Light stabilizers

Abstract

The present invention relates to symmetric diesters of hydroxyalkyl-4-hydroxy-tetraalkylpiperidine compounds and their use as light stabilizers. They are compatible with and soluble in coating formulations of different polarity.

Claims

1. A compound having the formula (I) ##STR00022## wherein A is CH(R.sup.3)CH.sub.2 or CH.sub.2 CH(R.sup.3); each R.sup.1 is the same and is C.sub.1-C.sub.21 alkyl or C.sub.3-C.sub.7 cycloalkyl; R.sup.2 is H or C.sub.1-C.sub.3 alkyl; and R.sup.3 is H or C.sub.1-C.sub.4 alkyl.

2. The compound according to claim 1, wherein each R.sup.1 is C.sub.1-C.sub.17 alkyl.

3. The compound according to claim 1, wherein each R.sup.1 is selected from C.sub.1, C.sub.2, C.sub.3, C.sub.4, C.sub.5, C.sub.6, C.sub.7, C.sub.8, C.sub.9, C.sub.10, C.sub.11, C.sub.12, C.sub.13, C.sub.14, C.sub.15, C.sub.16, and C.sub.17 alkyl.

4. The compound according to claim 1, wherein each R.sup.1 is C.sub.1-C.sub.21 alkyl substituted with at least one substituent selected from C.sub.1-C.sub.4 alkoxy and OH.

5. The compound according to claim 1, wherein R.sup.2 is H.

6. The compound according to claim 1, wherein A is CH.sub.2CH.sub.2, CH(CH.sub.3)CH.sub.2, or CH.sub.2CH(CH.sub.3).

7. A compound of the formula ##STR00023##

8. A composition comprising the compound according to claim 1 and an organic material.

9. The composition according to claim 8, in the form of a coating composition.

10. The composition according to claim 8, wherein the organic material is a polyethylene or polypropylene or polyurethane or styrenic polymer or a polyvinylchloride.

11. The composition according to claim 8, which further comprises one or more UV absorbers of the hydroxy-phenyl-benzotriaziole or hydroxy-phenyl-triazine or hydroxyl-benzophenone or oxanilide class or cyanoacrylate or malonate and combinations thereof.

12. The composition according to claim 8, which further comprises a sterically hindered amine compound.

13. The composition according to claim 8, which further comprises one or more of the following compounds: Bis-(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl)sebacate; condensate of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid dimethylester; 2,2-methylenebis(6-(2H-benzotriazol-2-yl)-4-1,1,3,3-tetramethylbutyl)phenol; 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol; 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol; 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione; tris(2,4-di-tert-butylphenyl)phosphite; ethylenebis(oxyethylene)bis-(3-(5-tert-butyl-4-hydroxy-m-tolyl)-propionate); reaction product of methyl 3-(3-(2H-benzotriazole-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate/polyethyleneglykol 300; 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid C.sub.7-C.sub.9alkylester, optionally in admixture with 1-methoxy-2-propyl acetate; pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]; Bis[2,4-di-tert-butylphenyl] pentaerythritol diphosphate; 2-(2H-benzotriazol-2-yl)-4,6-bis(1,1-dimethylpropyl)phenol; Reaction product of methyl 3-(3-(2H-benzotriazole-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate/polyethyleneglykol 300; or a compound of the formula ##STR00024## wherein n is a number such that the molecular weight is from 2600 to 3400 g/mol.

14. A coated article which is coated with the composition according to claim 8.

15. A coated article which is coated with a composition comprising the compound according to claim 1 and an organic material comprising a metal substrate, and coat comprising a) a primer coat which is electrodeposited onto the metal substrate; b) at least one pigmented base coat which is in direct contact with the primer coat, and a clear coat that is in direct contact with the pigmented base coat and comprises a compound of claim 1.

16. A light stabilizer comprising the compound according to claim 1.

17. A process for preparing a coating on a substrate which comprises coating the substrate with the compound according to claim 1.

18. The process according to claim 17, wherein the substrate is a metal, metal alloy, woods, plastic, ceramic or another coating.

19. The compound according to claim 1, wherein each R.sup.1 is C.sub.3-C.sub.12 alkyl.

20. The compound according to claim 1, wherein each R.sup.1 is C.sub.3-C.sub.6 cycloalkyl.

Description

EXAMPLES

Example 1: 2-[4-(2,2-dimethylpropanoyloxy)-2,2,6,6-tetramethyl-1-piperidyl]ethyl 2,2-dimethylpropanoate (compound 1)

(1) ##STR00007##

(2) A three-necked 1 L flask was charged with 53.8 g, (0.27 mol) of 1-(2-Hydroxy-ethyl)-2,2,6,6-tetramethyl-piperidin-4-ol (referred to as HE-HTMP in the following) and THF (100 g). The flask was then attached to a rotary evaporator, and 30 ml of THF (andif presentany water) was distilled off at normal pressure. Then the flask was disconnected from the rotary evaporator, and pyridine (67.0 g, 0.85 mol) was added to the flask.

(3) After cooling to ca. 30? C., a solution of pivalic acid chloride (68.30 g, 0.57 mol) in THF (40 ml) was added within 15 minutes into the cooled (15-20? C.) flask. A viscous suspension was forming during the addition of the acid chloride. After control for complete conversion of the HE-HTMP, water (4.5 ml) was added and the mixture was stirred for another hour in order to decompose the excess pivalic acid chloride. Then the solvent was removed from the reaction mixture on a rotary evaporator, and the residue dissolved in dichloromethane (300 ml). This solution was washed with diluted hydrogen chloride (40 g of a 8% solution), diluted sodium hydroxide (260 g of a 1% solution) and water (250 g). After drying (Na.sub.2SO.sub.4), the solvent was removed on the rotary evaporator to leave the crude product as colorless crystalline residue.

(4) This material and the material of a similarly performed batch (from 0.395 mol HE-HTMP) were combined and distilled in vacuum to give 125.8 g of the product (51% yield based on HE-HTMP) as colorless crystals.

(5) bp.=145? C., 9.Math.10.sup.?3 mbar

(6) mp.=85? C.

(7) .sup.1H-NMR (CDCl.sub.3, 400 MHz), ? 1.06, 1.14 (2 s, 6H each, CH3, H-5, H-5); 1.15, 1.17 (2 s, 9H each, CH3, H-10, H-10); 1.40 (tr, 2H, H-3), 1.77 (dd, 2H, H-3); 2.63 (dd, 2H, H-6); 3.91 (m, 2H, H-7); 5.00 (tr tr, 1H, H-4).

(8) .sup.13C-NMR (CDCl3, 100 MHz), ? 22.28, 33.60 C-5, C-5; 27.06, 27.21 C-10, C-10; 38.55, 38.64 C-9, C-9; 41.77 C-6; 45.40 C-3; 55.66 C-2; 66.64 C-7; 67.04 C-4; 178.14, 178.52 C-8, C-8.

Example 2: 3,5,5-Trimethylhexanoic acid 2,2,6,6-tetramethyl-1-[2-(3,5,5-trimethyl-hexanoyloxy)-ethyl]-piperidin-4-yl ester (compound 2)

(9) ##STR00008##

(10) A 250 ml jacketed vessel was fitted with an anchor stirrer, an inner thermometer, a gas inlet tube, a pressure equalized dropping funnel, a Dean-Stark apparatus and a reflux condenser. The outlet from the condenser was connected to a gas absorber in order to trap the hydrogen chloride formed in the reaction.

(11) The flask was checked for air-tightness, and then charged with HE-HTMP (50.3 g, 0.25 mol) and xylene isomer mixture (114.9 g). The reservoir of the Dean-Stark apparatus was filled with xylene isomer mixture, and a slow flow of nitrogen (adjusted to ca. 0.2 L/hour) led through the gas inlet tube into the suspension in the reactor. The mixture was heated at reflux (140? C., mantle temperature 165? C.), and any traces of water were removed via the Dean-Stark apparatus.

(12) Then 3,5,5-trimethyl hexanoyl chloride (86.6 g, 0.49 mol) was added at reflux via the dropping funnel in such a rate that the evolution of the formed hydrogen chloride could be controlled. After complete addition of the acid chloride the initially formed suspension turned into a pale yellow solution which was heated for another hour at reflux and then cooled to 80? C. After washings with water (200 ml), sodium carbonate (twice 50 g of a 10% solution of sodium carbonate in water, twice 100 g of a 5% solution of sodium carbonate in water) the solvent and residual water was removed on the rotary evaporator (initially 100 mbar, 80? C., to finally 0.3 mbar, 80? C.) to leave the product as pale yellow oily liquid (112.0 g, 93% based on HE-HTMP).

(13) NMR: HSQC (CDCl.sub.3, RT, 400 MHz) ?.sup.1H/? .sup.13C 1.02, 22.20 (H, C-14); 1.02/22.68, 0.91/22.80 (H, C-5/H, C-5); 1.96, 27.03/27.07 (H, C-10/H, C-10); 0.84/30.01, 30.04 C-13, C-13; 31.05 (C-12, C-12); 1.09, 33.79 (H, C-5/H, C-5); 2.61, 41.95 (H, C-6); 2.03, 43.99/2.20, 44.28 (H, C-9/H, C-9); 1.36, 45.71/1.73, 45.74 (H, C-3/H, C-3); 1.18, 50.52/1.05, 50.54 (H, C-11/H, C-11); 55.76 (C-2); 3.88, 66.38 (H, C-7); 5.00, 67.06 (H, C-4); 172.58/172.85 (C-8/C-8).

Example 3: 2-Ethyl-hexanoic acid 2-[4-(2-ethyl-hexanoyloxy)-2,2,6,6-tetramethyl-piperidin-1-yl]-ethyl ester (compound 3)

(14) ##STR00009##

(15) A 250 ml jacketed vessel was fitted with an anchor stirrer, an inner thermometer, a gas inlet tube, a pressure equalized dropping funnel, a Dean-Stark apparatus and a reflux condenser. The outlet from the condenser was connected to a gas absorber in order to trap the hydrogen chloride formed in the reaction.

(16) The flask was checked for air-tightness, and then charged with HE-HTMP (45.0 g, 0.224 mol) and a mixture of xylene isomers (132.4 g). The reservoir of the Dean-Stark apparatus was filled with xylene isomer mixture, and a slow flow of nitrogen (adjusted to ca. 0.2 L/hour) led through the gas inlet tube into the suspension in the reactor. The mixture was heated at reflux (155? C., mantle temperature 165? C.), and ca. 5 ml of xylene was distilled off to remove any residual traces of water. Then 2-ethyl hexanoyl chloride (72.7 g, 0.447 mol) was added at reflux via the dropping funnel in such a rate that the evolution of the formed hydrogen chloride can be controlled. After complete addition of the acid chloride the initially formed suspension turned into a pale yellow solution which was heated for another four hours at reflux and then cooled to 20? C.

(17) The solution was washed with sodium carbonate solution (twice 60 g of a 10% solution of sodium carbonate in water), and water (until the pH of the aqueous layer was neutral and no chloride could be detected in the organic layer; eight times 100 g of water). Checking for chloride was done after the seventh and eighth washing as follows: ca. 0.5 g of the organic layer was dissolved in 10 ml glacial acetic and a few drops of a 5% aqueous solution of silver nitrate added. When the mixture remained clear, the organic phase was considered chloride free). Then the organic layer was separated, and the xylene removed on the rotary evaporator (initially 100 mbar, 80? C., to finally 30 mbar, 80? C.). The last traces of xylene were removed in high vacuum (170? C., 10.sup.?3 mbar) to leave the product as yellowish oily liquid (83.2 g, 82% yield based on HE-HTMP).

(18) NMR: HSQC (CDCl.sub.3, RT, 400 MHz) ?.sup.1H, ? .sup.13C 0.84, 11.73/11.78 (H, C-15/C15); 0.83, 13.85/13.87 (H, C-13/C-13); 1.04, 22.09 (H, C-5); 1.24, 22.54 (H, C-12/C12); 1.44/25.44, 1.54/25.43 (H, C-14/C-14); 1.20, 29.49/29.59 (H, C-11/C-11); 1.39/31.70, 1.54,/31.72 (H, C-10/C-10); 1.11, 33.67 (H, C-5); 1.37, 1.76/45.64 (H, C-3); 2.62, 41.86 (H, C-6); 2.17, 47.18/47.31 (C-9, C-9); 55.66 (C-2); 3.92, 66.30 (H, C-7); 5.02, 66.86 (H, C-4); 175.87/176.20 (C-8/C-8).

Example 4: Octadecanoic acid 2-(2,2,6,6-tetramethyl-4-octadecanoyloxy-piperidin-1-yl)-ethyl ester (compound 4)

(19) ##STR00010##

(20) A jacketed 1.5 L flask was fitted with an anchor stirrer, an inner thermometer and a Dean-Stark apparatus with reflux condenser. This flask was charged with xylene (435 g, mixture of isomers) and HE-HTMP (100.6 g, 0.5 mol). The mixture was heated at reflux to remove azeotropically any present water via the Dean-Stark apparatus. Then the temperature was reduced to 100? C., and methyl stearate (316.5 g, 1.03 mol) and tetrabutyl orthotitanate (0.102 g, 0.3 mmol) were added. The mixture was heated at reflux for totally 8 hours (interrupted by 60 h) and then transferred warm into a flask. The solvent was removed on a rotary evaporator, and the remaining melt of the product poured into methanol (ca. 1 L). After standing over night at ambient temperature the crystallized product was filtered off and washed with methanol (ca. 400 ml). After drying colorless crystals (218.6 g, 59.5%) were obtained.

(21) .sup.13C-NMR (APT, CDCl.sub.3, 100 MHz, RT) ? 14.07 (C-25, C-25); 22.13 (C-5); 22.65 (C-24, C-24); 24.92, 24.97 (C-10, C-10); 26.09, 29.14, 29.24 (2 C), 29.33 (2 C), 29.43, 29.44, 29.58 (2 C), 29.62 (2 C), 29.63 (2 C), 29.65 (2 C), 29.66-29.68 (8 C), (C10-C22, C-10-C22); 31.90 (C-23, C-23), 33.70 (C-5), 34.21, 34.61 (C-9, C-9); 41.89 (C-6); 45.62 (C3); 55.73 (C-2); 66.45 (C-7); 67.10 (C-4), 173.41, 173.68 (C-8, C-8).

Example 5: Hexadecanoic acid 2-(4-hexadecanoyloxy-2,2,6,6-tetramethyl-piperidin-1-yl)-ethyl ester (compound 5)

(22) ##STR00011##

(23) A 250 ml jacketed vessel was fitted with an anchor stirrer, an inner thermometer, a gas inlet tube, a pressure equalized dropping funnel, a Dean-Stark apparatus and a reflux condenser.

(24) The flask was charged with HE-HTMP (16.1 g, 80 mmol), Petrol (80 g), (Petrol is an aryl free mixture of alkanes with a boiling range from 150-190? C.), and methyl palmitate (42.6 g, 158 mmol). The Dean-Stark apparatus was filled with Petrol (30 g), and then the mixture was heated at reflux (mantle temperature 190? C.) and ca. 30 ml of petrol was distilled off to remove any residual traces of water. Then the mixture was cooled to 100? C., and aluminium tri-isopropylate (0.32 g, 1.57 mmol, 1 mol %) was added. The mixture was again heated at reflux (mantle temperature 190? C.), and kept stirring for seven hours. Then, a light vacuum was applied to remove the last traces of the formed methanol, and finally the mixture was cooled to ambient temperature. The cooled mixture was dissolved in ethanol (250 ml) and bleached with a bleaching earth for about ten minutes at reflux. After removal of the bleaching earth by filtration, the product crystallized from the filtrate and was filtered off, washed with methanol (ca. 25 g) and dried to give the product (23.0 g, 44%) as colourless crystals.

(25) The product is prepared more efficiently as follows: A 250 mil jacketed vessel was fitted with an anchor stirrer, an inner thermometer and a descending condenser was charged with HE-HTMP (50.1 g, 0.249 mol) and methyl palmitate (134.3 g, 0.497 mol). This mixture was heated at 151? C., and then tetrabutyl orthotitanate (0.14 g, 0.4 mmol) was added. The mixture was kept at 151? C. for 24 hours (GC conversion ca. 99%) and then cooled to 80? C. The contents of the reactor were then added into refluxing methanol (300 g). The obtained emulsion was allowed to cool slowly and seeded when the temperature was at 35? C. A suspension of seed crystals was obtained by taking ca. 1 ml of the emulsion into a test tube and scratching with a spatula. After cooling to ambient temperature and stirring for another couple of hours the crystallised product was filtered off, washed with methanol (ca. 100 ml) and dried on the rotavapor (30? C., 6 hours) to give 158.4 g of colorless crystals (94.1% of theory).

(26) .sup.1H-NMR (CDCl.sub.3, 400 MHz, RT) ? 0.88, 0.89 (t, 3H each, H-23, H-23); 1.10, 1.17 (s, 6H each, H-5, H-5); 1.27 (m, 48H, H-11 to H-22, H11 to H-22); 1.43, 1.83 (t, dd, 2H each, H-3, H-3); 1.63 (dq, 2H each, H-11, H-11); 2.28 (q, 4H, H-9, H-9); 2.69 (t, 2H, H-6); 3.97 (t, 2H, H-7); 5.08 (m, 1H, H-4)

(27) 13C-NMR (CDCl.sub.3, 100 MHz, RT,) ? 14.11 C23, C-23; 22.17, 33.74 C-5, C-5; 22.69 C22, C-22; 24.96, 25.01 C-10, C-10; 29.12-29.69 C-11 to C-22, C-11 to C-22; 31.93 C21, C-21; 34.27, 34.67 C-9, C-9; 41.91 C-6; 45.64 C-3; 55.77 C-2; 66.49 C-7; 67.17 C-4.

Example 6: Tetradecanoic acid 2-(2,2,6,6-tetra-methyl-4-tetradecanoyloxy-piperidin-1-yl)-ethyl ester (compound 6)

(28) ##STR00012##

(29) A jacketed 250 ml flask was fitted with an anchor stirrer, inner thermometer, gas inlet tube and a Dean-Stark apparatus with reflux condenser. The flask was charged with HE-HTMP (17.1 g, 84 mmol), Petrol (80 g), (Petrol is defined above), and methyl laurate (42.4 g, 171 mmol). The mixture was heated at reflux (mantle temperature 200? C.), and any residual water was removed via the Dean-Stark apparatus. Then the temperature was reduced (mantle temperature 80? C.), and aluminium tri-isopropylate (0.37 g, 1.8 mmol) was added. Then the mixture was again heated at reflux (mantle temperature=190? C.) for four hours and then the solvent was removed at slightly reduced pressure (800 mbar) within four hours. The remaining molten product (57.4 g) was a brownish oily liquid which solidified on standing,

(30) mp.=42?44? C.

(31) The product can be prepared also as follows: A 250 ml jacketed vessel was fitted with an anchor stirrer, an inner thermometer and a descending condenser was charged with HE-HTMP (30.6 g, 0.15 mol) and methyl tetradecanoate (80.9 g, 0.33 mol). This mixture was heated and at an inner temperature of 143? C. tetrabutyl orthotitanate (0.178 g, 0.052 mmol) was added. The mantel temperature was set to 180? C. and mixture was kept stirring for 23 hours, when the inner temperature had reached 148? C. A GC-sample showed ca. 94% conversion. Thus, the mixture was cooled to 80? C. and then added into refluxing methanol (300 g). The obtained emulsion was allowed to cool slowly and seeded when the temperature was at 35? C. A suspension of seed crystals was obtained by taking ca. 1 ml of the emulsion into a test tube and scratching with a spatula. After cooling to ambient temperature and stirring for another couple of hours the crystallized product was filtered off, washed with methanol (ca. 100 ml) and dried on the rotavapor (30? C., 23 mbar, 4 hours) to give 89.8 g (96.2% based on HE-HTMP) of colorless crystals

(32) .sup.1H-NMR (CDCl.sub.3, 400 MHz, RT) ? 0.89 (t; 6H, H-12, H-12); 1.10, 1.16 (s, 12H, H-5, H-5); 1.27 (m, 40H, H-11 to H-20, H-11 to H-20); 1.43 (t, 2H, H-3); 1.62 (q, 4H, H-10, H-10); 1.82 (dd, 2H, H-3); 2.27, 2.29 (2 t, 2H each, H-9, H-9); 2.69 (t, 2H, H-6); 3.97 (t, 2H, H-7); 5.08 (tr tr, 1H, H-4).

(33) .sup.13C-NMR (CDCl.sub.3, 100 MHz, RT) ? 14.24, C-21, C-21; 22.30 C-5, 22.82, C-20, C-20; 25.09, 25.13 C-10, C-10; 29.24, 29.29, 29.40, 29.48, 29.59, 29.73, 29.78, 29.80 C-11 to C-18, C11 to C-18; 32.05 C-19, C-19; 33.87 C-5; 34.39, 34.79 C-9, C-9; 42.04 C-6; 45.78 C-3; 55.90 C-2; 66.62 C-7; 67.28 C-4; 173.62, 173.89 C-21, C-21.

Example 7: Dodecanoic acid 2-(4-dodecanoyloxy-2,2,6,6-tetramethyl-piperidin-1-yl)-ethyl ester (compound 7)

(34) ##STR00013##

(35) A jacketed 250 ml flask was fitted with an anchor stirrer, inner thermometer, and a Dean-Stark apparatus with reflux condenser. The flask was charged with HE-HTMP (17.1 g, 84 mmol), Petrol (78.6 g), (Petrol is defined above), methyl laurate (38.4 g, 176 mmol) and aluminium tri-isopropylate (0.4 g, 1.96 mmol). The obtained mixture was heated at reflux (mantle temperature 190? C.) for four hours. A slight vacuum (800 mbar) was applied and heating was continued for another 5 hours. The conversion was 95% as determined by NMR after removal of the solvent in vacuum (136? C., 0.19 mbar) the product was obtained as yellow oil (50.9 g, 102%), which crystallized slowly at ambient temperature.

(36) The product can be prepared also as follows: A 250 ml jacketed vessel was fitted with an anchor stirrer, an inner thermometer and a descending condenser was charged with HE-HTMP (38.41 g, 0.191 mol) and methyl laurate (86.01 g, 0.40 mol). This mixture was heated and at an inner temperature of 151? C. tetrabutyl orthotitanate (0.16 g, 0.47 mmol) was added. The mantel temperature was set to 180? C. and mixture was kept stirring for 24 hours. A GC-sample showed ca. 99% conversion. Thus, the mixture was cooled to 80? C. and then added into refluxing methanol (300 g). The obtained emulsion was allowed to cool slowly and seeded when the temperature was at 35? C. A suspension of seed crystals was obtained by taking ca. 1 ml of the emulsion into a test tube and scratching with a spatula. After cooling to ambient temperature and stirring for another couple of hours the crystallised product was filtered off, washed with methanol (ca. 100 ml) and dried on the rotavapor (30? C., 23 mbar, 6 hours) to give 98.4 g (91.1% based on HE-HTMP) of colorless crystals

(37) .sup.1H-NMR (CDCl.sub.3. 400 MHz, RT) ? 0.89 (tr, 6H, H-19, H-19); 1.10, 1.16 (2 s, 6H each, H-5, H-5); 1.20-1.38 (br m, 32H, H-11-H-18, H-11-H-18); 1.43 (tr, 2H, H-3); 1.62 (m, 4H, H-10, H-10); 1.83 (dd, 2H, H-3); 2.28 (m, 4H, H-9, H-9); 2.68 (tr, 2H, H6); 3.97 (tr, 2H, H-7); 5.08 (tr tr, 1H, H-4).

(38) .sup.13C-NMR (CDCl.sub.3, 100 MHz, RT) ? 14.10 (2 C, C-19, C-19); 22.16 (2 C, C-5); 22.67 (2 C, C-18, C-18); 24.95, 25.00 (2 C, C-10, C-10); 29.10 (1 C), 29.16 (1 C), 29.26 (2 C), 29.32 (2 C), 29.44 (1 C), 29.45 (1 C), 29.59 (4 C) C-11-C16, C-11-C-16; 31.90 (2 C, C-17, C-17); 33.73 2 C C-5; 34.26, 34.65 (C-9, C-9); 41.90 (C-6); 45.64 (C-3); 55.76 (C-2); 64.48 (C-7); 67.15 (C-4); 173.50, 173.76 (C-8, C-8).

Example 8: Hexanoic acid 2-(4-hexanoyloxy-2,2,6,6-tetramethyl-piperidin-1-yl)-ethyl ester (compound 8)

(39) ##STR00014##

(40) A jacketed 250 ml flask was fitted with an anchor stirrer, inner thermometer, and a reflux condenser which was connected to a gas absorber. Into this flask was charged HE-HTMP (50.14 g, 0.249 mol) and xylene (isomer mixture, 120 g). The mixture was heated at reflux, and then at an inner temperature of 1420? C. was added hexanoic acid chloride (67.77 g 0.503 mol) within one hour. Shortly after the beginning of the addition of the acid chloride the reaction mixture turned into a viscous suspension which later became rather liquid again. After the complete addition of the acid chloride the mixture was kept at 142? C. for another two hours and then cooled to 80? C. The mixture was then washed twice with a solution of sodium carbonate (each 50 g of a 10% solution) and water (40 g). After removal of the xylenes on the rotavapor the product was distilled in vacuum (b.p. 190-200? C. at 0.001 mbar) to give 81.5 g (82.3% yield) of the product as colourless oil.

(41) .sup.1H-NMR (CDCl.sub.3, 400 MHz, RT) ? 0.89 (t, 3H each, H-13, H-13); 1.08, 1.15 (s, 6H each, H-5, H-5); 1.32 (m, 8H, H-11-H-12, H11-H12); 1.41, 1.80 (t, q; 2H each, H3, H-3); 1.61 (q, 2H each, H-10, H-10); 2.27 (q, 4H, H-9, H-9); 2.67 (t, 2H, H-6); 3.95 (t, 2H, H-7); 5.06 (m, 1H, H-4).

(42) .sup.13C-NMR (CDCl.sub.3, 100 MHz, RT) ? 13.88 C-13, C-13; 22.15, 33.72 C-5, C-5; 22.30 C-12, C-12; 24.61, 24.65 C-10, C-10; 31.26, 31.61 C-11, C-11; 34.19, 34.58 C-9, C9; 41.89 C-6; 45.62 C-3; 55.75 C-2; 66.47 C-7; 67.14 C-4; 173.45, 173.73 C-8, C-8

Example 9: Propionic acid 2-(2,2,6,6-tetramethyl-4-propionyloxy-piperidin-1-yl)-ethyl ester (compound 9)

(43) ##STR00015##

(44) A three necked flask with magnetic stirrer, reflux condenser, and pressure equalized dropping funnel was charged with HE-HTMP (100.0 g, 0.497 mol). The apparatus was flushed thoroughly with nitrogen, and then immersed in an oil bath of 140? C. Then propionic acid anhydride (131.4 g, 1.011 mol) was added via the dropping funnel within 75 minutes. During the addition of the propionic anhydride, the reaction mixture liquefied, after the addition of the propionic anhydride was complete, the mixture was heated at 150? C. for 90 minutes (after 90 minutes gas chromatography indicated completion of the reaction).

(45) The propionic acid was removed from the reaction mixture on a rotary evaporator, and the residue poured into a beaker containing water (ca. 250 ml) and dichloromethane (ca. 300 ml). The pH of the bi-phasic mixture was carefully adjusted with sodium hydrogen carbonate to pH=7.0, and then the organic layer separated with a separatory funnel, dried (sodium sulphate) and distilled in vacuum. The product (144.1 g, 92.6% yield) was obtained as pale yellow oil (bp 120-141? C., 5.Math.10.sup.?3?7.Math.10.sup.?3 mbar), which solidified on standing.

(46) mp.?25? C.

(47) .sup.1H-NMR (CDCl.sub.3. 400 MHz, RT) ? 0.98, 1.05 (2 s, 6H each, H-5, H-5); 1.01, 1.03 (2 tr, 3H each, J=7.5 Hz, H-10, H-10); 1.31 (tr, 2H), 1.71 (dd, 2H) H-3, H3; 2.18, 2.21 (2 q, 2H each, H-9, H-9); 2.58 (tr, 2H, H-6); 2.58 (tr, 2H, H-7); 4.96 (tr tr, J=11.6 Hz, J=4.1 Hz, 1H, H-4). .sup.13C-NMR (CDCl.sub.3, 100 MHz, RT) ? 8.96, 8.97 C-10, C-10; 27.28, 27.70 C-5, C-5; 41.79 C-6; 45.54 C-3; 55.63 C-2; 66.36 C-7; 67.02 C-4; 173.76, 174.05 C-8, C-8.

Example 10: Acetic acid 2-(4-acetoxy-2,2,6,6 tetramethyl-piperidin-1-yl)-ethyl ester (compound 10)

(48) ##STR00016##

(49) A three necked flask with over-head stirrer, reflux condenser, pressure equalized dropping funnel was charged with HE-HTMP (101.0 g, 0.502 mol). The apparatus was flushed thoroughly with nitrogen, and then immersed in an oil bath of 130? C. Then acetic acid anhydride (103.2 g, 1.011 mol) was added via the dropping funnel within ca. one hour. During the addition of the acid anhydride, the reaction mixture liquefied. Four hours after the addition of the acetic anhydride was completed, the conversion of the HE-HTMP was 93%, as indicated by gas chromatography. After another 90 minutes at 130? C., the reaction mixture was allowed to cool to ambient temperature, diluted with dichloromethane (ca. 200 ml) and poured into water. The pH of the bi-phasic mixture was carefully adjusted with sodium hydrogen carbonate to pH=7.0. The organic layer was then separated with a separatory funnel, and washed twice with water (ca. 200 ml each), dried (sodium sulphate) and the solvent removed on a rotary evaporator. The residue (141 g reddish oil) was distilled in vacuum (bp.=115?-125? C. at 0.01-0.019 mbar) to give a yellowish oil (129.5 g, 90.4% yield) which solidified on standing.

(50) mp.=53-54? C.

(51) .sup.1H-NMR (CDCl.sub.3. 400 MHz, RT) ? 1.08, 1.15 (2 s, 6H each, H-5, H-5); 1.41 (tr, 2H), 1.82 (dd, 2H), H-3, H-3; 2.02, 2.04 (2 s, 3H each, H-9, H-9); 2.68 (tr, 2H, H-6); 3.96 (tr, 2H, H-7); 5.06 (tr tr, 1H, H-4).

(52) .sup.13C-NMR (CDCl.sub.3. 100 MHz) ? 20.92, 21.40 C-9, C-9; 22.14, 33.72 C-5, C-5; 41.85 C-6; 45.60 C-3; 55.60 C-2; 66.64 C-7; 67.40 C-4; 170.61, 171.89 C-8, C-8.

Example 11: 3-Methoxy-propionic acid 2-[4-(3-methoxy-propionyl-oxy)-2,2,6,6-tetra-methyl-piperidin-1-yl]-ethyl ester (compound 11)

(53) ##STR00017##

(54) A jacketed 250 ml flask was fitted with an anchor stirrer, inner thermometer, gas inlet tube and a Dean-Stark apparatus with reflux condenser. The flask was charged with HE-HTMP (138 g, 0.69 mol) and xylenes (108 g, mixture of isomers). The mixture was heated at reflux (mantle temperature=150? C.), and ca. 40 ml of the solvent was distilled off in order to remove the water as azeotrope with the xylenes. Then the temperature was reduced to 80? C., and 3-methoxypropionic acid methyl ester (92.0 g, 0.75 mol) and tetrabutyl ortho-titanate (0.1 g) were added. The mixture was then heated again at reflux, and the forming methanol distilled off. After completion of the reaction the mixture was allowed to cool, and the resulting solution of the product was washed three times with water (250 ml each time). After drying (sodium sulphate) and removal of the xylenes on the rotary evaporator the residue was distilled in vacuum (boiling point 167? C./1.1*10.sup.?2 mbar) to give the product as clear, pale yellow liquid.

(55) .sup.1H-NMR (CDCl.sub.3, 400 MHz) ? 1.08, 1.15 (2 s, 6H each, H-5, H-5); 1.43 (tr, 2H), 1.83 (d d, 2H) H-3, H-3; 2.53, 2.56 (2 tr, 2H each, H-9, H-9); 2.69 (dd, 2H, H-6); 3.34, 3.35 (2 s, 3H each, H-11, H-11); 3.64, 3.65 (2 tr, 2H each, H10, H-10); 3.98 (dd, 2H, H-7); 5.10 (tr tr, 1H, H-4).

(56) .sup.13C-NMR (CDCl.sub.3, 100 MHz) ? 22.09, 33.63 C-5, C-5; 34.83, 35.18 C-9, C-9; 41.75, C-6; 45.49, C-3; 55.70, C-2; 58.63, 58.65 C-11, C-11; 66.64 C-7; 67.53 C-4; 67.86, 67.88 C-10, C-10; 171.04, 171.34 C-8, C-8.

Example 12: Methoxy-acetic acid 2-[4-(2-methoxy-acetoxy)-2,2,6,6-tetramethyl-piperidin-1-yl]-ethyl ester (compound 12)

(57) ##STR00018##

(58) This compound was prepared in an analogous manner as described in Example 11 using 2-methoxyacetic acid methyl ester instead of 3-methoxypropionic acid methyl ester. The crude products from two batches (in one batch 0.2 mol HE-HTMP were used, in the other batch 0.4 mol HE-HTMP were used, both crude products were brown oils) were combined for purification. The combined crude materials were dissolved in toluene (250 ml), and the dark brown solution de-colorized with bleaching earth (75 g and 50 g of Tonsil Optimum FF, Clariant). After filtration, the solvent was removed from the obtained light brown solution on the rotary evaporator. On cooling to ambient temperature the product started to crystallize. Thus, the material was re-dissolved in a minimum quantity of toluene at reflux (ca. 100 ml) and the solution allowed to cool slowly to 0? C. Then n-hexane (170 g) was added to bring crystallization to completion. The obtained almost colorless crystals were filtered off, washed with little n-hexane and dried to give 115.9 g (62% combined yield based on HE-HTMP) of almost colorless crystals.

(59) mp.=57-58? C.

(60) .sup.1H-NMR (CDCl.sub.3, 400 MHz) ? 0.80, 0.86 (2 s, 6H each, H-5, H-5); 1.15 tr, 2H, 1.55 dd, 2H, H-3, H-3; 2.41 (dd, 2H, H-6); 3.11, 3.17 (2 s, 3H each, H-10, H-10); 3.67, 3.71 (2 s, 2H each, H-9, H-9); 3.73, dd, 2H, H-7); 4.83 (tr tr, 1H, H-4).

(61) .sup.13C-NMR (CDCl3, 100 MHz) ? 21.91, 33.35 C-5, C-5; 41.51 C-6; 45.29 C-3; 55.49 C-2; 58.78 58.83 C-10, C-10; 66.28 C-7; 67.56 C-4; 69.33, 69.52 C-9, C-9; 169.38, 169.68 C-8, C-8.

Example 13: 4-Oxo-hexanoic acid 2,2,6,6-tetramethyl-1-[2-(4-oxo-pentanoyloxy)-ethyl]-piperidin-4-yl ester (compound 13)

(62) ##STR00019##

(63) A 250 ml jacketed vessel was fitted with an anchor stirrer, an inner thermometer and a descending condenser. It was charged with HE-HTMP (84.5 g, 0.42 mol) and methyl laevulinate (114.76 g, 0.882 mol). This mixture was heated and at an inner temperature of 151? C. tetrabutyl orthotitanate (0.12 g, 0.36 mmol) was added. The mantel temperature was set to 180? C. and mixture was kept stirring for 24 hours. Then the excess methyl laevulinate was removed in vacuum (1 h at 3 mbar), and then cooled to 80? C. The product was obtained as a very viscous brown oil, 154.4 g (92.5% based on HE-HTMP).

(64) .sup.1H-NMR (CDCl.sub.3, 400 MHz, RT) ? 0.89, 0.96 (2 s, 6H each, H-5, H-5); 1.24, 1.63 (2 m, 2H each, H-3, H-3); 2.00 (s, 6H, H-12, H-12); 2.36 (tr, 4H, H-9, H-9); 2.49 (tr, 2H, H-6); 2.56 (tr, 4H, H-10, H-10); 3.77 (tr, 2H; H-7); 4.86 (trtr, 1H, H-4).

(65) .sup.13C-NMR (CDCl.sub.3, 100 MHz, RT,) ? 21.87, 33.41 (C-5, C-5); 27.57, 28.03 (C-9, C-9); 29.50, 29.52 (C-12, C-12); 37.56, 37.59 (C-10, C-10); 41.51 (C-6); 45.24 (C-3); 55.45 (C-2); 66.42 (C-7); 67.34 (C-4); 171.89, 172.25 (C-8, C-8); 206.10; 206.17 (C-11, C11).

Application Examples

(66) Coating Formulations A: (Acid Catalyzed High Solid Clear Coating Formulation)

(67) TABLE-US-00001 Weight-% Joncryl? 510 (80% in n-butyl acetate) (SGO acrylic resin, 56.2 BASF SE) Luwipal? 066 (95%) (hexamethoxymethyl melamine resin, 19.2 BASF SE) n-butanol (solvent) 24.0 Dow Corning? 57 (10% in n-butanol) (slip and leveling 0.6 agent) 100.0 Hardener (catalyst): p-toluenesulfonic acid (40% in n-butanol) 2.0

(68) The formulations A were stabilized with 3.1 wt % (based on resin solids) Tinuvin? 384-2 (UV absorber, BASF SE).

(69) Each coating formulation A further contained 1.6 wt % (based on resin solids) of one of compounds 1 to 13, or of Tinuvin 622, or of Tinuvin 123.

(70) The clear coat formulations were subsequently sprayed onto a silver metallic base coat (DFT base coat: 18 ?m) in a thickness resulting after cure (130? C., 30) in a dry film thickness of 40 ?m.

(71) Coating Formulations B: (Epoxy Carboxy Coating Formulation: Ultra Gloss F 3000 (BASF Coatings, Japan))

(72) Component A/component B (50/50) [A=backbone, B=hardener component]

(73) The formulations B were stabilized with 2 wt. % (based on resin solids) Tinuvin 384-2. Each coating formulation B further contained 1 weight-% (based on resin solids) of one of compound 1 to 13, or of Tinuvin 622, or of Tinuvin 123.

(74) Solid content component A plus B: 57%

(75) The clear coat formulations were subsequently sprayed onto a silver metallic base coat (DFT base coat: 18 ?m) in a thickness resulting after cure (140? C., 30) in a dry film thickness of 40 ?m.

(76) Coating Formulations C: (Thermo-Setting Acrylic Melamine Clear Coating Formulation)

(77) TABLE-US-00002 Weight-% Viacryl? SC 303 (60% in xylene/butanol; 26/9) (acrylic 30.2 resin, Cytec) Viacryl? SC 370 (75% in SN/butylacetate) (acrylic resin, 25.6 Cytec) Maprenal? MF 650 (55% in isobutanol) (isobutylated 29.9 melamine-formaldehyde resin, lneos) Butyl acetate/butanol (37:8) (solvent) 4.7 Isobutanol (solvent) 5.3 Solvesso? 150 (solvent, Exxon Mobil Chemicals) 3.0 Baysilone? MA (1% in Solvesso 150) (leveling agent, 1.3 Momentive) 100.0

(78) Solids content: 53%

(79) The formulations C were stabilized with 2 wt. % (based on resin solids) Tinuvin? 384-2 (UV absorber, BASF SE).

(80) Each coating formulation C further contained 1 weight-% (based on resin solids) of one of compound 1 to 13, or of Tinuvin 622, or of Tinuvin 123.

(81) The clear coat formulations were subsequently sprayed onto a silver metallic base coat (DFT base coat: 18 ?m) in a thickness resulting after cure (130? C., 30) in a dry film thickness of 40 ?m.

(82) Coating Formulations D: (Long Oil Alkyd Clear Wood Coating Formulation)

(83) TABLE-US-00003 Weight-% Worleekyd B 870, 75% Exxsol D40 (long oil alkyd, Worlee- 45.70 Chemie GmbH) Octa-Soligen Calcium 5 (metal drier, OMG Borchers) 2.75 Octa-Soligen Zirconium 12 (metal drier, OMG Borchers) 0.30 Octa-Soligen Cobalt 10 (metal drier, OMG Borchers) 0.35 Exkin 2 (anti-skinning agent, Elementis) 0.20 Exxsol D30 (solvent, ExxonMobil Chemicals) 50.00 Tinuvin? 99-2 (UV absorber, BASF SE) 0.70 100.00

(84) Solids content: 34%

(85) Each coating formulation D further contained 1 wt. % (based on resin solids) of one of compounds 1 to 13, of Tinuvin 622, or of Tinuvin 123.

(86) The clear coat formulations were subsequently applied by brush (thickness: 3 layers a 80 g/m.sup.2 resulting after drying at room temperature in a dry film thickness of 70 ?m).

(87) Solubility Tests

(88) The solubility of above described coating formulations A, B, C, and D (each containing one of compounds 1 to 13, of Tinuvin 622, or of Tinuvin 123 in the amounts given above), was tested. The solubility was assessed qualitatively by visual aspect of turbidity of the solution and residual not dissolved particles in the solution. Results are given in the following table:

(89) TABLE-US-00004 Compound Formulations A Formulations B Formulations C Formulations D Tinuvin 622 not soluble not soluble not soluble not soluble Tinuvin 123 soluble soluble soluble Soluble Compound 1 soluble slow dissolution soluble Soluble Compound 2 soluble soluble soluble soluble Compound 3 soluble soluble soluble soluble Compound 4 slow dissolution not soluble soluble soluble Compound 5 Not soluble Not soluble slow dissolution slow dissolution Compound 6 Not soluble Not soluble slow dissolution soluble Compound 7 Soluble soluble slow dissolution soluble Compound 8 Soluble soluble slow dissolution soluble Compound 9 soluble soluble soluble soluble Compound 10 soluble soluble soluble slow dissolution Compound 11 soluble soluble soluble soluble Compound 12 soluble soluble soluble soluble Compound 13 soluble soluble soluble soluble
Compatibility Tests:

(90) For assessment of the compatibility (exudation due to incompatibility in the coating) the gloss of coatings B was measured after curing (BYK Haze-Gloss device 4601).

(91) TABLE-US-00005 Compound gloss (20?) Tinuvin 123 81 Compound 1 87 Compound 2 87 Compound 3 89 Compound 7 90 Compound 9 88 Compound 10 88 Compound 11 88 Compound 12 88 Compound 13 88

(92) The compounds do not indicate any negative effect on compatibility in the cured coating like gloss loss.

(93) Accelerated Weathering Tests:

(94) Coatings A, B, C, and D, as given in the tables below were tested under artificial weathering cycles to evaluate the stabilization, as indicated by the gloss retained after a given time of the artificial weathering cycle and crack formation.

(95) Coatings A, Xenon Lamps (SAE J 1960):

(96) TABLE-US-00006 Compound gloss (20?) after 3000 hours Without HALS 77 Tinuvin 123 90 Example 1 90 Example 2 90 Example 3 90 Example 4 <80 Example 7 91 Example 8 91 Example 9 90 Example 10 92 Example 11 92 Example 12 89 Example 13 95
Coatings B, Xenon Lamps (SAE J 1960):

(97) TABLE-US-00007 Gloss (20?) Gloss (20?) Compound after 3500 hours after 4500 hours Without HALS 77*) Tinuvin 123 87 87 Example 1 85 79 Example 2 87 87 Example 3 90 83 Example 7 88 84 Example 9 84 77 Example 10 84 70*) Example 11 88 87 Example 12 88 86 Example 13 88 84 *)cracking
Coatings B, UVB-313 nm Lamps (Q-UV DIN EN ISO 4292-3):

(98) TABLE-US-00008 Gloss (20?) Compound Gloss (20?) after 3000 hours after 3500 hours Without HALS 61*) Tinuvin 123 89 82 Example 1 71 *) Example 2 89 88 Example 3 87 76 Example 7 89 86 Example 9 76*) Example 10 70*) Example 11 78 72 Example 12 74 65 Example 13 83 80 *)cracking
Coatings C, Xenon Lamps (SAE J 1960):

(99) TABLE-US-00009 Compound Gloss (20?) after 4000 hours Without HALS 73 Tinuvin 123 93 Example 1 93 Example 2 91 Example 3 89 Example 9 87 Example 10 84 Example 11 92 Example 12 91 Example 13 93
Coatings C, UVB-313 nm Lamps (Q-UV DIN EN ISO 4292-3):

(100) TABLE-US-00010 Gloss (20?) Compound Gloss (20?) after 3000 hours after 3500 hours Without HALS <5 Tinuvin 123 86 85 Example 1 74 <35 Example 2 85 81 Example 3 85 83 Example 9 83 64*) Example 10 13 Example 11 81 54 Example 12 12 Example 13 87 77 *)cracking
Coatings D, UV-A 340 nm Fluorescence Bulbs (EN 927-6), Formulation D:

(101) TABLE-US-00011 Compound Extent of delamination/degradation after 1250 hours Without HALS Severe Tinuvin 123 Slight to moderate Example 2 slight Example 10 Moderate Example 12 Slight to moderate

(102) The compounds are suitable for stabilizing different types of coatings by retaining gloss and preventing from cracking, degradation or delamination.

(103) The following examples illustrate the invention further. All percentages and parts are by weight, unless stated otherwise. Compound 2 (3,5,5-trimethylhexanoic acid 2,2,6,6-tetramethyl-1-[2-(3,5,5-trimethyl-hexanoyloxy)-ethyl]-piperidin-4-yl ester) corresponds to the formula

(104) ##STR00020##

Example A-1: Stabilization of a Polymethylmethacrylate (PMMA) Solution Cast Film (1)

(105) 10 g of Plexiglas 7 N are dissolved in 40 g methylene chloride together with 50 mg of compound 2. Films are drawn with the help of an automatic blade (Erichsen?) with a blade speed of 12 mm/sec and a gap height of 120 ?m. The films are then exposed to xenon light in accordance to former ASTM G 26 C (Xe light, 2 borosilicate filters S, 0.35 W/m2 at 340 nm, 63? C.?3? C., 50-60% rel. humidity, continuous light, no water spray). The color is measured in accordance to DIN 6167 (1980-01). The results are shown in Table A-1.

(106) TABLE-US-00012 TABLE A-1 hours 0 99 263 472 1006 YI (Yellowness Index)*.sup.) ?0.5 0.5 0.3 0.3 0.5 ?E (Color difference)*.sup.) 0.0 1.0 0.8 0.9 1.1 b* (Color coordinate)*.sup.) ?0.2 0.4 0.3 0.3 0.4 *.sup.)Low values are desired.

Example A-2: Stabilization of a Polymethylmethacrylate (PMMA) Solution Cast Film (2)

(107) 10 g of Plexiglas 7 N are dissolved in 40 g methylene chloride together with 50 mg of compound 2 and 100 mg of 2,2-methylenebis(6-(2H-benzotriazol-2-yl)-4-1,1,3,3-tetramethylbutyl)phenol (Tinuvin?360). Films are drawn with the help of an automatic blade (Erichsen?) with a blade speed of 12 mm/sec and a gap height of 120 ?m. The freshly drawn film is dried for 10 minutes. The resulting film with a thickness of 25 ?m has a yellowness index of 16.3. (DIN 6167(1980-01)). This film is then exposed to xenon light in accordance to former ASTM G 26 C (Xe light, 2 borosilicate filters S, 0.35 W/m2 at 340 nm, 63? C.?3? C., 50-60% rel. humidity, continuous light, no water spray). The color is measured in accordance to DIN 6167 (1980-01). The results are shown in Table A-2.

(108) TABLE-US-00013 TABLE A-2 hours 0 99 263 472 1006 YI (Yellowness Index)*.sup.) 0.2 0.5 0.5 0.7 0.9 ?E (Color difference)*.sup.) 0.0 0.4 0.3 0.5 0.9 b* (Color coordinate)*.sup.) 0.2 0.4 0.4 0.5 0.7 *.sup.)Low values are desired.

Example A-3: Stabilization of a Polymethylmethacrylate (PMMA) Thick Sheet (1)

(109) 70 g of freshly distilled methylmethacrylate are mixed with 70 mg of lauroylperoxide and 105 mg of compound 2. The mixture is degassed and heated in a twist-off glass for 3 hours in a waterbath at 60? C. The prepolymerized syrup is poured between two glass plates, with 1.8 mm distance, which are sealed on three sides. This glass sandwich is kept for 16 hours at 60? C. in an oven, followed by 3 hours at 120? C. The resulting polymethylmethacrylate (PMMA) sheet has a yellowness index of 32.2 (DIN 6167 (1980-01)). This sheet is then exposed to xenon light in accordance to former ASTM G 26 C (Xe light, 2 borosilicate filters S, 0.35 W/m2 at 340 nm, 63? C.?3? C., 50-60% rel. humidity, continuous light, no water spray). The color is measured in accordance to DIN 6167 (1980-01). The results are shown in Table A-3.

(110) TABLE-US-00014 TABLE A-3 hours 0 257 494 754 986 YI (Yellowness Index)*.sup.) 10.31 0.87 1.14 0.91 0.91 ?E (Color difference)*.sup.) 10.00 0.35 0.60 0.55 0.55 b* (Color coordinate)*.sup.) 0.30 0.62 0.77 0.63 0.62 *.sup.)Low values are desired.

Example A-4: Stabilization of a Polymethylmethacrylate (PMMA) Thick Sheet (2)

(111) 70 g of freshly distilled methylmethacrylate are mixed with 70 mg of lauroylperoxide, 105 mg of compound 2 and 105 mg of 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol (Tinuvin?571). The mixture is degassed and heated in a twist-off glass for 3 hours in a waterbath at 60? C. The prepolymerized syrup is poured between two glass plates, with 1.8 mm distance, which are sealed on three sides. This glass sandwich is kept for 16 hours at 60? C. in an oven, followed by 3 hours at 120? C. The resulting PMMA sheet has a yellowness index of 32.2 (DIN 6167 (1980-01)). This sheet is then exposed to xenon light in accordance to former ASTM G 26 C (Xe light, 2 borosilicate filters S, 0.35 W/m2 at 340 nm, 63? C.?3? C., 50-60% rel. humidity, continuous light, no water spray). The color is measured in accordance to DIN 6167 (1980-01). The results are shown in Table A-4.

(112) TABLE-US-00015 TABLE A-4 hours 0 257 494 754 986 YI (Yellowness Index)*.sup.) 0.98 1.03 1.42 1.42 1.55 ?E (Color difference)*.sup.) 0.00 0.13 0.61 0.62 0.76 b* (Color coordinate)*.sup.) 0.72 0.75 0.96 0.97 1.03 *.sup.)Low values are desired.

Example A-5: Stabilization of a Polycarbonate/Acrylonitrile Butadiene Styrene (PC/ABS) Plaque

(113) 4000 g of PC/ABS (Pulse?A35-105 natural) is cryo-ground and dried in a vacuum oven at 80? C. for 4 hours. In a Henschel? high-speed mixer the ground polymer is mixed with 4 g of compound 2 and 12 g of 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (Tinuvin?234). The powder mixture is then compounded on a Berstorff?ZE 25?32D at 270? C. and after drying in a Heliomat.sup.22000 6K drier injection molded on an Engel?EK65 at 260? C. to 2?60?60 mm.sup.3 thick plaques. These plaques are exposed to xenon light in accordance to former ASTM G 155 Cycle 1 (Xe light, 2 borosilicate filters S, 0.35 W/m2 at 340 nm, 63? C.?3? C., 50-60% rel. humidity, continuous light, 102 minutes dry followed by 18 minutes water spray). The color is measured in accordance to DIN 6167 (1980-01). The results are shown in Table A-5.

(114) TABLE-US-00016 TABLE A-5 hours 0 259 529 742 1008 YI (Yellowness Index)*.sup.) 17.3 7.3 11.8 16.2 29.3 ?E (Color difference)*.sup.) 0 5.79 3.15 0.62 7.15 b* (Color coordinate)*.sup.) 10.7 5.0 7.6 10.1 17.7 *.sup.)Low values are desired.

Example A-6: Stabilization of High Density Polyethylene (HDPE) (1)

(115) 4000 g of HDPE (Tipelin?BS 501-17; unstabilized) is mixed with 4 g of compound 2 in a Brabender?PL 2000 for 10 minutes at 200? C. with 30 rpm. The material is then pressed in a pneumatic press at 190? C. for 2 minutes to 1 mm thick plaques which are subjected to the following test a) or b).

(116) a) The plaques obtained are exposed to xenon light in accordance to ASTM G 155 Cycle 1 (Xe light, 2 borosilicate filters S, 0.35 W/m2 at 340 nm, 63? C.?3? C., 50-60% rel. humidity, continuous light, 102 minutes dry followed by 18 minutes water spray). The color is measured in accordance to DIN 6167 (1980-01). The results are shown in Table A-6a.

(117) TABLE-US-00017 TABLE A-6a hours 0 259 YI (Yellowness Index)*.sup.) 2.47 ?1.53 ?E (Color difference)*.sup.) 0 2.14 b* (Color coordinate)*.sup.) 1.63 ?0.42 *.sup.)Low values are desired.

(118) b) The plaques obtained are exposed in an oven with circulating air at 110? C. The color is measured in accordance to DIN 6167 (1980-01). The results are shown in Table A-6b.

(119) TABLE-US-00018 TABLE A-6b days 0 4 7 11 14 18 YI (Yellowness Index)*.sup.) 0.67 1.79 1.88 1.72 1.72 1.72 ?E (Color difference)*.sup.) 0 0.67 0.72 1.36 1.36 1.36 b* (Color coordinate)*.sup.) 0.7 1.34 1.39 1.31 1.31 1.31 *.sup.)Low values are desired.

Example A-7: Stabilization of High Density Polyethylene (HDPE) (2)

(120) 4000 g of HDPE (Tipelin?BS 501-17; unstabilized) is mixed with 2 g of compound 2 and 2 g of the condensate of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid dimethylester (Tinuvin?622) in a Brabender?PL 2000 for 10 minutes at 200? C. with 30 rpm. The material is then pressed in a pneumatic press at 190? C. for 2 minutes to 1 mm thick plaques which are subjected to the following test a) or b).

(121) a) The plaques obtained are exposed to xenon light in accordance to ASTM G 155 Cycle 1 (Xe light, 2 borosilicate filters S, 0.35 W/m2 at 340 nm, 63? C.+3? C., 50-60% rel. humidity, continuous light, 102 minutes dry followed by 18 minutes water spray). The color is measured in accordance to DIN 6167 (1980-01). The results are shown in Table A-7a.

(122) TABLE-US-00019 TABLE A-7a hours 0 259 YI (Yellowness Index)*.sup.) 2.85 ?1.39 ?E (Color difference)*.sup.) 0 2.37 b* (Color coordinate)*.sup.) 1.97 ?0.35 *.sup.)Low values are desired.

(123) b) The plaques obtained are exposed in an oven with circulating air at 110? C. The color is measured in accordance to DIN 6167 (1980-01). The results are shown in Table A-7b.

(124) TABLE-US-00020 TABLE A-7b days 0 4 7 11 14 18 YI (Yellowness Index)*.sup.) 3.79 9.11 9.62 8.83 8.83 8.83 ?E (Color difference)*.sup.) 0 2.97 3.26 3.32 3.32 3.32 b* (Color coordinate)*.sup.) 2.48 5.41 5.69 5.20 5.20 5.20 *.sup.)Low values are desired.

Example A-8: Stabilization of Polypropylene (PP) (1)

(125) 2000 g unstabilized PP is mixed with 1 g of 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (Irganox?3114), 1 g of tris(2,4-di-tert-butylphenyl)phosphite (Irgafos?168) and 2 g of compound 2 in a high speed mixer and then compounded at 220? C. on a Berstorff?ZE 25?32D twin screw extruder. The composition is injection molded at 230? C. on an Engel?EK 65 into 2?60?60 mm.sup.3 plaques which are subjected to the following test a) or b).

(126) a) The plaques obtained are exposed to xenon light in accordance to ASTM G 155 Cycle 1 (Xe light, 2 borosilicate filters S, 0.35 W/m2 at 340 nm, 63? C.?3? C., 50-60% rel. humidity, continuous light, 102 minutes dry followed by 18 minutes water spray). The color is measured in accordance to DIN 6167 (1980-01). The results are shown in Table A-8a.

(127) TABLE-US-00021 TABLE A-8a hours 0 100 262 504 1007 YI (Yellowness Index)*.sup.) 17.7 9.2 8.8 9.3 2.2 ?E (Color difference)*.sup.) 0 5.08 5.5 5.45 12.59 b* (Color coordinate)*.sup.) 8.4 4.5 4.4 4.6 1.2 *.sup.)Low values are desired.

(128) b) The plaques obtained are exposed in an oven with circulating air at 135? C. The color is measured in accordance to DIN 6167 (1980-01). The results are shown in Table A-8b.

(129) TABLE-US-00022 TABLE A-8b days 0 1 4 7 10 14 YI (Yellowness Index)*.sup.) 18.1 18.1 19.7 20.4 21.1 21.7 ?E (Color difference)*.sup.) 0.0 0.9 0.8 1.2 1.5 1.9 b* (Color coordinate)*.sup.) 8.6 8.5 9.3 9.7 10.1 10.4 *.sup.)Low values are desired.

Example A-9: Stabilization of Polypropylene (PP) (2)

(130) 2000 g of unstabilized PP is mixed with 1 g of 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (Irganox?3114), 1 g of tris(2,4-di-tert-butylphenyl)phosphite (Irgafos?168), 1 g of compound 2 and 1 g of Chimassorb?2020 in a high speed mixer and then compounded at 220? C. on a Berstorff?ZE 25?32D twin screw extruder. The composition is injection molded at 230? C. on an Engel?EK 65 into 2?60?60 mm.sup.3 plaques which are subjected to the following test a) or b).

(131) Chimassorb?2020:

(132) (Chemical Abstracts No. 192268-64-7)

(133) ##STR00021##

(134) Molecular weight: 2600-3400 g/mol

(135) a) The plaques obtained are exposed to xenon light in accordance to ASTM G 155 Cycle 1 (Xe light, 2 borosilicate filters S, 0.35 W/m2 at 340 nm, 63? C.?3? C., 50-60% rel. humidity, continuous light, 102 minutes dry followed by 18 minutes water spray). The color is measured in accordance to DIN 6167 (1980-01). The results are shown in Table A-9a.

(136) TABLE-US-00023 TABLE A-9a hours 0 100 262 504 1007 YI (Yellowness Index)*.sup.) 17.5 8.9 8.2 8.4 8.7 ?E (Color difference)*.sup.) 0 4.9 5.44 5.43 5.68 b* (Color coordinate)*.sup.) 8.6 4.4 4.0 4.1 4.4 *.sup.)Low values are desired.

(137) b) The plaques obtained are exposed in an oven with circulating air at 135? C. The color is measured in accordance to DIN 6167 (1980-01). The results are shown in Table A-9b.

(138) TABLE-US-00024 TABLE A-9b days 0 1 4 YI (Yellowness Index)*.sup.) 17.4 17.3 21.1 ?E (Color difference)*.sup.) 0.0 1.1 1.9 b* (Color coordinate)*.sup.) 8.6 8.5 10.0 *.sup.)Low values are desired.

Example A-10: Stabilization of Polypropylene (PP) (3)

(139) 2000 g of unstabilized PP is mixed with 1 g of 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (Irganox?3114), 1 g of tris(2,4-di-tert-butylphenyl)phosphite (Irgafos?168), 1 g of compound 2 and 1 g of the condensate of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid dimethylester (Tinuvin?622) in a high speed mixer and then compounded at 220? C. on a Berstorff?ZE 25?32D twin screw extruder. The composition is injection molded at 230? C. on an Engel?EK 65 to 2?60?60 mm.sup.3 plaques which are subjected to the following test a) or b).

(140) a) The plaques are exposed to xenon light in accordance to ASTM G 155 Cycle 1 (Xe light, 2 borosilicate filters S, 0.35 W/m2 at 340 nm, 63? C.?3? C., 50-60% rel. humidity, continuous light, 102 minutes dry followed by 18 minutes water spray). The color is measured in accordance to DIN 6167 (1980-01). The results are shown in Table A-10a.

(141) TABLE-US-00025 TABLE A-10a hours 0 100 262 504 1007 YI (Yellowness Index)*.sup.) 19.8 9.4 8.6 8.5 6.1 ?E (Color difference)*.sup.) 0 5.97 6.55 6.65 9.37 b* (Color coordinate)*.sup.) 9.5 4.7 4.2 4.2 3.1 *.sup.)Low values are desired.

(142) b) The plaques obtained are exposed in an oven with circulating air at 135? C. The color is measured in accordance to DIN 6167 (1980-01). The results are shown in Table A-10b.

(143) TABLE-US-00026 TABLE A-10b days 0 1 4 7 10 YI (Yellowness Index)*.sup.) 19.7 19.6 21.1 22.4 23.8 ?E (Color difference)*.sup.) 0.0 0.8 0.8 1.3 2.0 b* (Color coordinate)*.sup.) 9.4 9.2 10.0 10.7 11.3 *.sup.)Low values are desired.

Example A-11: Stabilization of Polybutadiene Terephthalate (PBT) (1)

(144) 2500 g of PBT (Crastin?6134) is cryo-ground and dried in a vacuum oven at 80? C. for 4 hours. In a Henschel? high-speed mixer the ground polymer is mixed with 1.25 g of ethylenebis(oxyethylene)bis-(3-(5-tert-butyl-4-hydroxy-m-tolyl)-propionate) (Irganox?245), 3.75 g of tris(2,4-di-tert-butylphenyl)phosphite (Irgafos?168), 12.5 g of 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (Tinuvin?234) and 2.5 g of compound 2. The powder mixture is then compounded on a Berstorff?ZE 25?32D at 245? C. and after drying in a Heliomat?2000 6K drier injection molded on an Engel?EK65 at 250? C. to 2?60?60 mm.sup.3 thick plaques. These plaques are exposed to xenon light in accordance to ASTM G 155 Cycle 1 (Xe light, 2 borosilicate filters S, 0.35 W/m2 at 340 nm, 63? C.?3? C., 50-60% rel. humidity, continuous light, 102 minutes dry followed by 18 minutes water spray). The color is measured in accordance to DIN 6167 (1980-01). The results are shown in Table A-11.

(145) TABLE-US-00027 TABLE A-11 hours 0 100 243 500 YI (Yellowness Index)*.sup.) 32.2 35.9 39.1 42.2 ?E (Color difference)*.sup.) 0 2.3 4.1 5.9 b* (Color coordinate)*.sup.) 17.2 19.5 21.2 23.0 *.sup.)Low values are desired.

Example A-12: Stabilization of Polybutadiene Terephthalate (PBT) (2)

(146) 2500 g of PBT (Crastin?6134) is cryo-ground and dried in a vacuum oven at 80? C. for 4 hours. In a Henschel? high-speed mixer the ground polymer is mixed with 1.25 g of ethylenebis(oxyethylene)bis-(3-(5-tert-butyl-4-hydroxy-m-tolyl)-propionate) (Irganox?245), 3.75 g tris(2,4-di-tert-butylphenyl)phosphite (Irgafos?168), 12.5 g 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (Tinuvin?234), 1.25 g of the condensate of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid dimethylester (Tinuvin?622) and 1.25 g of compound 2. The powder mixture is then compounded on a Berstorff?ZE 25?32D at 245? C. and after drying in a Heliomat?2000 6K drier injection molded on an Engel?EK65 at 250? C. to 2?60?60 mm.sup.3 thick plaques. These plaques are exposed to xenon light in accordance to ASTM G 155 Cycle 1 (Xe light, 2 borosilicate filters S, 0.35 W/m2 at 340 nm, 63? C.?3? C., 50-60% rel. humidity, continuous light, 102 minutes dry followed by 18 minutes water spray). The color is measured in accordance to DIN 6167 (1980-01). The results are shown in Table A-12.

(147) TABLE-US-00028 TABLE A-12 hours 0 100 243 500 YI (Yellowness Index)*.sup.) 32.8 36.2 39.2 42.1 ?E (Color difference)*.sup.) 0 2.1 3.8 5.5 b* (Color coordinate)*.sup.) 17.8 19.9 21.5 23.1 *.sup.)Low values are desired.

Example A-13: Stabilization of a Polyurethane (PUR) Soft Foam

(148) a) Preparation of the Polyether/Polyurethane Soft Foams:

(149) 0.71 g (0.45% by weight based on the polyol) of anti-scorch stabilizer Irgastab?PUR 68 of BASF and 4.73 g (3.00% by weight referred to polyol) of the light stabilizer composition listed in Table A-13a are dissolved in 157.1 g of a polyether polyol (Lupranol?2074 of BASF, trifunctional polyether polyol containing predominantly secondary hydroxyl groups; hydroxyl number 48 mg KOH/g, water content less than 0.1%, acid number less than 0.06 mg KOH/g), 9.84 g of a solution consisting of 1.89 g of Tegostab?BF 2370 (a silicone surfactant of Evonik Industries), 0.24 g of Tegoamin?33 (amine catalyst of Evonik Industries, 33% by weight of triethylenediamine and 67% by weight of dipropyleneglycol) and 7.5 g of deionized water are added and the reaction mixture is stirred vigorously for 10 seconds at 2600 rpm. 0.31 g Kosmos?29 (catalyst based on stannous octoate of Evonik Industries) is then added and the reaction mixture is again stirred vigorously for 18 seconds at 2600 rpm. 92.19 g of an isocyanate [Lupranat?T80 of BASF; toluene-2,4- and toluylene-2,6-diisocyanate mixture] is then added with continuous stirring for 5 to 7 seconds at 2600 rpm. The mixture is then poured into a 20?20?20 cm.sup.3 cake-box and the exothermic temperature is measured during foaming to a foam block. The foam blocks are cooled and stored at room temperature for 24 hours. The next day the foams are cut into 4.4 cm?3 cm?1 cm specimens for the weathering tests.

(150) TABLE-US-00029 TABLE A-13a PUR Light stabilizer mixture PUR 1 2.365 g of compound 2 and 2.365 g of stabilizer 1 PUR 2 2.365 g of compound 2 and 2.365 g of stabilizer 2 PUR 3 2.365 g of compound 2 and 2.365 g of stabilizer 3 Stabilizer 1: 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol (Tinuvin?571) Stabilizer 2: Reaction product of methyl 3-(3-(2H-benzotriazole-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate/polyethyleneglykol 300 (Tinuvin?213) Stabilizer 3: Mixture of 95% of 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid C.sub.7-C.sub.9alkylester and 5% of 1-methoxy-2-propyl acetate (Tinuvin?384-2)

(151) b) Weathering is used in order to assess the foam stability upon light exposure. The foam samples are put in the weathering chamber and are exposed according to ASTM G 155-Cycle 4. The color change is determined as a function of time. The foam color quality is reported in terms of Yellowness Index (YI) determined on the foam samples in accordance with the ASTM 1926-70. The results are listed in Table A-13b.

(152) TABLE-US-00030 TABLE A-13b hours PUR 0 3 6 9 12 18 24 PUR 1 YI*.sup.) ?0.9 4.5 8.4 13.8 15.5 18.6 24.7 PUR 2 YI*.sup.) ?0.5 5.5 8.9 15.0 16.0 18.3 26.6 PUR 3 YI*.sup.) ?0.4 4.7 9.4 14.5 15.2 19.9 26.0 *.sup.)Low values are desired.

Example A-14: Stabilization of Thermoplastic Polyurethane (TPU)

(153) a) 3000 g of cryoground TPU (Desmopan?385 E) are dried in a vacuum oven at 80? C. for 12 hours. In a Henschel? mixer heated to 80? C. the polymer is mixed with the stabilizer system indicated in Table A-14a and then compounded on a twin screw extruder Berstorff?ZE 25?32D at 2100 C. After drying with a hot air drier the compounds are injection molded on a Engel?HL 60 machine into 2?44?68 mm.sup.3 plaques.

(154) TABLE-US-00031 TABLE A-14a TPU Stabilizer system TPU 1 10.2 g of Irganox?1010, 4.8 g of Irgafos?126, 45 g of compound 2 and 45 g of Tinuvin?PA 328 TPU 2 10.2 g of Irganox?1010, 4.8 g of Irgafos?126, 45 g of compound 2 and 45 g of Tinuvin?571 TPU 3 10.2 g of Irganox?1010, 4.8 g of Irgafos?126, 45 g of compound 2 and 45 g of Tinuvin?213 Irganox?1010: Pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] Irgafos?126: Bis[2,4-di-tert-butylphenyl] pentaerythritol diphosphite Tinuvin?PA 328: 2-(2H-benzotriazol-2-yl)-4,6-bis(1,1-dimethylpropyl)phenol Tinuvin?571: 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol Tinuvin?213: Reaction product of methyl 3-(3-(2H-benzotriazole-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate/polyethyleneglykol 300

(155) b) These plaques are exposed to xenon light in accordance to former ISO 105 B 06 (Xe light, inner filter borosilicate S and outer filter sodalime, 0.45 W/m2 at 340 nm, 100? C.?3? C., 20-30% rel. humidity, continuous light, no water spray). The color is measured in accordance to DIN 6167 (1980-01). The results are shown in Table A-14b.

(156) TABLE-US-00032 TABLE A-14b hours TPU 0 8 24 48 96 TPU 1 YI*.sup.) 13.62 13.09 13.15 13.22 14.46 TPU 2 YI*.sup.) 11.61 10.56 10.69 11.08 13.18 TPU 3 YI*.sup.) 11.88 10.64 10.79 11.46 12.71 *.sup.)Low values are desired for the yellowness index (YI).

Example A-15: Stabilization of Flexible Polyvinyl Chloride (f-PVC)

(157) A base mixture of 64.73 phr PVC (Norvinyl?S7060 of Ineos), 32.36 phr diisononylphthalate plasticizer (Palatinol?N of BASF), 1.61 phr epoxidized soybean oil (Drapex?39 of Galata Chem.) and 1.30 phr heat stabilizer (Baerostab?CT 9051?RF of Baerlocher; liquid CaZn stabilizer) is prepared (phr means parts per hundred rubber). 40 g of this PVC blend is mixed with 0.1 g of 2-hydroxy-4-octyloxybenzophenone (Chimassorb?81) and 0.1 g of compound 2 in a glass beaker and then calendered for 8 minutes at 160? C. with f=1:1.2 on a two roll mill with a gap width of 0.4 mm. The sheets obtained are then exposed to xenon light in accordance to ASTM G 155 Cycle 1 (Xe light, 2 borosilicate filters S, 0.35 W/m2 at 340 nm, 63? C.?3? C., 50-60% rel. humidity, continuous light, 102 minutes dry followed by 18 minutes water spray). The color is measured in accordance to DIN 6167 (1980-01). The results are shown in Table A-15.

(158) TABLE-US-00033 TABLE A-15 hours 0 243 500 1005 1501 YI (Yellowness Index)*.sup.) 3.2 2.0 2.1 2.0 2.4 ?E (Color difference)*.sup.) 0 0.7 0.6 0.7 0.4 b* (Color coordinate)*.sup.) 1.9 1.2 1.3 1.3 1.5 *.sup.)Low values are desired.