

11. The composition according to claim 1, wherein component (h) is compound (101) as defined in claim 1.

12. The composition according to claim 1, wherein component (b) is compound (102) as defined in claim 1.

13. The composition according to claim 1, wherein component (h) is compound (103) as defined in claim 1.

14. The composition according to claim 1, wherein component (b) is compound (104) as defined in claim 1.

15. The composition according to claim 1, wherein component (b) is compound (105) as defined in claim 1.

16. The composition according to claim 1, wherein component (b) is compound (106) as defined in claim 1.

17. The composition according to claim 1, wherein component (b) is compound (107) as defined in claim 1.

18. The composition according to claim 1, wherein component (b) is compound (108) as defined in claim 1.

19. The composition according to claim 1, wherein component (b) is compound (109) as defined in claim 1.

20. A process for protecting an organic material susceptible to oxidative, thermal or light-induced degradation, the process comprising incorporating the organic material into, or applying the organic material onto, a compound (101), (102), (103), (104), (105), (106), (107), (108) or (109): ##STR00045## ##STR00046## ##STR00047## ##STR00048##

21. The process according to claim 20, wherein: the organic material is a polymer; the incorporating into the polymer is carried out at a temperature between 135? C. to 350? C.; and the polymer is a polyolefin or a copolymer thereof, a polystyrene or a copolymer thereof, a polyurethane or a copolymer thereof, or a polyether, which is obtained by a method comprising polymerizing an epoxide, an oxetane or tetrahydrofuran, or a copolymer thereof, a polyester or a copolymer thereof, a polycarbonate or a copolymer thereof, a poly(vinyl chloride) or a copolymer thereof, a poly(vinylidene chloride) or a copolymer thereof, a polysulfone or a copolymer thereof, a polybutadiene or a copolymer thereof, a poly(vinyl acetate) or a copolymer thereof, a poly(vinyl alcohol) or a copolymer thereof, a poly(vinyl acetal) or a copolymer thereof, or a polyamide or a copolymer thereof.

22. A compound (101), (102), (103), (104), (105), (106), (107), (108) or (109): ##STR00049## ##STR00050## ##STR00051## ##STR00052##

23. The compound according to claim 22, wherein the compound is compound (101).

24. The compound according to claim 22, wherein the compound is compound (102).

25. The compound according to claim 22, wherein the compound is compound (103).

26. The compound according to claim 22, wherein the compound is compound (104).

27. The compound according to claim 22, wherein the compound is compound (105).

28. The compound according to claim 22, wherein the compound is compound (106).

29. The compound according to claim 22, wherein the compound is compound (107).

30. The compound according to claim 22, wherein the compound is compound (108).

31. The compound according to claim 22, wherein the compound is compound (109).

32. An additive composition, comprising: b) a compound (101), (102), (103), (104), (105), (106), (107), (108) or (109); and c) a first further additive, which is a phosphite or phosphorite different to component b), an acid scavenger, a phenolic antioxidant or an aminic antioxidant: ##STR00053## ##STR00054## ##STR00055## ##STR00056##

33. The additive composition according to claim 32, which comprises, as component c), a phenolic antioxidant, which is an ester of ?-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid.

34. The additive composition according to claim 32, further comprising: as a component d), a second further additive, which is a phosphite or phosphonite different to component b), an acid scavenger, a phenolic antioxidant or an aminic antioxidant, with the proviso that component d) is a different substance than component c).

Description

SYNTHETIC EXAMPLES

(1) The synthetic procedures are conducted under a nitrogen atmosphere.

(2) If not otherwise stated, the starting materials are commercially available, for example from Aldrich Corp.

Example S-1: Synthesis of Compound (101)

(3) ##STR00032##

(4) 18.6 g (55 mmol) of compound (201) (obtainable according to EP 2500341 A, page 8, example 1) are heated to 65? C. in 85 ml of dry 1,2-dichloroethane. 5.19 g (65 mmol) dry pyridine are added. 2.5 g (18 mmol) phosphorous-trichloride, which are dissolved in 2 mL of dry 1,2-dichloroethane, are added over 20 minutes. The reaction mass is stirred for 2 hours at 65? C. After cooling to ambient temperature, 120 mL cyclohexane are added and the white precipitate formed is filtrated and washed with another 120 mL cyclohexane. The combined cyclohexane portions are concentrated to dryness and the white residue is dried at 70? C. under vacuum for 3 hours. 15.0 g (80% of theory) of compound (101) as a white amorphous solid are obtained.

(5) .sup.31P-NMR (toluene-d.sub.8): 128 ppm

(6) .sup.1H-NMR (toluene-d.sub.8): 4.7 ppm (s, 3H, CH at lactone-ring)

(7) MS (LC/MS, ACPI positive mode): [M+1].sup.+=1044

Example S-2: Synthesis of Compound (102)

(8) ##STR00033##

(9) Compound (102) is prepared in analogy to example 1 from compound (202) (obtainable according to EP 2500341 A, page 8, example 1 by using the corresponding 4-tertoctyl-phenol) and obtained in a yield of 71% of theory as an amorphous solid.

(10) .sup.31P-NMR (toluene-d.sub.8): 128 ppm

(11) .sup.1H-NMR (toluene-d.sub.8): 4.7 ppm (s, 3H, CH at lactone-ring)

(12) MS (LC/MS, ACPI positive mode): [M+1].sup.+=1381

Example S-3: Synthesis of Compound (103)

(13) ##STR00034##

(14) Compound (103) is prepared in analogy to example 1 from compound (203) (obtainable according to EP 0648765 A, page 30, compound 115) and obtained in a yield of 89% of theory as an amorphous solid.

(15) .sup.31P-NMR (toluene-d.sub.8): 142 ppm

(16) .sup.1H-NMR (toluene-d.sub.8): 4.2 ppm (s, 3H, CH at lactone-ring)

(17) MS (LC/MS, ACPI positive mode): [M+1]+=1128

Example S-4: Synthesis of Compound (104)

(18) ##STR00035##

(19) 20.0 g (55 mmol) of compound (203) are heated to 65? C. in 85 mL of dry 1,2-dichlorethane. 4.75 g (60 mmol) dry pyridine is added. 4.98 g (27 mmol) of compound (301) (=dichlorophenylphosphane) dissolved in 5 mL of dry 1,2-dichloroethane is added over 20 minutes. The reaction mass is stirred for 4 hours at reflux. After cooling to room temperature, the solvent is removed under vacuum and the solid residue is dried at 70? C. under vacuum for 3 hours. 15.4 g of compound (104) is obtained (67% of theory) as a white solid.

(20) .sup.31P-NMR (toluene-ds): 169 ppm

(21) .sup.1H-NMR (toluene-d.sub.8): 4.2 ppm (s, 2H, CH at lactone ring)

(22) MS (LC/MS, ACPI positive mode): [M+1]+=840

Example S-5: Synthesis of Compound (105)

(23) ##STR00036##

(24) 2.0 g (5 mmol) of compound (203) are dissolved in 10 mL of dry dichloroethane at 65? C. To the solution are subsequently added 0.52 g (7 mmol) of dry pyridine and within 20 minutes 2.59 g (5 mmol) of compound (302) (=2,4,8,10-tetra-t-butyl-6-chlorobenzo[d][1,3,2]benzodioxaphosphepine, obtainable according to U.S. Pat. No. 5,858,905, page 2, example 1). The reaction mass is stirred under reflux for 6 hours, cooled to room temperature and 10 mL of pentane are added. The suspension is filtrated, the residue is washed with 2 portions of 10 mL dichloroethane and the combined solvent fractions are evaporated to dryness under vacuum. The glassy solid residue is further dried at 70? C. in vacuum. 2.92 g of compound (105) are obtained (66% of theory) as a white glassy solid.

(25) .sup.31P-NMR (toluene-d.sub.8): 141 ppm

(26) .sup.1H-NMR (toluene-d.sub.8): 4.2 ppm (s, 1H, CH at lactone ring)

(27) MS (LC/MS, ACPI positive mode): [M+1].sup.+=806

Example S-6: Synthesis of Compound (106)

(28) ##STR00037##

(29) Compound (106) is prepared in analogy to example 5 from compound (201) and compound (302) and obtained in a yield of 82% of theory as a solid.

(30) .sup.31P-NMR (toluene-ds): 143 ppm

(31) .sup.1H-NMR (toluene-ds): 4.8 ppm (s, 1H, CH at lactone ring)

(32) MS (LC/MS, ACPI positive mode): [M+1].sup.+=778

Example S-7: Synthesis of Compound (107)

(33) ##STR00038##

(34) Compound (107) is prepared in analogy to example 5 from compound (203) and compound (303) (=1,3,7,9-tetratert-butyl-11-chloro-5H-benzo[d][1,3,2]benzodioxa-phosphocine, obtainable according to U.S. Pat. No. 5,858,905, page 2, example 1) and is obtained in a yield of 87% of theory as a solid.

(35) .sup.31P-NMR (toluene-d.sub.8): 137 ppm

(36) .sup.1H-NMR (toluene-ds): 4.3 ppm (s, 1H, CH at lactone ring)

(37) MS (LC/MS, ACPI positive mode): [M+1].sup.+=820

Example S-8: Synthesis of Compound (108)

(38) ##STR00039##

(39) Compound (108) is prepared in analogy to example 5 from compound (203) and compound (304) (=1,3,7,9-tetratert-butyl-11-chloro-5-methyl-5H-benzo[d][1,3,2]benzodi-oxaphosphocine, obtainable according to U.S. Pat. No. 5,858,905, page 2, example 1) and is obtained in a yield of 90% of theory as a solid.

(40) .sup.31P-NMR (toluene-d.sub.8): 138 ppm

(41) .sup.1H-NMR (toluene-d.sub.8): 4.3 ppm (s, 1H, CH at lactone ring)

(42) MS (LC/MS, ACPI positive mode): [M+1].sup.+=834

Example S-9: Synthesis of Compound (109)

(43) ##STR00040##

(44) Compound (109) is prepared in analogy to example 5 from compound (204) (obtainable according to EP 0648765 A, page 30, compound 115) and compound (304) and is obtained in a yield of 75% of theory as a solid.

(45) .sup.31P-NMR (toluene-d.sub.8): 137 ppm

(46) .sup.1H-NMR (toluene-d.sub.8): 4.9 ppm (s, 1H, CH at lactone ring)

(47) MS (LC/MS, ACPI positive mode): [M+1].sup.+=876

APPLICATION EXAMPLES

(48) The following known stabilizers are partly employed in addition to the inventive compounds:

(49) AO-1 is Irganox 1010 (RTM BASF), which contains pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate).

(50) AO-2 is Irganox 1076 (RTM BASF), which contains octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate.

(51) Phos-1 is Irgafos 168 (RTM BASF), which contains tris(2,4-di-tert-butylphenyl) phosphite.

(52) CaSt is commercially available calcium stearate, which acts as acid scavenger.

(53) ZnSt is commercially available zinc stearate, which acts as acid scavenger.

(54) ZnO is commercially available zinc oxide, which acts as acid scavenger.

Example A-1: Stabilization of a Molding Grade Ziegler-Natta Polypropylene Homopolymer Polymer Processing Experimental

(55) A molding grade Ziegler-Natta polypropylene homopolymer (zn-PP-homopolymer) from a bulk/slurry phase polymerization process is evaluated. The processing conditions are described below. The various additives are blended according to table A-1-1 with the granular polymer, which is essentially free of any stabilization additives. The blending is carried out using a M 10 FU mixer from MTI.

(56) The thoroughly blended formulations are then melt compounded in a single screw extruder (Teach-Line Extruder E20T SCD 15 from Dr. Collin; L/D=25, compression 3.08) at lower temperature of 200? C. under nitrogen, which is denoted in the table A-1-1 as the zero pass extrusion. This ensures good melt mixing with minimal damage to the polymer due to oxidative degradation.

(57) The resultant zero pass extrudate is then extruded multiple times a single screw extruder, fitted with a Maddock mixing section, at higher temperature (280? C.), open to air. Extrusion at higher temperatures in combination with the presence of oxygen (air) enhances the rate of polymer degradation. Pelletized samples of zero, first, third and fifth pass extrudate are collected and stored in sealed plastic bags at room temperature in storage boxes in the dark.

(58) Melt Flow Rates: The samples are tested for retention of molecular mass (weight). This is measured by melt flow rate retention (according to ASTM-1238) on a MD-P melt index tester from Goettfert at the test conditions of 230? C. and 2.16 kg. Melt flow rates are measured in grams of polymer that flow out of a defined orifice in 10 minutes and are stated as grams/10 minutes (decigrams per minute).

(59) TABLE-US-00001 TABLE A-1-1 composition No. 1 .sup.a) 2 .sup.a) 3 .sup.b) 4 .sup.b) 5 .sup.b) zn-PP-homopolymer 99.879 99.825 99.8685 99.8685 99.8685 CaSt 0.050 0.050 0.050 0.050 0.050 AO-1 0.050 0.050 0.050 0.050 0.050 Phos-1 0.021 0.075 0.021 0.021 0.021 compound (106) 0.0105 compound (105) 0.0105 compound (102) 0.0105 total additives content 0.121 0.175 0.1315 0.1315 0.1315 280? C. melt processing melt flow rates zero pass 9.6 9.3 9.1 9.0 9.0 1.sup.st pass 16.6 13.2 14.3 12.3 10.9 3.sup.rd pass 33.3 22.7 29.6 19.2 14.8 5.sup.th pass 58.0 42.6 49.0 30.1 19.8 Footnotes: .sup.a) reference; .sup.b) inventive

(60) The addition of 0.0105 parts of an inventive compound at formulation No. 3 to 5 improves the melt stability versus formulation No. 1. It allows also a disproportionate reduction of phosphite stabilizer content.

Examples A-2-1 to A-2-9

(61) Polymer Processing Experimental

(62) The various additives are blended with the stated applied granular polymer, which is essentially free of any stabilization additives, in a composition according to the respective tables A-2-1 to A-2-9. The blending is carried out using a Henschel, a Turbula or a Kitchen-Aid mixer.

(63) The thoroughly blended formulations are melt compounded in a twin screw extruder at a lower temperature of 210? C. (410? F.) under nitrogen, which is denoted in the tables as the zero pass extrusion. This ensures good melt mixing with minimal damage to the polymer due to oxidative degradation.

(64) The resultant zero pass extrudate is then extruded multiple times a single screw extruder, fitted with a Maddock mixing section, at a higher temperature of 260? C. (500? F.) or 280? C. (535? F.), open to air. Extrusion at higher temperatures in combination with the presence of oxygen (air) enhances the rate of polymer degradation. Pelletized samples of zero, first, third and fifth pass extrudate are collected and stored in sealed plastic bags at room temperature in storage boxes in the dark.

(65) Melt Flow Rates: The samples are tested for retention of molecular mass (weight). This is measured by melt flow rate retention according to ASTM-1238 on a Tinius-Olsen Extrusion Plastometer. For polypropylene type polymer samples, the test conditions are 230? C. and 2.16 kg. For polyethylene type polymer samples, the test conditions are 190? C. and 2.16 kg or 21.6 kg. The melt flow ratio is calculated as the melt flow rate at 21.6 kg divided by the melt flow rate at 2.16 kg. Melt flow rates are measured in grams of polymer that flow out of a defined orifice in 10 minutes and are stated as grams/10 minutes (decigrams per minute).

(66) Yellowness Index: The yellowness index of some samples is tested for color development observed during the multiple extrusion and is measured according to ASTM-1925 on compression molded plaques of 3.2 mm (125 mil). Color is measured on a DCI SF600 spectrophotometer with large area view, spectral component included, C illuminant and 2 degree observer. Color in these measurements is expressed as Yellowness Index.

(67) Oven Aging: Some samples are tested for oxidative stability below the melting point of the polymer using oven aging to accelerate polymer degradation. This is done by putting compression molded plaques of 1 mm (40 mils) in a Blue M forced draft oven equipped with a rotating carousel in order to homogenize the exposure to an elevated temperature of 135? C. inside the oven. Failure is measured by days to embrittlement by bending the plaque every 3 to 4 days until the plaque snapped due to oxidative degradation. The time is stated in days.

(68) Oxidative Induction Time: Some samples are tested for oxidative stability above the melting point of the polymer using oxidative induction time (OIT) as a means of measuring the activity of the stabilizer in the polymer melt at a high temperature of 190? C. in an oxidative environment (oxygen). The experiments are run on a differential scanning calorimeter (DSC). Scans are collected using a heating rate of 10? C./min under nitrogen from 50? C. to 190? C., then switching to oxygen and holding at isothermal conditions until catastrophic oxidation. Time to onset of catastrophic oxidation (observed as a strong exotherm) is stated in minutes.

Example A-2-1: Stabilization of a Molding Grade Ziegler-Natta Polypropylene Homopolymer

(69) A molding grade Ziegler-Natta polypropylene homopolymer (zn-PP-homopolymer) with a melt flow rate of 4 dg/min from a bulk/slurry phase polymerization process is evaluated.

(70) TABLE-US-00002 TABLE A-2-1 composition No. 1 .sup.a) 2 .sup.a) 3 .sup.a) 4 .sup.b) 5 .sup.b) zn-PP-homopolymer 99.890 99.840 99.790 99.8575 99.8575 CaSt 0.060 0.060 0.060 0.060 0.060 AO-1 0.050 0.050 0.050 0.050 0.050 Phos-1 0.050 0.100 0.022 0.022 compound (103) 0.0105 compound (104) 0.0105 total additives content 0.110 0.160 0.210 0.1425 0.1425 260? C. (500? F.) melt processing melt flow rates zero pass 6.03 4.59 3.90 4.38 4.30 1.sup.st pass 9.78 6.05 4.38 5.07 4.99 3.sup.rd pass 13.85 7.20 5.41 6.26 5.89 5.sup.th pass 17.27 9.91 6.32 6.90 7.11 oven ageing at 135? C. zero pass 52 58 62 58 62 280? C. (535? F.) melt processing melt flow rates zero pass 6.03 4.59 3.90 4.38 4.30 1.sup.st pass 12.03 7.04 5.19 5.77 5.59 3.sup.rd pass 21.84 10.49 6.81 6.78 6.91 5.sup.th pass 34.35 17.07 9.13 8.58 9.09 Footnotes: .sup.a) reference; .sup.b) inventive

(71) The compositions comprised of a low concentration of an inventive compound (105 ppm), a phenolic antioxidant (500 ppm) and a traditional phosphite melt processing stabilizer (220 ppm) provide good performance as measured by retention of melt flow rates in comparison to a common binary blend of the phenolic antioxidant (500 ppm) and the traditional phosphite melt processing stabilizer (500 or 1000 ppm). The ternary blends comprising an inventive compound provide as good or better performance at lower concentrations (825 ppm) in comparison to the common binary blends at higher concentrations (1000 or 1500 ppm). There are no deleterious effects to the long term thermal stability provided by the phenolic antioxidant observed when measured by oven aging at 135? C.

Example A-2-2: Stabilization of a Molding Grade Ziegler-Natta Polypropylene Copolymer

(72) A molding grade Ziegler-Natta polypropylene copolymer (zn-PP-copolymer; ethylene as comonomer in around 2% by weight) with a melt flow rate of 3 dg/min from a bulk/slurry phase polymerization process is evaluated.

(73) TABLE-US-00003 TABLE A-2-2 composition No. 1 .sup.a) 2 .sup.a) 3 .sup.a) 4 .sup.b) 5 .sup.b) zn-PP-copolymer 99.890 99.840 99.790 99.8575 99.8575 CaSt 0.060 0.060 0.060 0.060 0.060 AO-1 0.050 0.050 0.050 0.050 0.050 Phos-1 0.050 0.100 0.022 0.022 compound (103) 0.0105 compound (104) 0.0105 total additives content 0.110 0.160 0.210 0.1425 0.1425 260? C. (500? F.) melt processing melt flow rates zero pass 4.60 3.34 2.79 3.55 3.30 1.sup.st pass 7.98 4.64 3.34 4.57 3.80 3.sup.rd pass 11.47 5.72 3.99 6.06 4.82 5.sup.th pass 16.03 7.49 4.89 6.98 5.10 Yellowness index zero pass 8.00 8.20 7.60 8.60 9.20 1.sup.st pass 9.30 9.50 9.00 9.10 10.50 3.sup.rd pass 10.80 11.40 11.10 10.10 11.90 5.sup.th pass 12.40 13.30 13.00 11.20 12.10 280? C. (535? F.) melt processing melt flow rates zero pass 4.60 3.34 2.79 3.55 3.30 1 .sup.st pass 10.50 5.11 3.68 4.79 4.64 3.sup.rd pass 20.24 9.81 5.89 7.23 6.05 5.sup.th pass 32.38 15.02 8.45 10.13 9.18 Footnotes: .sup.a) reference; .sup.b) inventive

(74) The compositions comprised of a low concentration of an inventive compound (105 ppm), a phenolic antioxidant (500 ppm) and a traditional phosphite melt processing stabilizer (220 ppm) provide good performance as measured by retention of melt flow rates in comparison to a common binary blend of the phenolic antioxidant (500 ppm) and the traditional phosphite melt processing stabilizer (500 or 1000 ppm). The ternary blends comprising an inventive compound provide nearly as good or better performance at lower concentrations (825 ppm) in comparison to the common binary blends at higher concentrations (1000 or 1500 ppm).

Example A-2-3: Stabilization of a Film Grade Ziegler-Natta Linear Low Density Polyethylene Copolymer

(75) A film grade Ziegler-Natta polyethylene copolymer (zn-LLDPE-copolymer; butene as comonomer, density 0.92 g/cm.sup.3) with a melt flow rate of 2 dg/min at 190? C. and 2.16 kg from a gas phase polymerization process is evaluated.

(76) TABLE-US-00004 TABLE A-2-3 composition No. 1 .sup.a) 2 .sup.a) 3 .sup.a) 4 .sup.b) 5 .sup.b) zn-LLDPE-copolymer 99.935 99.915 99.845 99.925 99.925 ZnO 0.015 0.015 0.015 0.015 0.015 AO-2 0.020 0.020 0.020 0.020 0.020 Phos-1 0.030 0.050 0.130 0.030 0.030 compound (103) 0.010 compound (104) 0.010 total additives content 0.065 0.085 0.155 0.075 0.075 260? C. (500? F.) melt processing melt flow rates (190? C./2.16 kg) zero pass 2.17 2.12 2.15 2.11 2.12 1.sup.st pass 1.81 1.90 2.01 1.96 1.97 3.sup.rd pass 1.46 1.60 1.89 1.75 1.76 5.sup.th pass 1.24 1.36 1.64 1.56 1.57 melt flow rates (190? C./21.6 kg) zero pass 54.12 53.48 54.51 53.58 53.00 1.sup.st pass 51.85 52.43 51.55 52.48 52.39 3.sup.rd pass 49.34 50.27 50.63 50.84 51.37 5.sup.th pass 47.53 47.99 46.47 49.43 49.54 melt flow ratio (190? C.; 21.6 kg/2.16 kg) zero pass 24.93 25.27 25.37 25.41 25.00 1.sup.st pass 28.62 27.65 25.68 26.79 26.61 3.sup.rd pass 33.75 31.48 26.86 29.12 29.20 5.sup.th pass 38.23 35.31 28.30 31.76 31.64 yellowness index zero pass ?0.80 ?0.80 ?1.20 6.60 6.00 1.sup.st pass 1.10 1.40 1.00 7.60 8.30 3.sup.rd pass 3.00 3.90 2.00 10.30 11.40 5.sup.th pass 4.70 6.00 5.00 11.70 13.00 oxidative induction time (10 mil films/onset at 190? C.) zero pass 26 39 74 43 48 Footnotes: .sup.a) reference; .sup.b) inventive

(77) The composition comprised of a low concentration of an inventive compound (100 ppm), in combination with a phenolic antioxidant (200 ppm) and common phosphite melt processing stabilizer (300 ppm), provides good performance as measured by retention of melt flow rates in comparison to a traditional binary blend of the phenolic antioxidant (200 ppm) and the common phosphite melt processing stabilizer (500 or 1300 ppm). The ternary blends provide as good or better performance at lower concentrations (600 ppm) in comparison to the common binary blends at higher concentrations (700-1300 ppm). No deleterious effects to the oxidative stability provided by the phenolic antioxidant are observed as measured by oxidative induction time.

Example A-2-4: Stabilization of a Molding Grade Cr Based High Density Polyethylene

(78) A molding grade chromium catalyzed polyethylene (Cr-HDPE; density 0.955 g/cm.sup.3) with a melt flow rate of 0.3 dg/min at 190? C. and 2.16 kg from a gas phase polymerization process is evaluated.

(79) TABLE-US-00005 TABLE A-2-4 composition No. 1 .sup.a) 2 .sup.a) 3 .sup.a) 4 .sup.b) 5 .sup.b) Cr-HDPE 99.935 99.915 99.845 99.925 99.925 AO-1 0.050 0.050 0.050 0.050 0.050 Phos-1 0.050 0.100 0.022 0.022 compound (103) 0.011 compound (104) 0.011 total additives content 0.050 0.100 0.150 0.083 0.083 260? C. (500? F.) melt processing melt flow rates (190? C./2.16 kg) zero pass 0.22 0.28 0.29 0.32 0.31 1.sup.st pass 0.20 0.26 0.29 0.29 0.31 3.sup.rd pass 0.18 0.25 0.25 0.25 0.29 5.sup.th pass 0.13 0.17 0.21 0.22 0.28 melt flow rates (190? C./21.6 kg) zero pass 26.73 28.27 28.43 29.81 29.84 1.sup.st pass 28.37 29.35 29.89 30.42 31.49 3.sup.rd pass 28.74 28.39 29.59 30.36 32.15 5.sup.th pass 26.77 27.82 29.06 30.67 32.85 melt flow ratio (190? C.; 21.6 kg/2.16 kg) zero pass 121.72 100.03 99.37 93.96 95.55 1.sup.st pass 140.00 112.18 104.62 106.28 102.37 3.sup.rd pass 162.47 134.80 120.51 121.67 109.35 5.sup.th pass 200.50 165.00 138.98 140.14 119.25 yellowness index zero pass 7.70 4.10 3.50 4.50 9.50 1.sup.st pass 8.70 5.80 5.50 5.60 10.50 3.sup.rd pass 10.30 7.10 7.00 7.30 12.10 5.sup.th pass 10.90 8.30 8.00 8.20 12.00 oxidative induction time (10 mil films/onset at 190? C.) zero pass 68 106 151 109 110 Footnotes: .sup.a) reference; .sup.b) inventive

(80) The composition comprised of a low concentration of an inventive compound (110 ppm) in combination with a phenolic antioxidant (500 ppm) and a common phosphite melt processing stabilizer (220 ppm) provide good performance as measured by retention of melt flow rates in comparison to a common binary blend of the phenolic antioxidant (500 ppm) and the common phosphite melt processing stabilizer (500 or 1000 ppm). The ternary blends provide nearly as good or better performance at lower concentrations (830 ppm) in comparison to the common binary blends at higher concentrations (1000-1500 ppm). No deleterious effects to the oxidative stability provided by the phenolic antioxidant are observed as measured by oxidative induction time.

Example A-2-5: Stabilization of a Blown Film Grade Metallocene Based Catalyst Linear Low Density Polyethylene Copolymer

(81) A blown film grade metallocene based catalyst linear low density polyethylene copolymer (metallocene based catalyst LLDPE-copolymer; hexene as co-monomer) with a density of 0.918 g/cm.sup.3 and a melt flow rate of 1.0 dg/min at 190? C./2.16 kg from a gas phase polymerization process is evaluated.

(82) TABLE-US-00006 TABLE A-2-5 composition No. 1.sup.a) 2.sup.a) 3.sup.a) 4.sup.b) 5.sup.b) 6.sup.b) metallocene 99.900 99.850 99.800 99.844 99.844 99.844 based catalyst LLDPE- copolymer ZnSt 0.050 0.050 0.050 0.050 0.050 0.050 AO-2 0.050 0.050 0.050 0.050 0.050 0.050 Phos-1 0.050 0.100 0.045 0.045 0.045 compound 0.011 (105) compound 0.011 (107) compound 0.011 (108) total additives 0.100 0.150 0.200 0.156 0.156 0.156 content 260? C. (500? F.) melt processing melt flow rates (190? C./2.16 kg) zero pass 0.66 0.82 0.91 0.90 0.90 0.90 1.sup.st pass 0.52 0.67 0.84 0.83 0.82 0.80 3.sup.rd pass 0.37 0.48 0.69 0.68 0.70 0.65 5.sup.th pass 0.29 0.37 0.53 0.57 0.59 0.54 melt flow rates (190? C./21.6 kg) zero pass 12.46 13.71 14.27 14.46 14.40 14.43 1.sup.st pass 11.70 12.76 13.94 13.97 13.92 13.85 3.sup.rd pass 10.79 11.61 13.06 13.13 13.28 13.03 5.sup.th pass 10.12 10.87 12.10 12.67 12.75 12.49 melt flow ratio (190? C.; 21.6 kg/2.16 kg) zero pass 18.88 16.77 15.72 15.98 16.02 16.08 1.sup.st pass 22.44 19.02 16.59 16.86 16.94 17.35 3.sup.rd pass 29.02 24.28 18.81 19.28 19.06 20.16 5.sup.th pass 34.47 29.06 22.90 22.37 21.61 23.04 oxidative induction time (10 mil films/onset at 190? C.) zero pass 25 35 89 64 54 66 Footnotes: .sup.a)reference; .sup.b)inventive

(83) The compositions comprised of a low concentration of an inventive compound (110 ppm), a phenolic antioxidant (500 ppm) and a traditional phosphite melt processing stabilizer (450 ppm) provide good performance as measured by retention of melt flow rates in comparison to a common binary blend of the phenolic antioxidant (500 ppm) and the traditional phosphite melt processing stabilizer (500 or 1000 ppm). The ternary blends comprising an inventive compound provide as good or better performance at comparable or lower concentrations (1060 ppm) in comparison to the common binary blends (1000 or 1500 ppm). There are no deleterious effects to the oxidative stability provided by the phenolic antioxidant as measured by oxidative induction time.

Example A-2-6: Stabilization of a Molding Grade Ziegler-Natta Polypropylene Copolymer

(84) A molding grade Ziegler-Natta polypropylene copolymer (zn-PP-copolymer-2.5; ethylene as co-monomer in around 2% by weight) with a melt flow rate of 2.5 dg/min from a bulk/slurry phase polymerization process is evaluated.

(85) TABLE-US-00007 TABLE A-2-6 composition No. 1.sup.a) 2.sup.a) 3.sup.a) 4.sup.b) 5.sup.b) 6.sup.b) zn-PP- 99.890 99.840 99.790 99.834 99.834 99.834 copolymer- 2.5 CaSt 0.060 0.060 0.060 0.060 0.060 0.060 AO-1 0.050 0.050 0.050 0.050 0.050 0.050 Phos-1 0.050 0.100 0.045 0.045 0.045 compound 0.011 (105) compound 0.011 (107) compound 0.011 (108) total additives 0.110 0.160 0.210 0.166 0.166 0.166 content 260? C. (500? F.) melt processing melt flow rates (230? C./2.16 kg) zero pass 3.87 2.92 2.65 2.73 2.57 2.58 1.sup.st pass 6.36 4.19 2.99 3.13 3.04 2.97 3.sup.rd pass 8.47 5.41 3.37 3.31 3.48 3.52 5.sup.th pass 11.65 5.70 3.85 3.71 4.10 4.02 yellowness index zero pass 8.50 7.90 6.60 6.30 6.60 7.40 1.sup.st pass 9.80 8.90 8.10 7.20 7.20 7.80 3.sup.rd pass 11.20 10.70 9.90 8.90 9.10 9.20 5.sup.th pass 12.50 11.80 11.30 9.70 10.10 9.70 oven ageing at 135? C. zero pass 60 69 72 77 72 77 oven ageing at 150? C. zero pass 5 9 9 9 9 9 oxidative induction time (10 mil films/onset at 190? C.) zero pass 20 25 34 81 32 31 Footnotes: .sup.a)reference; .sup.b)inventive

(86) The compositions comprised of a low concentration of an inventive compound (110 ppm), a phenolic antioxidant (500 ppm) and a traditional phosphite melt processing stabilizer (450 ppm) provide good performance as measured by retention of melt flow rates in comparison to a common binary blend of the phenolic antioxidant (500 ppm) and the traditional phosphite melt processing stabilizer (500 or 1000 ppm). The ternary blends comprising an inventive compound provide as good or better performance at comparable or lower concentrations (1060 ppm) in comparison to the common binary blends (1000 or 1500 ppm). There are no deleterious effects to the long thermal stability provided by the phenolic antioxidant as measured by oven ageing.

Example A-2-7: Stabilization of a Molding Grade Ziegler-Natta Polypropylene Homopolymer

(87) A molding grade Ziegler-Natta polypropylene homopolymer (zn-PP-homopolymer) with a melt flow rate of 4 dg/min at 230? C./2.16 kg from a bulk/slurry phase polymerization process is evaluated.

(88) TABLE-US-00008 TABLE A-2-7 composition No. 1.sup.a) 2.sup.a) 3.sup.a) 4.sup.b) 5.sup.b) 6.sup.b) zn-PP- 99.890 99.840 99.790 99.840 99.840 99.840 homopolymer CaSt 0.060 0.060 0.060 0.060 0.060 0.060 AO-1 0.050 0.050 0.050 0.050 0.050 0.050 Phos-1 0.050 0.100 0.0375 0.0375 0.0375 compound 0.0125 (105) compound 0.0125 (107) compound 0.0125 (108) total additives 0.110 0.160 0.210 0.160 0.160 0.160 content 260? C. (500? F.) melt processing melt flow rates (230? C./2.16 kg) zero pass 18.15 13.79 12.77 13.90 13.49 13.74 1.sup.st pass 23.40 15.18 14.30 15.36 15.79 15.30 3.sup.rd pass 31.90 18.27 15.62 16.00 16.94 17.71 5.sup.th pass 42.49 21.74 17.88 17.28 18.81 19.77 yellowness index zero pass 4.40 4.20 3.70 4.90 4.20 5.10 1.sup.st pass 5.10 5.40 4.90 6.30 5.00 5.60 3.sup.rd pass 5.70 6.10 5.90 7.50 5.50 6.00 5.sup.th pass 6.30 7.90 7.30 8.60 6.40 7.20 Footnotes: .sup.a)reference; .sup.b)inventive

(89) The compositions comprised of a low concentration of an inventive compound (125 ppm), a phenolic antioxidant (500 ppm) and a traditional phosphite melt processing stabilizer (375 ppm) provide good performance as measured by retention of melt flow rates in comparison to a common binary blend of the phenolic antioxidant (500 ppm) and the traditional phosphite melt processing stabilizer (500 or 1000 ppm). The ternary blends comprising an inventive compound provide as good or better performance at comparable or lower concentrations (1000 ppm) in comparison to the common binary blends (1000 or 1500 ppm).

Example A-2-8: Stabilization of a Film Grade Ziegler-Natta Linear Low Density Polyethylene Copolymer

(90) A cast film grade Ziegler-Natta linear low density polyethylene copolymer (zn-LLDPE-copolymer; butene as comonomer, density 0.92 g/cm.sup.3) with a melt flow rate of 2 dg/min at 190? C./2.16 kg from a gas phase polymerization process is evaluated.

(91) TABLE-US-00009 TABLE A-2-8 composition No. 1.sup.a) 2.sup.a) 3.sup.a) 4.sup.b) 5.sup.b) 6.sup.b) 7.sup.b) zn-LLDPE- 99.925 99.885 99.845 99.915 99.915 99.915 99.915 copolymer ZnO 0.015 0.015 0.015 0.015 0.015 0.015 0.015 AO-2 0.020 0.020 0.020 0.020 0.020 0.020 0.020 Phos-1 0.040 0.080 0.120 0.040 0.040 0.040 0.040 compound (105) 0.010 compound (107) 0.010 compound (108) 0.010 compound (109) 0.010 total additives 0.075 0.115 0.155 0.085 0.085 0.085 0.085 content 260? C. (500? F.) melt processing melt flow rates (190? C./2.16 kg) zero pass 2.05 2.22 2.22 2.22 2.17 2.03 2.10 1.sup.st pass 1.77 2.01 2.16 2.00 1.98 1.97 2.02 3.sup.rd pass 1.39 1.54 2.00 1.81 1.72 1.74 1.75 5.sup.th pass 0.99 1.32 1.73 1.60 1.51 1.56 1.48 melt flow rates (190? C./21.6 kg) zero pass 51.92 53.02 52.66 52.30 52.19 52.56 52.54 1.sup.st pass 48.68 51.64 52.88 50.76 50.56 51.28 50.84 3.sup.rd pass 45.13 48.28 51.15 49.24 48.79 48.87 48.63 5.sup.th pass 43.10 46.75 48.93 47.49 46.61 47.54 46.18 melt flow ratio (190? C.; 21.6 kg/2.16 kg) zero pass 25.36 23.88 23.68 23.53 24.06 25.94 25.05 1.sup.st pass 27.49 25.69 24.44 25.38 25.60 26.03 25.20 3.sup.rd pass 32.56 31.37 25.61 27.22 28.32 28.07 27.73 5.sup.th pass 43.49 35.31 28.35 29.65 30.78 30.45 31.14 yellowness index zero pass 3.20 0.80 ?0.10 2.40 0.80 0.60 1.70 1.sup.st pass 3.80 3.00 1.20 3.20 1.60 1.20 1.90 3.sup.rd pass 7.60 5.60 2.30 3.40 2.60 1.80 3.00 5.sup.th pass 8.30 7.10 4.00 4.80 3.90 2.70 3.40 oxidative induction time (10 mil films/onset at 190? C.) zero pass 27 41 60 47 42 51 54 Footnotes: .sup.a)reference; .sup.b)inventive

(92) The compositions comprised of a low concentration of an inventive compound (100 ppm), a phenolic antioxidant (200 ppm) and a traditional phosphite melt processing stabilizer (400 ppm) provide good performance as measured by retention of melt flow rates in comparison to a common binary blend of the phenolic antioxidant (200 ppm) and the traditional phosphite melt processing stabilizer (800 or 1200 ppm). The ternary blends comprising an inventive compound provide as good or better performance at lower concentrations (700 ppm) in comparison to the common binary blends (800 or 1200 ppm). There are no deleterious effects to the oxidative stability provided by the phenolic antioxidant as measured by oxidative induction time.

Example A-2-9: Stabilization of a Molding Grade Cr Based High Density Polyethylene

(93) A molding grade chromium catalyzed polyethylene (Cr-HDPE; density 0.955 g/cm.sup.3) with a melt flow rate of 0.3 dg/min at 190? C./2.16 kg from a gas phase polymerization process is evaluated.

(94) TABLE-US-00010 TABLE A-2-9 composition No. 1.sup.a) 2.sup.a) 3.sup.a) 4.sup.b) 5.sup.b) 6.sup.b) 7.sup.b) Cr-HDPE 99.950 99.900 99.850 99.906 99.906 99.906 99.906 AO-1 0.050 0.050 0.050 0.050 0.050 0.050 0.050 Phos-1 0.050 0.100 0.033 0.033 0.033 0.033 compound (105) 0.011 compound (107) 0.011 compound (108) 0.011 compound (109) 0.011 total additives 0.050 0.100 0.150 0.094 0.094 0.094 0.094 content 260? C. (500? F.) melt processing melt flow rates (190? C./2.16 kg) zero pass 0.30 0.32 0.32 0.29 0.30 0.31 0.31 1.sup.st pass 0.25 0.30 0.32 0.29 0.29 0.29 0.30 3.sup.rd pass 0.18 0.26 0.30 0.26 0.27 0.28 0.27 5.sup.th pass 0.15 0.23 0.27 0.25 0.25 0.26 0.26 melt flow rates (190? C./21.6 kg) zero pass 28.00 28.56 28.70 26.56 28.11 27.70 27.93 1.sup.st pass 28.13 29.35 30.07 28.50 30.00 28.16 29.65 3.sup.rd pass 26.50 29.40 30.24 28.71 28.73 30.04 30.00 5.sup.th pass 25.50 29.04 29.91 29.21 29.90 30.02 29.98 melt flow ratio (190? C.; 21.6 kg/2.16 kg) zero pass 93.33 89.25 89.69 91.59 93.70 89.35 90.10 1.sup.st pass 112.52 97.83 93.97 98.28 103.45 97.10 98.83 3.sup.rd pass 147.22 113.08 100.80 110.42 106.41 107.29 111.11 5.sup.th pass 170.00 126.26 110.78 116.84 119.60 115.46 115.31 Footnotes: .sup.a)reference; .sup.b)inventive

(95) The compositions comprised of a low concentration of an inventive compound (110 ppm), a phenolic antioxidant (500 ppm) and a traditional phosphite melt processing stabilizer (330 ppm) provide good performance as measured by retention of melt flow rates in comparison to a common binary blend of the phenolic antioxidant (500 ppm) and the traditional phosphite melt processing stabilizer (500 or 1000 ppm). The ternary blends comprising an inventive compound provide as good or better performance at lower concentrations (940 ppm) in comparison to the common binary blends (1000 or 1500 ppm).