GB2179650A

GB2179650A - 2,2,6,6-Tetramethylpiperidylamides of substituted carboxylic acids and polymeric compositions containing them

Info

Publication number: GB2179650A
Application number: GB08521293A
Authority: GB
Inventors: Vladimir Ivanovich Paramonov
Original assignee: Individual
Current assignee: Individual
Priority date: 1985-08-27
Filing date: 1985-08-27
Publication date: 1987-03-11
Also published as: CH666028A5; DE3533451A1; GB2179650B; NL8502481A; JPS6267072A; GB8521293D0

Abstract

2,2,6,6-tetramethylpiperidylamides of substituted carboxylic acids of the formula: <IMAGE> in which n is 1 or 2; and A, when n is 1, is a phenoxymethyl, phenylthiomethyl, 4-t-butyl-phenoxymethyl, phenylaminomethyl, 2-benzylamino-ethyl, 2-(2',2',6',6'-tetramethylpiperid-4-ylamino)-propen-1-yl group, or a group -(CH2)m-X (in which m is 1 or 2, and X is a 2,2,6,6-tetramethylpiperid-4-ylamino, cyclohexylamino, N-piperidyl or N-morpholinyl group); or, when n is 2, a group <IMAGE> (in which n and m have the meanings defined above). are useful photostabilizers of polymeric compositions.

Description

SPECIFICATION 2,2,6,6-Tetramethylpiperidylamides of substituted Carboxylic Acids and Polymeric compositions containing them The present invention relates to derivatives of 2,2,6,6,-tetramethylpiperidine and, more particularly, to 2,2,6,6,-tetramethylpiperidylamides of subsitituted carboxylic acids and to polymeric compositions containing them.

It has now been found, in accordance with the present invention, that certain 2,2,6,6tetramethylpiperidylamides of substituted carboxylic acids, as hereinafter defined may be used as photostabilizors for polymeric materials for use, for example, in the manfacture of polymeric films for making greenhouses, fibres and injection moulded articles such as tubes.

According to the invention, therefore, there are provided as new compounds, compounds of the formula

inwhichnisl or 2, and A, when n is 1, is a phenoxymethyl, phenylthiomethyl, 4-t.butyl-phenoxymethyl phenylaminomethyl, 2 (benxylamino 2-benzylaminoethyl, or 2-(2',2',6',6'-tetramethyl-piperidyl-4-yl)-propen-l-yl group, or a group - (CH2)m-X (in which m is 1 or 2 and X is a 2,2,6,6-tetramethylpiperid-4-yl-amino, cyclohexylamino, N-piperidino or N-morpholino group); or,

(in which n and m have the meanings detail above).

The compounds according to the invention are white crystalline substances with melting points from 82 to 230"C and are soluble in in aliphatic alcohols and chlorinated hydrocarbons.

The invention further provides a polymeric composition comprising a polymer and, as photostabilzer, a compound of formula (I), suitably in an amount of from 0.05 to 1% by weight, based on the weight of the compound of formula (I) and the polymer.

The polymer may be a well-known polymer such as a polyolefin (e.g. high or low-density polyethylene, polypropylene and copolymers thereof), polystyrene and copolymers of styrene, polyvinyl chloride, polyamides, polyurethanes and the like).

In order to improve the thermal stability of the photostable polymeric composition according to the invention, it is advisable to incorporate therein a thermostabilizer, suitably in an amount of from 0.05 to 0.3% by weight based on the weight of the polymer. As thermostabilizers then can be used compounds selected from the generally known classes of thermostabilizers such as sterically hindered phenol derivatives, for example the tetraester of 3,5-di-tert.butyl-4- hydroxyphenylpropionic acid and pentaerythritol (Irganox 1010), the octadecyl ester of 3,5-di-tert.-butyl-4-hydroxy-phenylpropionic acid (Irganox 1076), and 2,2'-methylene-bis-(4-methyl- 6-tert.butylphenol) (AO-2246); phosphites such as tri-(para-nonylphenyl)-phoshite (Polygard); and the like.

In order to enhance the photostabilizing effect it is advisable to also introduce a UV-light stabilizer (UV-absorber) in the photostable polymeric composition suitably in an amount of from 0.1 to 0.3% by weight based on the weight of the polymer. Examples of UV-absorbers include o-hydroxybenxophenone derivatives such as 2-hydroxy-4-octyloxybenzophenon (Cyasorb 531); and o-hydroxybenzotriazole derivatives such as 2-(3',5'-ditert.butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole (tinuvin 327) and 2-(2'-hydroxy-5'methylp- henyl)-benxotriazole (Tinuvin P).

The amount of the photostabilizers (the compounds of formula 1), thermostabilizers and UV-absorbers is limited by the achievement of a maximum stabilizing effect, on the one hand, and by economic efficiency of the composition, on the other.

Polymeric materials stabilized by the compounds according to the invention can be used to produce a variety of articles such films, fibres, plates and rods.

Photostable polymeric compositions stablized by the compounds of formula (I) are from 1.5 to 4 times superior, in their photostability, to photostable polymeric compositions stabilized by o-hydroxybenzophenone and O-hydroxybenxotriazole derivatives and from 10 to 15% superior to compositions based on esters of 2,2,6,6-tetramethyl-4-hydroxypiperidine and carboxylic acids. Furthermore, the compounds of formula (I) have a thermostabilizing effect in polystyrene plastics.

The processes as for producing the compounds of formula (I) and for producing photostable polymeric compositions stabilized there with, are simple, make use of standard equipment and can be practised in the following manner.

The process for the preparation of the compounds according to the invention is based on the amidation of acids or their lower alkyl esters with 2,2,6,6-tetramethyl-4-aminopiperidine (triacetonediamine) at a temperature of from 170 to 21 0'C with the simultaneous distilling-off of lower alcohols or water evolved (cf.

Veigand-Hilgetag "Experimental Methods in Organic Chemistry", "Khimiya" Publishers, Moscow, 1968, pp.

445, 454). The desired products may be isolated by recrystallization from organic solvents.

Photostable polymeric compositions are produced by standard instrustrial processes. The photostabilizer is introduced into the polymer either in the stage of the polymer production or in the stage of processing it into an article.

The process is performed using any standard equipment e.g. an extruder, mill or injection-moulding machine.

The photostabilizer can be introduced into the polymer either individually or in the form of a solution of suspension in a corresponding solvent or a dispersing agent.

Thermostabilizers and UV-absorbers can be introduced both in the stage of the polymer production and in the stage of its processing.

In order that the invention may be well understood the following examples are given by way of illustration only.

Example 1 A 100 ml three-neck flask provided with a stirrer, thermometer, Wurtz packing with a descending condenser and a receiver was charged with 15.62 g of triacetonediamine and 18.39 g of the ethyl ester of N-cyclohexylaminoacetic acid. The charged flask was heated at a temperature of from 180 to 210"C until the evolution of ethanol ceased.After cooling the reaction mixture, the product was recrystallized from toluene to give 25.1 g (85% of the theoretical value as calculated for triacetonediamine) of the desired product, namely: the 2,2,6,6-tetramethylpiperidylamide of N-cyclohexylaminoacetic acid (compound I) melting at 83"C. Anaylsis (C13H33N3) Calculated. %: -C 69.11 H 11.26, N 14.23 found, %: C 68.98, H 11.56, N 14.08 Molecular weight: calculated 295.47 found 290.7 IR - specroscopy data: vC= O (amide I) = 1665cm1; b NH (amide 11) - 1510 cm~1; vNH = 336- cm-l.

Example 2 The compound of this Example, namely 2,2,6,6-tetramethylpiperidylamide of N-morpholinacetic acid (compound II), was obtained following the procedure described in Example 1 from 15.52 g of triacetonediamine and 17.28 g of N-morpholineoacetic acid ethylate. The yield was 26.24 g (92.6% of the theoretical value as calculated for triacetonediamine) and it melting point was 103"C (toluene).

Elemental composition: C,5H29N302. Molecular weight: Calculated, %: C 63.57, H 10.31, N 14.82 283.42 Found, %: C 63.74, H 10.28, N 14.48 317.8 IR-spectroscopy data: vC=O (amide I) = 1685 CM -1-6NH (amide ll) = 1515 cm' vNH = 3385 cm.

Example 3 The compound of this Example, namely, the 2,2,6,6-tetramethylpiperidylamide of N-piperidinoacetic acid (compound Ill), was produced in a manner similar to that described in Example 1 from 62.5g of triacetonediamine and 68.34 g of N-piperidinoacetic acid ethylate. The yield of the desired product was 90.74 g (80.6% of the theoretical value as calculated for triacetonediamine), and the melting point was 77"C (toluene).

Elemental Composition: C16H31N3O. Molecular weight: Calculated, %: C 68.28, H 11.10, N 14.93 281.45 Found %: C 68.61, H 10.91, N 14.83 280.4 IR-spectroscopy data: vc=O (amidel) = 1680 cm~1; bNH (amide 11) = 1510 cm-', aNH= 3375 cm~1.

Example 4 The compound of this Example, namely the 2,2,6,-tetramethylpiperidylamide of anilineacetic acid (compound IV), was produced following the procedure described in Example 1 from 23.44 g of triacetonediamine and 26.8 g of anilinoacetic acid ethylate.

The yield of the desired product was 35.7 g (82.2% of the theoretical value as calculated for triacetonediamine) and the melting point was 175"C (isopropanol).

Elemental composition: C,7H27N3O. Molecular weight: Calculated, %, C 70.55, H 9.40, N 14.52. 289.4 Found, %: C 70.34, H 9.96, N 14.68. 282.5 IR-spectroscopy data: #c=o (amide I) = 1655 cm~1; 6,, (amide II) = 1500 cm-l; aNH = 3390, 3440 cm-l.

Example 5 The compound of this Example, namely the N, N'-bis-(2,2,6,6-tetramethylpiperidyl)-acetamide of piperazine (compound V), was produced following the procedure described in Example 1 from 31.25 g of triacetonediamine and 25.75 g of N,N'-piperazinodiacetic acid diethylate.

The yield of the desired product was 37 g (77.3% of the theoretical value as calculated for triacetonediamine) and the melting point was 230"C (toluene).

Elemental composition: C26H50N6O2. Molecular weight: Calculated, %: C 65.23, H 10.53, N 17.55. 478.7 Found, %: C 65.30, H 10.60, N 17.78. 472.5 IR-spectroscopy data: vC=O (amide I) = 1650 cm-l; BNH (amide II) = 1530 cm~:,1500 cm~1; VNH = 3350 cm'.

Example 6 The compound of this Example, namely the 2,2,6,6-tetramethylpiperidylamide of N-cyclohexylaminopropionic acid (compound VI), was produced in a manner similar to that described in Example 1 from 31.25 g of triacetonediamine and 37.05 g of N-cyclohexylaminopropionic acid methylate. The yield of the desired product was 53.4 g (66.4% of the theorectical value as caluated for triacetonediamine) and the melting point was 122"C.

Elemental composition: C,8H35N3O. Molecular weight: Calculated: %: C 69.85, H 11.40, N 13.58. 309.5 Found, %: C 69.55, H 11.32, N 13.43. 308.2 IR-spectroscopy data: vC=O (amide I) = 1670 cm~1; Example 7 The compound of this Example, namely the N,N'-bis- (2,2,6,6-tetramethylpiperidyl) -propioamide of piperazine (compound VII), was produced in a manner similar to that described in Example 1 from 31.25 g of triacetonediamine and 25.8 g of N,N'-piperazinodipropionic acid dimethylate. The yield of the desired product was 34.4 g (68% of the theoretical value as calculated for triacetonediamine) and the melting point was 161 "C (toluene).

Elemental composition: C28HN6O2. Molecular weight: Calculated, %: C 66.36, H 10.74, N 16.58. 506.78 Found, %: C 66.64, H 10.71, N 16.01. 502.3 IR-spectroscopy data: vC=O (amide I) = 1,650 cm-l; 6,, (amide II) = 1530 cm-; 6,, = 3330,3400 cm-l.

Example 8 The compound of this Example, namely the 2,2,6,6-tetramethylpiperidylamide of benxylaminopropionic acid (compound VIII), was produced following the procedure described in Example 1 from 46.9 g of triacetonediamine and 58 g of benzylaminopropionic acid methylate. The yield of the desired product was 73.14 g (76.8% of the theoretical value as calculated for triacetonediamine) as the melting point was 132"C (toluene).

Elemental composition: C19H31N3O. Molecular weight: Calculated, %: C 71.88, H 9.84, N 13.24. 317.5 Found, %: C 71.92, H 9.68, N 13.71. 318.5 IR-spectroscopy data: vco (amide I) = 1660 cm-'; bNH (amide II) = 1565 cm-; VNH = 3330 cm-1.

Example 9 The compound of this Example, namely the 2,2,6,6-tetramethylpiperidylamide of N-morpholinopropionic acid (compound IX) was produced following the procedure described in Example 1 from 15.62 g of triacetonediamine and 17.32 g of N-morpholinopropionic acid methylate. The desired product yield was 27 g (90.8% of the theoretical value as calculated for triacetonediamine) and the melting point was 82"C (isopropanol) Elemental composition: C16H3' N3O2. Molecular weight: Calculated, %: C 64.61, H 10.51, N 14.13. 297.4 Found, %:C 64.45, H 10.26, N 14.22. 298.5 IR-spectroscopy data: Vco (amide I) = 1630 cm1; bNH (amide II) = 1510 cm-'; 6,, = 3450, 3270 cm~'.

Example 10 The compound of this Example, namely the 2,2,6,6-tetramethylpiperidylamide of N-piperidinopropionic acid (compound X) was produced in a manner similar to that described in Example 1 from 31.25 g of triacetonediamine and 34.20 g of N-piperidinopropionic acid methylate. The yield of the desired product was 29.3 g 49.6% of the theoretical value as calculated for triacetonediamine) and the melting point was 133"C (hexane).

Elemental composition: C17H33N3O. Molecular weight: Calculated, %: C 69.11, H 11.26, N 14.22. 295.47 Found, %: C 69.47, H 11.63, N 14.63. 298.3 IR-spectroscopy data: vc=O (amide I) = 1630 cm-l; bNH (amide II) = 1520 cm-l; VNH = 3400 cm-l.

Example 11 The compound of this Example, namely the 2,2,6,6-tetramethylpiperidylamide of 2'2.2'6'6' tetramethylpiperidylamino propionic acid (compound Xl) was produced in a manner similar to that described in Example 1 from 31.25 g of triacetonediamine and 8.6 g of methylacrylate. The desired product yield was 29.33 g (80% of the theoretical value as calculated for methylacrylate) and the melting point was 139"C (ethylacetate).

Elemental composition: C2, H42N4O. Molecular weight: Calculated, %: C 68.80, H 11.55, N 15.28. 366.6 Found, %: C 69.47, H 11.63, N 14.63. 365.8 IR-spectroscopy data: vC=O (amide I) = 1660 cm-'; BNH (amide II) = 1510 cm1; VNH - 3260 cm-'.

Example 12 The compound of this Example, namely the 2,2,6,6-tetramethylpiperidylamide of phenoxyacetic acid (compound Xli) was produced according to the procedure described in Example 1 from 15.21 g of phenoxyacetic acid and 15.62 g of triacetonediamine. The yield of the desired product was 24.5 g (84.3% of the theoretical value as calculated for triacetonediamine and the melting point was 85"C (toluene).

Elemental composition: C,7H26N202. Molecular weight: Calculated, %: C 70.31, H 9.02, N 9.65. 290.41 Found, %: C 69.91, H 8.91, N 9.48. 307.0 IR-spectroscopy data: vac=0 (amide I) = 1670 cm-'; 6,, (amide II) = 1500 cm; VNH - 3290 cm~1.

Example 13 The compound of this Example, namely the 2,2,6,6-tetramethylpiperidylamide of phenylthioacetic acid (compound XIII) was produced according in a manner similar to that described in Example 1 from 15.62 g of triacetonediamine and 20.6 g of phenylthioacetic acid ethlyate. The yield of the desired product is 23.25 g (75.9% of the theoretical value as calculated for triacetonediamine) and the melting point was 94"C (hexane).

Elemental composition: C,7H26N2SO. Molecular weight: Calculated, %: C 66.62, H 8.55, N 9.14, S.10.46. 290.41 Found, %: C 66.35, H 8.61, N 9.08, S.10.23. 307.4 IR-spectroscopy data: vC=O (amide 1) = 1680 cm-'; any (amide II) = 1505 cm-'; VNH - 3420 cm~'.

Example 14 The compound of this Example, namely the 2,2,6,6-tetramethylpiperidylamide of 4-tert.butylphenoxyacetic acid (compound XIV) was produced in a manner similar to that described in Example 1 from 15.62 g of triacetonediamine and 23.7 g of n-tert.butylphenoxyacetic acid ethylate. The yield of the desired product was 19.9 g (57.4% of the desired product was 19.9 g (57.4% of the theortical value as calculated for triacetonediamine) and the melting point was 88"C (hexane).

Elemental composition: C2, H34N2O2. Molecular weight: Calculated, %: C 72.79, H 9.89, N 8.08. 346.52 Found, %: C 72.70, H 9.94, N 8.08. 349.10 IR-spectroscopy data: vC=O (amide I) = 1685 cm-'; bNH (amide II) = 1530 cm-'; VNH - 3430 cm~1.

Example 15 The compound of this Example, namely the bis- (2,2,6,6-tetramethylpiperidylacetamido) -2', 2'phenoxypropane (compound Xl), was produced following the procedure described in Example 1 from 15.52 g of triacetonediamine and 18.42 g of 4,4'-diphenyloxypropionic acid diethylate. The yield of the desired product was 27.6 g (89% of the theoretical value as calculated for triacetonediamine) and the melting point was 79"C (gasoline/toluene).

Elemental composition C37H56N404. Molecular weight: Calculated, %: C 71.58, H 9.09, N 9.02. 620.88 Found, %: C 71.44, H 9.13, N 8.86. 627.00 IR-spectroscopy data: vC=O (amide I) = 1670 cm-'; 6,, (amide II) = 1520 cm~1; VNH - 3140, 3270 cm~'.

Example 16 The compound of this Example, namely the 2,2,6,6-tetramethylpiperidylamide of -(2', 2', 6', 6' tetramethylpiperidylamino)-crotonic acid (compound XVII), was produced in a manner similar to that described in Example 1 from 65.07 g of acetoacetic ether and 1 56/26g of triacetonediamine. The yield of the desired product was 11 5.3g (6 1.0% of the theoretical value as calculated for triacetonediamine) and the melting was 202"C (isopropanol).

Elemental composition: C22H42N4O Molecular weight: Calculated, %: C 69.79, H 11.18, N 14.80. 378.61 Found, %: C 69.94, H 11.20, N 14.70. 388.0 IR-spectroscopy data: vC=O (amide I) = 1680 cm-l; 6,, (amide II) = 1520 cm-1; vNH = 3400 cm~, vC=CO = 1640cm-1.

Example 17 0.3 Part by weight of compound Xl dissolved in acetone was introduced into 99.7 parts by weight of powdered polypropylene. The resulting mixture was stirred while evaporating off acetone and then introduced into a laboratory mixer and treated therein for 30 minutes. As a result, a homoggeneous mass was produced, from which films (120 um thick) were compression-moulded at a temperature of 210+ 2"C. The films were then subjected to photooxidizing ageing in a weathering cabinet (Xenotest 1200). The degree of film destruction was evaluated in a IR-spectrometer by the time of reaching a carbonyl index equal to 0.3.

Following the above-described procedure, polymeric films were produced using other photostabilizing agents according to the invention (compounds XII, XIV and XV).

To assess the photostabilizing efficency of the photostabilizers according to the present invention, photostable films stabilized by conventional stabilizing agents - Tinuvin 327, (Tinuvin 770 and Cyasorb UV-531) were produced in a similar manner.

The results of the tests are given in Table 1.

TABLE 1 Test No. Photostabilizer Content of the Time of reaching carbonyl photostabilizer, index of 0.3, (hours) parts by weight 1 2 3 4 1 Tinuvin 327 0.3 130 2 Cyasorb UV-531 0.3 210 3 Tinuvin 770 0.05 240 4 Tinuvin 770 0.1 380 5 Tinuvin 770 0.3 500 6 Tinuvin 770 1.0 650 7 Compound XI 0.05 275 8 Compound Xl 0.1 420 9 Compound Xl 0.3 530 10 Compound Xi 1.0 720 11 Compound Xil 0.1 460 12 Compound XII 0.3 625 13 Compound Xll 1.0 750 14 Compound XIV 0.1 420 15 Compound XIV 0.3 545 16 Compound XIV 1.0 760 17 Compound XV 0.05 310 18 Compound XV 0.3 540 19 Compound XV 1.0 780 The data given in Table 1 demonstrate that the photostability of polypropylene films stabilized with compounds Xl, XII, XIV and XV is about 2.5 times superior to that of films stabilized with Cyasorb UV-531 and about 15% above that of films stabilized with Tinuvin 770.

Example 18 0.1 Part by weight of compound XII dissolved in ethanol was introduced into 99.9 parts by weight of a powdered high density polyethylene. Ethanol was removed from the mixture in a vaccuum cabinet. As a result, a homogeneous mass was obtained, from which films (100 p thick) were compression moulded at temperature of 160"C under a pressure of 150 kg/cm2. The films were subjected to a photooxiding ageing in a weathering apparatus (Xenotest 1 The degree of destruction of the films was evaluated in a IR-spectrometer by the time of reaching the carbonyl index of 0.3 and by the time elapsed to their destruction.

Following this procedure, photostable polymeric films were prepared using other photostabilizing agents according to the present invention (compounds II, III VII, IX, XIII, XVI) and, for a comparative evaluation of their photostabilizing efficiency, using Tinuvin 770 and Cyasorb UV-531.

The results of the tests are shown in Table 2.

TABLE 2 Composition Photostabilizer Stabilizer content, parts Time of reaching Time up to the No. by weight carbonyl index of 0.3 destruction (hrJ (hr) 1 2 3 4 5 1 Cyasorb UV-531 0.1 975 1,700 2 Cyasorb UV-531 1,250 2,500 3 Tinuvin 770 0.05 1,100 1,900 4 Tinuvin 770 0.15 1,550 2,895 O Tinuvin 770 0.3 1,850 3.350 6 Tinuvin 770 1.0 2,100 3,900 7 Compound XVI 0.15 1,750 3,250 8 Compound XVI 0.3 2,050 3,700 9 Compound XII 0.3 1,795 3,360 10 Compound XII 1.0 2,420 4,500 11 Compound II 0.05 1,230 2,100 12 Compound II 0.3 1,995 3,685 13 Compound II 0.5 2,070 3,885 14 Compound lil 0.05 1,250 2,155 15 Compound III 1.0 2,360 4,295 1 2 3 4 5 17 Compound VII 0.1 1,710 3,200 18 Compound VII 0.3 2,100 3,685 19 Compound IX 0.1 1,720 3,340 20 Compound IX 0.5 2,000 3,580 21 Compound XIII 1.3 1,920 3,380 22 Compound XIIIQ 1.0 2,000 3,955 The data given in Table 2 demonstrate that the photostability of films of low-density polyethylene stabilized with compounds II, Ill, VII, IX, XII, XVI is about 1.5 times superior to that of films stabilized with Cyasorb UV-531 and about 10% superior to that of films stabilized with Tinuvin 770.

Example 19 0.05 Part by weight of compound VI dissolved in acetone was introduced into 99.75 parts by weight of a powdered polypropylene together with 0.2 part by weight of a phenolic thermostabilizing agent. Irganox 1010. The resulting mixture was mixed to evaporate off acetone, then charged into a laboratory mixer and treated therein for 30 minutes. As a result, a homogeneous mass was obtained which was then passed through a laboratory extruder at a temperature (by zones) of from 210 to 220"C and granulated. The granules are charged into the melting section of a laboratory fibre forming unit.The single filament extruded from the die was cooled in a water bath with a temperature of 1 8-20"C and then stretched fourfold at a temperature of 130"C. The obtained single filaments of the linear density of 8 tex are subjected to a photooxidizing destruction in a weathering cabinet (Xenotest 1200). The degree of destruction of the single filaments was evaluated by the retention of their tenacity after 400 hours of irradiation (in per cent).

Following the above-described procedure, single filments were produced using other photostabilizers according to the present invention (compounds I, 1 V, V, VI, X, XIII, and XV) and using another thermostabilizer Irganox 1076.

To evaluatethe photostabilizing efficiency, fib stabilized with Irganox 1010 together with Tinuvin 327 and Tinuvin 770 were produced in a similar manner.

The results are shown in Table 3.

TABLE 3 Composition No. Components Stabilizer content, % of tenacity retained after parts by weight 400 hours of irradiation 1 2 3 4 1 Tinuvin 327 0.3 20.0 Irganox 010 0.2 2 Tinuvin 770 0.1 Irganox 010 0.3 62.0 3 Tinuvin 770 0.2 Irganox 1010 0.1 60.0 Composition No. Components Stabilizer content, % of tenacity retained after parts by weight 400 hours of irradiation 1 2 3 4 4 Tinuvin 770 1.0 Irganox 1010 0.05 68.0 5 Compound XV 0.05 Irganox 1010 0.3 73.0 6 Compound XV 0.2 Irganox 1010 0.1 75.0 7 Compound XV 0.5 Irganox 1010 0.2 80.0 8 Compound XV 1.0 Irganox 1010 0.05 83.0 9 Compound IV 0.1 Irganox 1010 0.05 72.5 10 Compound V 0.2 Irganox 1010 0.1 74.0 11 Compound XIII 0.3 Irganox 1076 0.3 77.5 12 Compound X 1.0 Irganox 1076 0.05 80.0 13 Compound VI 0.05 Irganox 1076 0.2 72.0 14 Compound I 0.2 Irganox 1076 0.1 70.0 The data shown in Table 3 demonstrate that the photostability of fibres stabilized by compounds 1, IV, V, VI, X, XV according to the invention is 3-4 times superior to that of fibres stabilized by Tinuvin 327 and about 15% superior to that of fibres stabilized by Tinuvin 770.

Example 20 0.2 Part by weight of compound XIV was introduced into 99.95 parts by weight of a high-density polyethylene in a roll mill after 3 minutes of milling, along with 0.2 part by weight of Cyasorb UV-531 and 0.05 part by weight of AO 2246. The polymeric composition was prepared at a roll temperature of 160"C with continuous cutting-off the web for 10 minutes. From the milled web of the polymer, 2 mm plates were compression moulded at a temperature of 160i zt 2 C and two-side samples were cut-out from them. The samples were subjected to a photooxidizing ageing in a weathering cabinet, Xenotest 1200, for 2000 hours.

The degree of destruction of the samples were evaluated by the percentage of the retained relative elongation at rupture after 2,000 hours of ageing.

Photostable compositions with other photostabilizers according to the present invention and known additives (Tiuvin 327, Cyasorb UV-531 and Tinuvin 770) were produced in a similar manner. The results are shown in Table 4.

TABLE 4 Composition Component Content of stabilizer, % of retained relative No. part by weight elongation at rupture after 2000 h of ageing 1 2 3 4 1 Cyasorb UV-531 0.1 5.7 A0-2246 0.05 2 Cyasorb UV-531 0.2 7.0 A0-2246 0.05 3 Cyasorb UV-531 0.3 8.0 A0-2246 0.05 4 Tinuvin 327 0.3 Broken after A0-2246 0.05 1200 hours 5 Tinuvin 770 0.1 10.0 A0-2246 0.05 6 Tinuvin 770 0.2 21.5 A0-2246 0.05 7 Tinuvin 770 0.3 44.8 A0-2246 0.05 Composition Component Content of stabilizer, % of retained relative No. part by weight elongation at rupture after 2000 h of ageing 1 2 3 4 8 Compound XI 0.1 14.8 A0-2246 0.05 9 Compound XI 0.2 27.0 A0-2246 0.05 10 Compound XI 0.3 55.6 A0-2246 0.05 11 Compound XIV 0.1 10.5 A0-2246 0.05 12 Compound XIV 0.2 23.6 A0-2246 0.05 13 Compound XIV 0.3 45.0 A0-2246 0.05 14 Tinuvin 770 0.2 71.5 Tinuvin 327 0.2 A0-2246 0.05 15 Tinuvin 770 0.1 58.1 Cyasorb UV-531 0.1 A0-2246 0.05 16 Tinuvin 770 0.2 78.0 Cyasorb UV-531 0.2 A0-2246 0.05 17 Tinuvin 770 0.3 80.0 Cyasorb UV-531 0.3 A0-2246 0.05 18 Tinuvin 770 0.3 70.0 Cyasorb UV-531 0.1 A0-2246 0.05 19 Tinuvin 770 0.1 67.5 Cyasorb UV-531 0.3 A0-2246 0.05 20 Tinuvin 770 0.1 62.0 Tinuvin 327 0.3 A0-2246 0.05 21 Compound XI 0.1 67.9 Cyasorb UV-531 0.1 A0-2246 0.05 22 Compound XI 0.2 88.2 Cyasorb UV-531 0.2 A0-2246 0.05 23 Compound Xl 0.2 82.0 Tinuvin 327 0.2 A0-2246 0.05 24 Compound XI 0.3 90.0 Cyasorb UV-531 0.3 A0-2246 0.05 25 Compound XI 0.3 71.9 Cyasorb UV-531 0.1 A0-2246 0.05 26 Compound XI 0.1 72.5 Cyasorb UV-531 0.3 A0-2246 0.05 27 Compound XIV 0.1 56.5 Tinuvin 327 0.1 A0-2246 0.05 28 Compound XIV 0.1 60.0 Cyasorb UV-531 0.1 A0-2246 0.05 29 Compound XIV 0.2 80.5 A0-2246 0.05 The data given in Table 4 demonstrate that the photostability of plates from a low-density polyethylene stabilized with compounds XI or XIV according to the invention is about 3 times superior to that of plates stabilized with Cyasorb UV-531 or Tinuvin 327 and about 10% higher as compared to that obtained when using Tinuvin 770 as a stabilizer.

Example 21 1.0 Part by weight of compound XVI, 0.1 part by weight of Tinuvin 327 and 0.05 part by weight of Irganox 1010 were introduced into 98.85 parts by weight of a powdered polypropylene. The resulting mixture was agitated, granulated and shaped into single filaments of 10 tex following the procedure described in Example 19.

The single filaments were subjected to a photo-oxidizing ageing in a weathering cabinet, Xenotest 1200, for 5 hours.

The photostabilizing efficiency of the additive was assessed by the percentage of retained tenacity of the single filaments upon rupture thereof.

Following the above-described procedure photostable compositions are prepared and tested with other photostabilizers of the invention and with known additives (Tinuvin 327, Cyasorb UV-531 and Tinuvin 770).

The results are shown in Table 5.

TABLE 5 Composition Component Stabilizer content, parts % of tenacity retained after No. by weight 500 hours of irradiation 1 2 3 4 1 Tinuvin 327 0.3 19 Irganox 1010 0.1 2 Cyasorb UV-531 0.3 35 Irganox 1010 0.1 3 Tinuvin 770 0.05 70 Tinuvin 327 0.3 Irganox 1010 0.05 4 Tinuvin 770 1.0 76 Tinuvin 327 0.1 Irganox 1010 0.05 5 Tinuvin 770 0.1 72 Cyasorb UV-531 0.2 Irganox 1010 0.3 6 Compound XV 0.05 82 Tinuvin 327 0.3 Irganox 1010 0.05 7 Compound XVI 1.0 90 Tinuvin 327 0.1 Irganox 1010 0.05 8 Compound VIII 0.1 87 Cyasorb UV-531 0.2 Irganox 1010 0.3 9 Compound IX 0.05 85 Cyasorb UV-531 0.3 Irganox 1010 0.05 10 Compound XI 0.1 88 Cyasorb UV-531 0.3 Irganox 1010 0.1 The data shown in Table 5 demonstrate that the single filaments stabilized with compounds VIII, IX, Xl, XV and XVI according to the invention are 2-4 times more photostable than filaments stabilized with Tinuvin 327 or Cyasorb UV-531, and about 15% more photostable than filaments stabilized with Tinuvin 770.

Example 22 0.1 Part by weight of compound V was introduced into 99.9 parts by weight of a granulated impact-resistant polystyrene. From the resulting mixture a 5% benzene solution was prepared. After complete dissolution of the impact resistant polystyrene and the stabilizing additive, films with the thickness of 70 were produced by casting the solution.

After evaporation of the solvent (about 2 days) the resulting films were subjected to a photo-oxidizing ageing under non-filtered UV-light. The degree of destruction of the films was evaluated on a IR-spectrometer by accumulation of carbonyl groups at 1720 cm-' (relative units) and by retention of double bonds (C=C bonds) at 900 cm- (per cent of the initial value) after 100 hours of ageing.

Using the above-mentioned procedure, photostable compositions were prepared with other photostabilizers according to the invention and, for comparison, with a known stabilizer-Tinuvin P.

The results are shown in Table 6.

TABLE 6 Test No. Photostabilizer Content of Accumulation of carbonyl Double bonds retained, % of photostabilizer, parts groups, % of initial value the initial number by weight 1 2 3 4 5 1 Tinuvin P 0.05 8.8 15 2 Tinuvin P 0.10 7.4 20 3 Tinuvin P 0.30 6.2 30 4 Tinuvin P 1.00 7.0 32 5 Compound XI 0.05 4.1 45 6 Compound XI 0.30 3.0 69 7 Compound lil 0.10 3.7 59 8 Compound iV 0.30 3.1 65 9 Compound V 0.30 2.8 80 10 Compound XIII 0.10 3.4 62 11 Compound Vlil 0.05 4.8 42 12 Compound X 1.00 1.7 92 13 Compound X 0.30 2.7 82 The data shown in Table 6 demonstrate that compounds III. IV, V, VIII, X and Xl according to the invention impart a photostability to the impact-resistant polystyrene which is about 2-3 times higher than that obtained with Tinuvin P.

Example 23 Samples of films of an impact-resistant polystyrene were produced following the procedure described in Example 22.

Heat-resistant compositions were prepared using the stabilizers according to the present invention and, for comparison, using a known stabilizer Polygard.

The films were subjected to thermal ageing at a temperature of 120"C in an air thermostat. The degree of destruction of the films was determined as described in Example 22 after 500 hours of thermal ageing.

The results are shown in Table 7.

TABLE 7 No. Compound Content of Accumulation of Double bonds thermostabilizer, carbonyl groups C = C retained parts by weight 1 2 3 4 5 1 Polygard 0.05 Broken Broken 2 Ditto 0.10 5.0 29 3 Ditto 0.30 5.2 31 4 Ditto 0.50 3.4 37 5 Ditto 1.00 2.9 41 6 Compound XI 0.05 3.2 49 7 Compound V 0.10 2.5 53 8 Compound XIV 0.30 1.9 67 9 Compound XV 0.50 1.7 77 10 Compound IX 1.00 1.3 81 The data shown in Table 7 demonstrate that compounds V, IX, Xl, XIV and XV are 1.5-2 times more effective, as regards their thermostabilizing efficiency, than Polygard.

Example 24 0.5 Part by weight of compound XII was introduced into 99.5 parts by weight of a ternary copolymer (composition, parts by weight: styrene 54; acrylonitrile 28, polybutadiene 18). The composition was blended in a ball mill with subsequent homogenization in a mixer at a temperature of 190 to 210"C. From the thus-prepared mixture standard rods injection-moulded (50 x 6 x 4mm). The rods were subjected to photoageing under carbon-arc lamps for 200 hours. After ageing, the rods were subjected to a test to measure the drop in their resilience in kgf/cm2 (in per cent of the initial value) using a pendulum hammer.

The same procedure was used for the preparation and testing of photostable compositions with other photostabilizing agents according to the invention and with a known photostabilizer, Tinuvin P.

The results of the tests are shown in Table 8.

TABLE 8 No. Photostabilizer Content of the Resilience, per cent of photostabilizer, parts the initial value by weight 1 Tinuvin P 0.05 29 2 Tinuvin P 0.10 34 3 Tinuvin P 0.50 47 4 Tinuvin P 1.00 50 5 Compound XI 0.05 41 6 Compound I 0.10 68 7 Compound XIII 0.50 88 8 Compound VII 1.00 91 The data shown in Table 8 demonstrate that compounds I, VII, XI and XIII according to the invention are by about 2 times superior to Tinuvin P in their photostabilizing efficiency.

Claims

1. Compounds of the formula:

in which n is 1 or 2: and A, when n is 1, is a phenoxymethyl, phenylthiomethyl, 4-t-butyl-phenoxymethyl, phenylaminoethyl, 2benzylamino-ethyl, 2-(2', 2', 6', 6'-tetramethylpiperid-4-yl)-propen-l-yl group, or a group - (CH2)m-x (in which m is 1 or 2, and X is a 2,2,6,6-tetramethylpiperid-4-ylamino, cyclohexylamino, N-piperidyl or N-morpholinyl group); or, when n is 2, a group

(in which n and m have the meanings defined above).

2. A compound as claimed in claim 1 as described in any one of Examples 1-16 herein.

3. A polymeric composition comprising a polymer and, as photostabilizer, as a compound as claimed in claim 1 in an amount of from 0.05 to 1.0% by weight based on the weight of polymer and photostabilizer.

4. A polymeric composition as claimed in claim 3 also containing 0.05 to 0.3 g by weight, based on the weight of polymer, of a thermostabilizer.

5. A polymeric composition as claimed in claim 3 or claim 4 also containing from 0.1 to 0.7% by weight, based on the weight of polymer, of a UV-light absorber

6. A polymeric composition as claimed in claim 3 substantially as hereinafter described with reference to Examples 17-24 herein.

(in which mis 1 or 2).

Amendments to the claims have been filed, and have the following effect: (a) Claims 1 above has been deleted.

(b) New claim 1 has been filed as follows: CLAIMS

1. Compounds of the formula:

in which n is 1 or 2; and A, when n is 1, is a 2-(2',2',6',6'-tetramethylpiperid-4-yl)-propen-l-yI group, or a group - (CH2)2-X (in which X is a 2,2,6,6-tetramethylpiperid-4-ylamino, cyclohexyl- amino, N-piperidyl or N-morpholinyl group); or, when n is 2, a group.

(in which m is 1 or 2).